17

Edited by
ARNE P. RATVIK
The Minerals, Metals & Materials Series
Arne P. Ratvik
Editor

Light Metals 2017

123
Editor
Arne P. Ratvik
SINTEF
Trondheim
Norway

ISSN 2367-1181 ISSN 2367-1696 (electronic)

The Minerals, Metals & Materials Series
ISBN 978-3-319-51540-3 ISBN 978-3-319-51541-0 (eBook)
DOI 10.1007/978-3-319-51541-0
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Preface

It is a pleasure for me to welcome you to the TMS 2017 Annual Meeting & Exhibition in San
Diego and to present to you the proceedings of Light Metals 2017. First of all, I would like to
honor all of you who have contributed to make this an excellent reference for the develop-
ments within aluminium. All the efforts by you are extremely important for bringing better
processes and better products to our society, making aluminium the preferred metal for growth
and prosperity in a global perspective.
In 2016, the Hall-Héroult process celebrated its 130-year anniversary, in a period with
aluminum experiencing an exceptional growth, surpassing all other metals over a long period.
Moreover, there is no reason to believe this will not continue in the years to come.
The growth is adding extra pressure on the bauxite and alumina industry, especially on
environmental issues related to mining and the red mud residue. In addition, more alumina
refineries are located apart from the mines, making bauxite emerging as a bulk commodity in
the trading market.
The growth in aluminum production in the East, especially China, has been tremendous,
and more plants are on the drawing board. Unfortunately, this has caused an oversupply with
low market prices for aluminum, which may continue for several years to come unless
environmental restrictions on CO2 emissions in China slow down the expansive policy. The
recent growth, mostly based on coal-fired power plants, with an environmental footprint ten
times that of aluminum produced from hydro- or nuclear power is challenging aluminum as a
green metal.
As more aluminum is being recycled, in some areas reaching close to 50 %, both casting
and alloying operations are prone to become more demanding due to the variety in compo-
sition of recycled aluminum. Fortunately, we also see a healthy growth in aluminum replacing
more heavy metals in transportation, leading to better energy efficiency. The growth in both
electric and plug-in hybrid cars and trucks are promising for our industry and makes us eager
to reply to new demands for products and leaner production strategies.
In spite of the pressure on the aluminum price, which we have to cope with through process
and technology improvements, the overall picture of the industry is good. In times with low
market prices, it may be comfortable to cut back on R&D as a means to improve economical
results. However, lack of continuity in long-term R&D may eventually slow down the drive
for making the industry, even more cost-effective and environmentally sustainable. In this
perspective, industrial contributions and participation at The Minerals, Metals & Materials
Society’s (TMS) meetings are not reflecting an aggressive attitude. For highly educated people
recruited to the industry, not being able to participate with scientific contributions is a loss of
opportunity to meet experienced people in the industry and from academia, reducing the
opportunity to create networks and to get new inspiration useful in their daily work. We should
all work together, share ideas, and contribute to develop new opportunities for our industry
and our society.
In the organizing of the proceedings and the sessions, I would like to express my appre-
ciation to the efforts of the subject chairs: Yanjun Li, David Gildemeister, Houshang Alamdari,
Mark Dorreen, and Ting-an Zhang, as well as their session chairs that have reviewed the

v
vi Preface

manuscripts. I also have to mention Anne Kvithyld and John Grandfield for organizing the
LMD Symposium in Honor of Christian Simensen and Thorvald Abel Engh together with
David Gildemeister.
This year, the procedure for submitting manuscripts changed. This may have caused some
confusion; however, as it is with our industry, improvements are not possible unless we are
willing to change. And, the lessons learned this year will be used to improve next year’s
procedure. Finally, I would like to express my great appreciation to the TMS staff for their
devoted support in the preparation of this volume.

Arne P. Ratvik
Contents

Part I Alumina and Bauxite: Digestion and Calcination

CFB Alumina Calciners—New and Future Generation Opportunities for Green
Field Refineries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Linus Perander, Alessio Scarsella, Edgar Gasafi, and Hans-Werner Schmidt
Evolutional Development of Alkaline Aluminosilicates Processing
Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Andrey Panov, Sergey Vinogradov, and Svyatoslav Engalychev
Characterization and Ore Dressing of Bauxite from Brazil . . . . . . . . . . . . . . . . . . . 17
Karoline K. Ferreira, Bruna L. Novo, Danielle C. Castro, Daniel Barcellos,
Luiz C. Bertolino, Antônio C.O. Guerra, Carla N. Barbato, Adriana A.S. Felix,
Marta E. Medeiros, Francisco M.S. Garrido, and Fernanda A.N.G. Silva
Process Optimization for Diaspore Digestion Equilibrium Using Response
Surface Methodology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Zhengyong Zhang
Thermodynamic Analysis and Formation Law of Q Phase of Calcium
Aluminate Clinker . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Long Lu, Dongdong Ma, Di Zhang, Tianxu Zhang, and Bo Wang
Leaching Behavior of Alumina from Smelting Reduction Calcium
Aluminate Slag with Sodium Carbonate Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Zhifang Tong and Yingjie Li

Part II Alumina and Bauxite: Bauxite Residues Technology

Security Disposal and Comprehensive Utilization of Bauxite Residues . . . . . . . . . . 47
Songqing Gu, Zhonglin Yin, and Lijuan Qi
Bauxite Residue Amendment Through the Addition of Ca and or Mg
Followed by Carbonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Luis C.A. Venancio, José Antonio Silva Souza, Emanuel Negrão Macedo,
Fernando Aracati Botelho, Amanda Morais de Oliveira, and Raissa Silva Fonseca
Application of Tricalcium Aluminate Instead of Lime
for the Recovery of Aluminum in Middle-Low Grade Bauxite
in Calcification-Carbonization Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
Yanxiu Wang, Ting-an Zhang, Guozhi Lu, Weiguang Zhang, Xiaofeng Zhu,
and Liqun Xie
Low Temperature Reduction of Hematite in Red-Mud to Magnetite . . . . . . . . . . . 67
Sumedh Gostu, Brajendra Mishra, and Gerard P. Martins

vii
viii Contents

Recovery of Iron-, Titanium-Bearing Constituents from Bauxite Ore

Residue via Magnetic Separation Followed by Sulfuric Acid Leaching . . . . . . . . . . 75
Guanghui Li, Foquan Gu, Jun Luo, Bona Deng, Zhiwei Peng, and Tao Jiang
Processing Diasporic Red Mud by the Calcification-Carbonation Method . . . . . . . 83
Xiao-feng Zhu, Ting-an Zhang, Guo-zhi Lv, Fang-fang Guo, Wei-guang Zhang,
Yan-xiu Wang, Li-qun Xie, and Long Wang
Research of Flocculants and Dewatering Additives for Filtration
of Red Mud . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Cao Wenzhong, Zheng Fuliang, Tian Weiwei, and Zhong Hong
Characterization of Activated Alumina Production via Spray Pyrolysis . . . . . . . . . 93
Wang Long, Zhang Ting’an, Lv Guozhi, Zhao Aichun, Ma Sida,
and Zhang Weiguang

Part III Alumina and Bauxite: Non-traditional Resources

New Process Research on Aluminium Production from Non-Traditional
Aluminum Resource by Microwave Chlorination . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Ting-an Zhang, Guozhi Lv, Long Wang, Zhihe Dou, Weiguang Zhang,
Yukun Huang, and Yanxiu Wang
Opportunities of Pseudoboehmite Processing from Aluminum Content
Raw Material at Sintering Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Rustam A. Seytenov, Vadim A. Lipin, Evgeny A. Vlasov, and Natalia V. Maltseva
Chemical Alumina Preparation by Using High Alumina Content Fly Ash . . . . . . . 115
Guozhi Lv, Ting-an Zhang, Weiguang Zhang, Xiaofeng Zhu, Yan Liu, Long Wang,
Zhihe Dou, and Qiuyue Zhao
A Novel Process of Alumina Production from Low-Grade Bauxite
Containing Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
Bo Wang, Kai Zhao, Huilan Sun, Xuezheng Zhang, Zepeng Li, and Hongyou Ma
Iron Separation from Bauxite Through Smelting-Reduction Process . . . . . . . . . . . 127
Hanne Sellaeg, Leiv Kolbeinsen, and Jafar Safarian
Thermodynamic Behavior of Lime Desulfurization in Sodium
Aluminate Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Wu Xianxi, Zhu Weidong, Jiang Hongshi, and Wu Song

Part IV Alumina and Bauxite: Poster Session

A Study on Optimization of Processing Parameters for Synthesis
of Calcium Hydroaluminosulfate Using Response Surface Methodology. . . . . . . . . 147
W. Xianxi, Z. Weidong, L. Jun, and W. Song

Part V Aluminum Alloys, Processing and Characterization: Alloy

Development and Applications
Design of New 6xxx Series Al Alloy Using the Calphad Thermodynamic
Database. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
Senlin Cui, Raj Mishra, and In-Ho Jung
Study of an Al-Ca Alloy with Low Young’s Modulus . . . . . . . . . . . . . . . . . . . . . . . 167
Jun Yu, Yasuo Ishiwata, Yoshihiro Taguchi, Daisuke Shimosaka,
Ryosuke Taniguchi, Takutoshi Kondo, and Nobuki Tezuka
Contents ix

Production of 3004 Aluminum Alloy Sheet for Structural Applications

from Twin Roll Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
Ali Ulaş Malcıoğlu and Seda Ertan
Aluminum Alloys with Tailored TiB2 Particles for Composite Applications . . . . . . 181
Xingtao Liu, Yanfei Liu, David Yan, Qingyou Han, and Xiaoming Wang
Development of Low Expansion and High Strength Aluminum Matrix
Hybrid Composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
Jamuna Sethi, Siddhartha Das, and Karabi Das

Part VI Aluminum Alloys, Processing and Characterization: Solidification

and Casting
A Model for a-Al(Mn,Fe)Si Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Christian J. Simensen and Are Bjørneklett
Casting Characteristics of High Cerium Content Aluminum Alloys . . . . . . . . . . . . 205
David Weiss, Orlando Rios, Zachary Sims, Scott McCall, and Ryan Ott
In Situ Observation of Fragmentation of Primary Crystals by Ultrasonic
Cavitation in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
Feng Wang, Iakovos Tzanakis, Dmitry Eskin, Jiawei Mi, and Thomas Connolley
The Enhancement of Mechanical Properties of A356 Alloy Solidified
at Lower Cooling Rate via Effectively Grain Refinement . . . . . . . . . . . . . . . . . . . . . 221
Yijie Zhang, Shouxun Ji, and Zhongyun Fan
Secondary Aluminum Alloys Processed by Semisolid Process
for Automotive Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
F. D’Errico and D. Mattavelli
Integrated Casting-Extrusion (ICE) of an AA6082 Aluminium Alloy . . . . . . . . . . . 235
Shohreh Khorsand and Yan Huang
On Porosity Formation in Al–Si–Cu Cast Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
F.H. Samuel, A.M. Samuel, H.W. Doty, and S. Valtierra

Part VII Aluminum Alloys, Processing and Characterization:

Characterization
Algorithm for Finding the Correlation Between the Properties
of Wrought Aluminum Alloys, the Chemical Composition
and the Processing Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
Varužan M. Kevorkijan, Branko Hmelak, Peter Cvahte, Sara Hmelak,
Vukašin Dragojević, Uroš Kovačec, Marina Jelen, and Darja Volšak
Analysis of an Aluminium Alloy Containing Trace Elements . . . . . . . . . . . . . . . . . 265
Christian J. Simensen, Stephan Kubowicz, Børge Holme, and Joachim S. Graff
Determination of Aluminum Oxide Thickness on the Annealed Surface
of 8000 Series Aluminum Foil by Fourier Transform Infrared Spectroscopy . . . . . 273
Özlem İnanç Uçar, Ayten Ekin Meşe, Onur Birbaşar, Murat Dündar,
and Durmuş Özdemir
Using Guard Bands to Accommodate Uncertainty in the Spark AES
Analysis of Aluminum or Aluminum Alloys When Determining
Compliance with Specified Composition Limits . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
Thomas Belliveau, Denis Choquette, Olivier Gabis, Michael Ruschak, John Sieber,
Albert Wills, and Rebecca Wyss
x Contents

Laser Marking and 3D Imaging of Aluminum Products . . . . . . . . . . . . . . . . . . . . . 289

Alex Fraser, Michael Dallaire, and Xavier P. Godmaire
Production and Certification of Arconic Certified Reference Materials . . . . . . . . . 293
Jeneé L. Jacobs, Michael L. Ruschak, John L. Genna, Keith K. Trischan,
Louis A. Bono, and Samantha L. Stephens
Characterization of Large Strain Extrusion Machining (LSEM) of AA7050 . . . . . 301
Daniel R. Klenosky, David R. Johnson, Srinivasan Chandrasekar,
and Kevin P. Trumble
Influence of Trace Element Additions on Fe Bearing Intermetallic
Solidification of a 6063 Al Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
S. Kumar, J. Malisano, Y. Ito, and K.A.Q. O’Reilly

Part VIII Aluminum Alloys, Processing and Characterization: Heat Treatment

The Optimization of the Homogenization Treatment of AA7075 . . . . . . . . . . . . . . . 315
Gheorghe Dobra, Ioan Sava, Marin Petre, and Gheorghe Popa
Precipitation Modeling and Validation of Al–5%Cu–0.4%Mn Alloy
Using Quench Factor Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
Yisen Hu, Gang Wang, Wenguang Wang, Mao Ye, and Yiming Rong
Young’s Modulus of Al–Si–Mg–Cu Based Alloy Under Different
Heat Treatment Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
Sajjad Amirkhanlou, Yijie Zhang, Shouxun Ji, and Zhongyun Fan
Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod . . . . . . . . . . 343
Luisa Marzoli, Dominique Cance, Christiane Matthies, Magali Guizard,
Peter Baumgart, and Hubert Koch
The Influence of Process Parameters and Themomechanical History
on Streaking Defects in AA6060 Extrusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
Steven Babaniaris, Aiden Beer, and Matthew R. Barnett
Effect of Heat-Treatment on Microstructure and Mechanical Properties
of Sonicated Multicomponent AlMgSiCuZn Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . 379
Kwangjun Euh, Jae-Gil Jung, Eun-ji Baek, Jung-Moo Lee, and Hyoung-Wook Kim
Effect of Interrupted Quenching on Al–Zn–Mg–Cu Alloys . . . . . . . . . . . . . . . . . . . 385
Gernot K.-H. Kolb, Helmut Antrekowitsch, Daniel Pöschmann, Peter J. Uggowitzer,
and Stefan Pogatscher

Part IX Aluminum Alloys, Processing and Characterization: Plasticity

and Mechanical Behavior
New Yield Criterion for Description of Plastic Deformation of Face-Centered
Cubic Single Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
Nitin Chandola, Crystal Pasiliao, Oana Cazacu, and Benoit Revil-Baudard
Quantifying As-Cast and Homogenized AA7050 Mechanical Properties
Through Compression Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
Yunbo Wang, Matthew John M. Krane, and Kevin P. Trumble
Determining a Stable Texture Condition Under Complex Strain
Path Deformations in Face Centered Cubic Metals . . . . . . . . . . . . . . . . . . . . . . . . . 409
Usman Ali, Abhijit Brahme, Raja K. Mishra, and Kaan Inal
Contents xi

Microstructural Transition and Elevated Temperature Tensile Properties

of Modified Al–Si–Cu–Mg Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
Mehdi Rahimian, Shouxun Ji, Paul Blake, Douglas Watson, and Zhongyun Fan
Effect of Alloying Elements on Anneal-Hardening Behavior of Aluminum
Alloy Foils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
Takashi Suzuki, Shigeru Kuramoto, Masaya Endo, and Qi Cui
Increasing Strength and Corrosion Resistance of AlMgSi Alloys
by Tailor-Made Thermomechanical Processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
A. Wimmer
Microstructural Optimization of a High Mechanical Properties Aluminum
Alloy By Using CobaPress Process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
Mamadou Balde, Christophe Desrayaud, Véronique Bouvier, and Frédéric Perrier
Cyclic Stress-Strain Behavior and Low Cycle Fatigue Life of AA6061
Aluminum Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
F.A. Mirza, K. Liu and X. -G. Chen

Part X Aluminum Alloys, Processing and Characterization: Poster Session

Corrosion of Al–Mg Alloys in Ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
Gustavo Raúl Kramer, Estefanía Gauto, Roberto S. Rozicki,
Claudia Marcela Méndez, and Alicia Esther Ares
Warm Pressing of Al Powders: An Alternative Consolidation Approach . . . . . . . . 463
Peter Krizik, Martin Balog, Oto Bajana, Maria Victoria Castro Riglos,
and Peter Svec Sr.

Part XI Aluminum Reduction Technology: Dry Scrubbing, Alumina

Transport and Dissolution
Spreading of Alumina and Raft Formation on the Surface
of Cryolitic Bath . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
Csilla Kaszás, László Kiss, Sándor Poncsák, Sébastien Guérard,
and Jean-François Bilodeau
Fluoride Capture Capacity of SGA: The Interplay Between Particle
and Pore Size Distributions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
Gordon E.K. Agbenyegah, Grant J. McIntosh, Margaret M. Hyland,
and James B. Metson
Predictive Formula for the Competitive Adsorption of HF and SO2
on Smelter Grade Alumina Used in Dry Scrubbing Applications . . . . . . . . . . . . . . 487
Stephen J. Lindsay, Neal R. Dando, and Stephan Broek
Pot Gas Treatment at High Gas Temperatures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 495
Anders Sørhuus and Sivert Ose
Influence of Handling Parameter on Powder Properties . . . . . . . . . . . . . . . . . . . . . 501
Peter Hilgraf, Jan Paepcke, and Arne Hilck

Part XII Aluminum Reduction Technology: Anode Effect

and PFC Emissions
Preventive Treatment of Anode Effects Using on-Line Individual Anode Current
Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
Lukas Dion, Charles-Luc Lagacé, François Laflamme, Antoine Godefroy,
James W. Evans, László I. Kiss, and Sándor Poncsák
xii Contents

Reduction in EGA Jebel Ali Potroom GHG Emissions . . . . . . . . . . . . . . . . . . . . . . 519

Daniel Whitfield, Sergey Akhmetov, and Najeeba Al-Jabri
Partial Anode Effect in a Two-Compartment Laboratory Alumina
Reduction Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
Henrik Åsheim, Thor A. Aarhaug, Wojciech Gębarowski, Espen Sandnes,
Asbjørn Solheim, and Geir M. Haarberg
Co-evolution of Carbon Oxides and Fluorides During the Electrowinning
of Aluminium with Molten NaF–AlF3–CaF2–Al2O3 Electrolytes . . . . . . . . . . . . . . . 533
M.M.R. Dorreen, M.M. Hyland, R.G. Haverkamp, J.B. Metson, Ali Jassim,
B.J. Welch, and A.T. Tabereaux

Part XIII Aluminum Reduction Technology: Cell Lining Materials

Chemical Stability of Thermal Insulating Materials in Sodium
Vapour Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 543
Raymond Luneng, Søren N. Bertel, Jørgen Mikkelsen, Arne P. Ratvik,
and Tor Grande
Aging of Insulating Linings in Aluminium Electrolysis Cells . . . . . . . . . . . . . . . . . . 551
Ove Paulsen, Christian Schøning, Ove Darell, and Arne Petter Ratvik
Cathode Wear Based on Autopsy of a Shutdown Aluminium
Electrolysis Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
Samuel Senanu, Christian Schøning, Stein Rørvik, Zhaohui Wang,
Arne P. Ratvik, and Tor Grande
SPL Recycling and Re-processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
Victor Mann, Vitaliy Pingin, Aleksey Zherdev, Yuriy Bogdanov,
Sergey Pavlov, and Vladimir Somov
Alternative Applications of SPL: Testing Ideas Through Experiments
and Mathematical Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
Dawei Yu, Vishnuvardhan Mambakkam, Donghui Li, Kinnor Chattopadhyay,
and Lei Gao

Part XIV Aluminum Reduction Technology: Cell Voltage and Pot Control
Clustering Aluminum Smelting Potlines Using Fuzzy C-Means
and K-Means Algorithms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
Flávia A.N. de Lima, Alan M.F. de Souza, Fábio M. Soares, Diego Lisboa Cardoso,
and Roberto C.L. de Oliveira
Application of Multivariate Statistical Process Control with STARprobe™
Measurements in Aluminium Electrolysis Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599
Jean-Pierre Gagné, Rémi St-Pierre, Pascal Côté, Pascal Lavoie, and Albert Mulder
Study of the Impact of Anode Slots on the Voltage Fluctuations
in Aluminium Electrolysis Cells, Using Bubble Layer Simulator . . . . . . . . . . . . . . . 607
Sándor Poncsák, László I. Kiss, Sébastien Guérard, and Jean-François Bilodeau
Detecting, Identifying and Managing Systematic Potline Issues
with Generation 3 Process Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615
Nursiani Indah Tjahyono, Yashuang Gao, David S. Wong, Ron Etzion,
and Albert Mulder
Predicting Instability and Current Efficiency of Industrial Cells . . . . . . . . . . . . . . . 623
Patrice Côté, Olivier Martin, Bertrand Allano, and Véronique Dassylva-Raymond
Contents xiii

Part XV Aluminum Reduction Technology: Electrolyte and Fundamentals

Sodium in Aluminium as a Cell Performance Indicator:
A Quantitative Framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
Asbjørn Solheim
Bauxite Processing via Chloride Route to Produce Chloride Products
and Subsequent Electrolysis of Aluminium Chloride to Produce
Aluminium Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641
Sankar Namboothiri and Subash Mallick
Stability of Chlorides in Cryolitic Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 649
Xiangwen Wang and Luis Espinoza-Nava
Role of Heat Transfer and Interfacial Phenomena for the Formation
of Carbon Oxides in Smelting Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659
Mark M.R. Dorreen, Nolan E. Richards, Alton. T. Tabereaux, and Barry J. Welch

Part XVI Aluminum Reduction Technology: Modelling and Cell Design

Improving the Understanding of Busbar Design and Cell
MHD Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
Alexander Arkhipov, Abdalla Alzarooni, Amal Al Jasmi, and Vinko Potocnik
LES Turbulence Modeling Approach for Molten Aluminium
and Electrolyte Flow in Aluminum Electrolysis Cell . . . . . . . . . . . . . . . . . . . . . . . . 679
Mounir Baiteche, Seyed Mohammad Taghavi, Donald Ziegler, and Mario Fafard
MHD of Large Scale Liquid Metal Batteries. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 687
Valdis Bojarevics and Andrejs Tucs
Low Energy Consumption Cell Designs Involving Copper Inserts
and an Innovative Busbar Network Layout . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693
Marc Dupuis
Minimizing Cathode Voltage Drop by Optimizing Cathode Slot Design . . . . . . . . . 705
Ralph Friedrich, Frank Hiltmann, Andreas Lützerath, Richard Meier, Markus Pfeffer,
Till Reek, and Oscar Vera Garcia

Part XVII Aluminum Reduction Technology: Potroom Operations

Crane Electrical Insulation Monitoring in Potlines New
CANDI™ 4.0 Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
Serge Despinasse and Eric Norel
Surviving an Extended Power Outage After a Break Down
in the Sub Station . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 723
T. Reek and R. Düssel
Retrofit of Damaged Corner Risers by Means of Bolted Connections . . . . . . . . . . . 731
André Felipe Schneider, Donald P. Ziegler, Maxime Pouliot, Daniel Richard,
Jason Robillard, Jérémie Blais, Olivier Charette, and Pouya Zangeneh
Theory and Practice of High Temperature Gas Baking Technology for
Aluminium Electrolysis Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 739
Chengbo Wu, Yingwu Li, and Xudong Wang

Part XVIII Aluminum Reduction Technology: Technology Development

Implementation of D18+ Cell Technology at EGA’s Jebel Ali Smelter . . . . . . . . . . 749
Daniel Whitfield, Sergey Akhmetov, Jose Blasques, and Harishchandra Devadiga
xiv Contents

Integrating a New Smelter Supervision HMI in Existing Control Systems

at ALBRAS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 759
Vanderlei Oliveira Fernandes, Geir Sandnes, Leonel Vicente Mota Ivo,
and Rogério Cosendey Labanca
DX+ Ultra—EGA High Productivity, Low Energy Cell Technology . . . . . . . . . . . . 769
Ali Alzarouni, Abdalla Alzarooni, Nadia Ahli, Sergey Akhmetov,
and Alexander Arkhipov
Potroom HF Emission Reduction by Anode Inert Tray Technology
Performance of ALRO Industrial 1st of Class . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 775
Vincent Verin, El Hani Bouhabila, Jérémy Neveu, Serge Despinasse,
Gheorghe Dobra, and Marian Cilianu
Enabling Efficient Heat Recovery from Aluminium Pot Gas . . . . . . . . . . . . . . . . . . 783
Daniel Perez Clos, Trond Andresen, Petter Nekså, Sverre Gullikstad Johnsen,
and Ragnhild Elizabeth Aune
The Successful Implementation of AP40 Technology at Kitimat . . . . . . . . . . . . . . . 793
Patrice Desrosiers, Martin Robitaille, Pierre Luc Voyer, Silvino Caetano,
René Gariepy, Olivier Martin, and Pascal Robert

Part XIX Cast Shop Technology: Continuous Strip Casting

Effect of Grain Refiners on Aluminum Twin Roll Casting Process . . . . . . . . . . . . . 803
Yu Matsui, and Koichi Takahashi
Influence of Process Conditions on Segregation Behavior in Twin-Roll
Casting of an AlFeSi-Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
Christian W. Schmidt, Dag Mortensen, and Kai-Friedrich Karhausen
Effect of Magnesium Content on Microstructure and Mechanical
Properties of Twin-Roll Cast Aluminum Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . 821
Onur Meydanoglu, Cemil Işıksaçan, Hatice Mollaoğlu Altuner, Mert Günyüz,
and Onur Birbaşar
Influence of Sticking on the Roll Topography at Twin-Roll Casting
of Aluminum Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 827
Olexandr Grydin, Florian Nürnberger, and Mirko Schaper
Material Surface Roughness Change in Twin Roll Casting of Aluminium
as Cast Sheet Product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
Ceyhun Kuru, Sadık Kaan İpek, Eda Dağdelen, Özgür Özşahin, and Ali Ulus
Twin-Roll Casting of Aluminum-Steel Clad Strips: Static and Dynamic
Mechanical Properties of the Composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 843
M. Stolbchenko, O. Grydin, and M. Schaper

Part XX Cast Shop Technology: Foundry and Shape Casting

Multi-Component High Pressure Die Casting (M-HPDC): Influencing Factors
on the Material Temperature During the Joining of Metal-Plastic-Hybrids . . . . . . 855
Patrick Messer, Uwe Vroomen, and Andreas Bührig-Polaczek
X-Ray Computed Tomographic Investigation of High Pressure Die Castings . . . . 861
Shouxun Ji, Douglas Watson, and Zhongyun Fan
The Comparison of Intensive Riser Cooling of Castings After Solidification in
Three Classic Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 867
Haolong Shangguan and Jinwu Kang
Contents xv

Sequential Gravity Casting in Functionally Graded Aluminum

Alloys Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 877
Mario Rosso, Silvia Lombardo, and Federico Gobber
Assessment of Eutectic Modification Level in Al–Si Alloys
Via Thermal Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 885
Maiada S. Abdelrahman, Mahmoud T. Abdu, and Waleed Khalifa

Part XXI Cast Shop Technology: Melting, Energy, and Dross

Application and Results of Oxipyr® Diluted Combustion in Aluminum
Furnaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 899
Michael Potesser and Johannes Rauch
Case Study of Magnetically-Stirred Casting Furnaces
at New Zealand Aluminium Smelters Limited . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 909
Ray Cook, Marcos Varayud, Steve Iijima, and Eishin Takahashi
Energy Efficiency Status-Quo at UK Foundries:
The “Small-Is-Beautiful” Project . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
Mark R. Jolly, Konstantinos Salonitis, Fiona Charnley, Peter Ball,
Hamid Mehrabi, and Emanuele Pagone
Optimization of Recovery Efficiency for Briquetted Aluminum
Chips up to Briquetting Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 925
Ali Ulus, Hamdi Ekici, and Erdem Güler
The Evaluation of Hot Dross Processing Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . 933
David J. Roth

Part XXII Cast Shop Technology: DC Casting and Macrosegregation

A Study on DC Casting Trough/Launder Design and Material Selection . . . . . . . . 941
Bin Zhang
Critical Role of Thermal Management During Cast Start-Up
of the DC Casting Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 949
Sabrina Guy, André Larouche, and Josée Colbert
Modelling and Analysis of a Horizontal Direct Chill Casting Process . . . . . . . . . . . 955
Gardar Gardarsson, Throstur Gudmundsson, Magnus Th Jonsson,
and Halldor Palsson
Circulation of Grains During Ingot Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 967
Carolyn Joseph, Samuel R. Wagstaff, and Antoine Allanore
Minimization of Macrosegregation Through Jet Erosion of a
Continuously Cast Ingot . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 973
Samuel R. Wagstaff and Antoine Allanore
Full Size Measurement and Simple Prediction on Macro Segregation
of Aluminum Alloys Elements in Industrial Direct Chill Casting Slab . . . . . . . . . . 981
Tatsuya Yamada, Nobuhito Ishikawa, Takashi Kubo, and Koichi Takahashi
Ultrasonic Assisted Reduction of Hot-Tearing During High-Speed DC
Casting of 6000 Series Aluminum Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 989
Sergey Komarov, Yasuo Ishiwata, and Yoshihiro Takeda
xvi Contents

Part XXIII Cast Shop Technology: Grain Refining and Solidification

Effect of Ultrasonic Processing on a Direct Chill Cast AA6082
Aluminium Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 997
G. Salloum-Abou-Jaoude, D.G. Eskin, C. Barbatti, P. Jarry, M. Jarrett,
and Z. Fan
Shear Induced Grain Refinement of a Continuously Cast Ingot . . . . . . . . . . . . . . . 1005
Samuel R. Wagstaff and Antoine Allanore
Microstructure Control in A356 Al–Si Alloy Via Ultrasonic
Melt Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1013
Waleed Khalifa, Mahmoud T. Abdu, Maiada S. Abdelrahman,
and Yoshiki Tsunekawa
Grain Refiner Sedimentation in the Launder System of Twin Roll
Casting and Application of Electromagnetic Stirring . . . . . . . . . . . . . . . . . . . . . . . . 1021
Onur Birbasar, Murat Can Erdemir, Vedat Topaloğlu, Cemil Işıksaçan,
Onur Meydanoğlu, Mert Günyüz, Hatice Mollaoğolu Altuner,
and Murat Dündar
Thermal Analysis of Grain Refining in A319 Alloys . . . . . . . . . . . . . . . . . . . . . . . . . 1027
Waleed Khalifa
Peritectic Coupled Growth Solidification—a Review . . . . . . . . . . . . . . . . . . . . . . . . 1035
Peiman Shahbeigi-Roodposhti and Harold Brody

Part XXIV Cast Shop Technology: Casthouse Management

and Automation
Overpressure Due to a Molten Aluminum and Water Explosion
in a Casthouse . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1045
Jennifer Woloshyn, Andrew Gerber, Tom Plikas, Duane Baker,
and Adam Blackmore
Automation and Optimization of Sow Casting in Alouette . . . . . . . . . . . . . . . . . . . . 1053
JF Desmeules, JB Néron, and JP Bérubé
Radio Frequency Identification (RFID) Technology for the
Aluminum Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1061
Valérie Langelier, Guillaume Parenteau, Martin Lysight,
and Maryse Beaudry
Semi Finished Products Traceability Improvement with Laser Marking . . . . . . . . 1069
J.F. Desmeules, B. Côté, and J.D. Dufour
Structural Integrity Assessment of Pressurized Ladles
for Aluminum Smelting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1079
Maher Al-Dojayli, Pouya Zangeneh, Alexandre Lamoureux, Daniel Richard,
Pierre-Louis Allaire, and Hamid Ghorbani
Has Recent Advances in Direct Chill Casting Made
Us Less Safe? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1089
Alex W. Lowery

Part XXV Cast Shop Technology: Recycling

and Sustainability Joint Session
Tramp Element Accumulation and Its Effects on Secondary
Phase Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1097
Samuel R. Wagstaff, Robert B. Wagstaff, and Antoine Allanore
Contents xvii

Dross Formation Mechanisms of Thermally Pre-Treated

Used Beverage Can Scrap Bales with Different Density . . . . . . . . . . . . . . . . . . . . . . 1105
J. Steglich, R. Dittrich, G. Rombach, M. Rosefort, B. Friedrich, and A. Pichat
Influence of Coating and De-Coating on the Coalescence of
Aluminium Drops in Salt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1115
Stefano Capuzzi, Anne Kvithyld, Giulio Timelli, Arne Nordmark,
and Thorvald Abel Engh
The Scale-Up of High Shear Processing for the Purification
of Recycled Molten Scrap Aluminium Alloy: Key Features
of Fluid Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1123
Mingming Tong, Jayesh B. Patel, Ian Stone, Zhongyun Fan,
and David J. Browne
Centrifugal Casting of Al–Si Scrap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1131
Aya Assem, Shimaa El-Haddad, and Iman El Mahallawi
Improved Recyclability of Cast Al-Alloys by Engineering
b-Al9Fe2Si2 Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1139
C.B. Basak and N. Hari Babu

Part XXVI Electrode Technology: Electrodes: Raw Materials

and Anode Quality
Influence of Calcination Temperature and Sulfur Level
on Coke Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1151
Victor Buzunov, Victor Mann, Sergey Khramenko, and John Johnson
Pilot Anode Properties of Binder Pitches Softening
Between 110 and 150 °C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1157
Winfried Boenigk, Christopher Kuhnt, Jens Stiegert,
Joris Claes, and Les Edwards
Uniform Bulk Density for Calcined Petroleum Coke . . . . . . . . . . . . . . . . . . . . . . . . 1165
Ravindra Narayan Narvekar, Gajanan Bandodkar,
and Jagmohan Chhabra
Use of Thermally Desulfurized Shaft CPC for
Anode Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1173
Les Edwards, Kevin Harp, and Christopher Kuhnt
Anode Carbon Aggregate Packing Description Compared
to Relevant Industrial and Engineering Practises . . . . . . . . . . . . . . . . . . . . . . . . . . . 1183
Bjarte Øye and Lorentz Petter Lossius
CPC Testing and Relationship Between Coke and Anode
Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1193
Marvin L. Lubin, Les Edwards, Kevin Harp, and Christopher Kuhnt
Effect of Coke Properties on the Bubble Formation at the
Anodes During Aluminium Electrolysis in Laboratory Scale . . . . . . . . . . . . . . . . . . 1203
Wojciech Gebarowski, Arne Petter Ratvik, Stein Rørvik, Lorentz Petter Lossius,
Hogne Linga, and Ann Mari Svensson
Anode Quality Improvement at Inalum Smelter . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1213
S.S. Sijabat, Firman Ashad, Ade Buandra, and Edi Mugiono
xviii Contents

Coke Produced from Lower-Oxygen Fast-Pyrolysis Oil,

A New Approach to Produce Renewable Anode Raw Materials . . . . . . . . . . . . . . . 1221
Yaseen Elkasabi, Hans Darmstadt, and Akwasi A. Boateng

Part XXVII Electrode Technology: Electrodes: Baking/Characterization

25 Years of Natural Gas Purged Infrared Pyrometer Temperature
Measurement for the Operation of Open-Top Anodes Baking Furnaces . . . . . . . . 1231
Yvon Menard
Characterization of Prebake Anodes by Micro X-ray Computed
Tomography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1237
Stein Rørvik and Lorentz Petter Lossius
Development of Techniques and Tools for the Determination
of Carbon Anode Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1247
Duygu Kocaefe, Yasar Kocaefe, Dipankar Bhattacharyay,
Bazoumana Sanogo, Yao Ahoutou, Hang Sun, and Patrick Coulombe
Flow Detection Module—A New Model to Predict the
Flow in Open Pit Anode Baking Furnaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1255
Detlef Maiwald, Domenico Di Lisa, Florian Krummrich, and Frank Heinke
Formation of Carbon Build-Up on the Flue Wall of Anode
Baking Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1265
Zhaohui Wang, Stein Rørvik, Arne Petter Ratvik, and Tor Grande
Identification of the Stress Intensity Factor of Carbon Cathode
by Digital Image Correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1275
Donald Picard, Luca Sorelli, Julien Réthoré, Houshang Alamdari,
Marc-Antoine Bari, and Mario Fafard
Investigation of Spent Refractory Lining in an Anode
Baking Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1281
Trond Brandvik, Zhaohui Wang, Arne Petter Ratvik, and Tor Grande
Non-Destructive Testing of Baked Anodes Based
on Modal Analysis and Principal Component Analysis . . . . . . . . . . . . . . . . . . . . . . 1289
Moez Ben Boubaker, Donald Picard, Carl Duchesne, Jayson Tessier,
Houshang Alamdari, and Mario Fafard
3D Automated Anode Stub Inspection System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1299
Jean-Pierre Gagné, Rémi St-Pierre, Pascal Côté, and Harold Frenette
Impact of Cast Iron Degradation and Cathode Block Erosion
on the Current Path in the Cathodic Assembly of Aluminum
Production Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1307
Martin Brassard, Marc LeBreux, Martin Désilets, Gervais Soucy, Martin Forté,
and Jean-François Bilodeau

Part XXVIII Electrode Technology: Electrode Design and

Performance
Finite Element Analysis of Slot Size Effect on the
Thermal-Electrical Behaviour of the Anode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1315
H. Chaouki, M. Baiteche, A. Jacques, E. Gosselin, H. Alamdari, and M. Fafard
Contents xix

Hydrodynamic and Thermoelectric 3D Mathematical Model

of Aluminium Electrolysis Cell to Investigate Slotted Carbon
Anode Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1325
Mounir Baiteche, Hicham Chaouki, Edward Gosselin, Alain Jacques,
Houshang Alamdari, and Mario Fafard
Gas Anodes Made of Porous Graphite for Aluminium
Electrowinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1333
Babak Khalaghi, Henrik Gudbrandsen, Ole Sigmund Kjos,
Karen Sende Osen, Ove Bjørn Paulsen, Tommy Mokkelbost,
and Geir Martin Haarberg
The Impact of Anode Nails on the Stub to Carbon Electrical
Contact Resistance of Anode Assemblies with Simulated
Corroded Stubs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1341
W. Berends
Xelios 2.0: Return on Experience for the Advanced Eco-Designed
Vibro-Compactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1349
Vincent Philippaux and Bastien Aymard
Production of NiFe2O4 Nanocermet for Aluminium Inert Anode . . . . . . . . . . . . . . 1357
Wu Xianxi, Zhu Weidong, Luo Kunlin, and Wu Song
Reducing Cathode Voltage Drop and Reducing Peak Current
Density by Use of Cathode Nails Across the Carbon to
Cast Iron Interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1365
William Berends
Hexapod Fleet Migration in Order to Upgrade to
AP40LE Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1375
Marc Gagnon and Jonathan B. Reichelson
The Impact of Increased Anode Size and Amperage Creep on
Anode Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1385
James Anson, René Trudel, and Bertrand Vincent

Part XXIX The Science of Melt Refining: An LMD Symposium

in Honor of Christian Simensen and Thorvald Abel Engh:
TAE/CJS Honorary Symposium I: Inclusion Removal
The Contributions of Prof. Thorvald Engh and Christian Simensen
to the Science and Technology of Melt Refining and Oxidation . . . . . . . . . . . . . . . 1397
Anne Kvithyld and John Grandfield
The Fundamentals of Forming Microbubbles in Liquid Metal Systems . . . . . . . . . 1403
Roderick I.L. Guthrie, Mihaiela M. Isac, and Roger T. Ren
A Holistic Approach to Molten Metal Cleanliness . . . . . . . . . . . . . . . . . . . . . . . . . . 1411
D. Corleen Chesonis
Results of Trials with a Multi Stage Filtration System Employing
a Cyclone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1419
John Courtenay, Marcel Rosefort, and Phil Jankowski
Developments in Inclusion Removal Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1429
John Grandfield
xx Contents

Part XXX The Science of Melt Refining: An LMD Symposium

in Honor of Christian Simensen and Thorvald Abel Engh:
TAE/CJS II Degassing and Oxidation
Overview of Ultrasonic Degassing Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1437
Dmitry G. Eskin
Modelling of Hydrogen Removal in Gas Fluxing of Molten Aluminium . . . . . . . . . 1445
Dag Mortensen, Jinsong Hua, Arild Håkonsen, Terje Haugen, and John Olav Fagerlie
Oxide Skin Strength on Molten AA5XXX Aluminum
Alloy—Effect of Beryllium and Alternatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1451
Martin Syvertsen
Understanding of Interactions Between Pyrolysis Gases
and Liquid Aluminum and Their Impact on Dross Formation . . . . . . . . . . . . . . . . 1457
R. Dittrich, B. Friedrich, G. Rombach, J. Steglich, and A. Pichat
Effects of 2 ppm Beryllium on the Oxidation of a 5XXX
Aluminum Alloy at Temperatures Between 500 and 750 °C . . . . . . . . . . . . . . . . . . 1465
Nicholas Smith, Brian Gleeson, Anne Kvithyld, and Gabriella Tranell
The Use of Nitrogen to Degas Molten Aluminium—Comparison
of Metallurgical Results with Argon and Nitrogen Used in an ACDtm . . . . . . . . . . 1475
Étienne Tremblay and Bruno Maltais
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1481
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1487
About the Editor

Arne P. Ratvik is a senior scientist at SINTEF Materials and

Chemistry in Trondheim, Norway. He has his M.Sc. and Ph.D.
in inorganic chemistry from NTNU (Norwegian University of
Science and Technology) followed by a post doc period at the
University of Tennessee, all related to molten salt chemistry and
electrolytic production of light metals. He has industrial research
and production management experience from Elkem and
Falconbridge Nikkelverk (currently Glencore Nikkelverk),
respectively, followed by several positions in SINTEF (research
director, research manager and senior scientist). He served a
four-year term as head of Department of Materials Science and
Engineering at NTNU. Dr. Ratvik’s current research interests are
mainly within aluminum electrolysis with emphasis on materials
chemistry and electrochemical performance of carbon anodes
and cathodes, besides having experience from ferro-alloy and
silicon pyrometallurgical processes and metal electrowinning in
aqueous solutions. He has been project manager of several large
primary aluminum-related projects and co-authored more than
50 papers in addition to many company proprietary reports. He
has served The Minerals, Metals & Materials Society (TMS) as
session chair four times and subject chair for the Electrode
Technology in 2015.

xxi
Program Organizers

Alumina and Bauxite

Ting-an Zhang is a full professor at Nonferrous Metallurgy of

Northeastern University (NEU), China. He has his B.S., M.Sc.,
and Ph.D. in rare metal metallurgy, metallurgical physical
chemistry and energy engineering respectively from NEU
(Northeastern University), and studied at the National Univer-
sity of Science and Technology, Russia Federation, for half a
year. He served a ten-year term as Dean of School of
Metallurgy and Materials at NEU.
Dr. Zhang has more than 30 years’ experience in metallurgy
process and technology. He is currently Director of Special
Metallurgy and Process Engineering Institute, where his
research activities are focused on alumina clean production
with an emphasis on transformation of the red mud construc-
tion, besides pressure hydrometallurgy, SHS metallurgy, and
physical and mathematic simulations of metallurgical processes
and reactors. He has been project manager of more than 20
projects including National Key Research and Development
Program, National Natural Science Fund and alumina-related
projects for plants. Dr. Zhang has co-authored more than 300
papers and 7 books, and proposed more than 100 invention
patents. His work on calcification-carbonation method for red
mud treatment has been awarded both internationally and in
China.

Aluminum Alloys, Processing, and Characterization

Yanjun Li is a full professor at Norwegian University of

Science and Technology (NTNU), Norway. Yanjun has a
Ph.D. degree in materials science and engineering. Before
joining NTNU, he worked as a research metallurgist at Hydro
Aluminium for 3 years, and research scientist and senior
research scientist at SINTEF Materials and Chemistry for
6 years. Dr. Li’s research is focusing on physical metallurgy of
aluminum alloys, including solidification and casting, heat
treatment and phase transformation, deformation and mechan-
ical properties, advanced microstructure characterization, and
microstructure simulation model developments.

xxiii
xxiv Program Organizers

Aluminum Reduction Technology

Mark Dorreen After completing a Ph.D. focused on current

efficiency measurement and anode effect gases, Mark Dorreen
worked in various commercial and technical aspects of electric
arc steelmaking for 10 years. He then returned to the Light Metals
Research Centre at the University of Auckland in 2008, where he
now holds the role of director, with responsibility for all the
commercial activities and the day to day running of the centre.
Mark’s particular interests are in anode plant operations, in
particular the rodding room, as well as aspects of potroom
operations and pot emissions, and he has travelled widely to work
on many LMRC projects, most frequently to smelters in China.
In addition to his LMRC role, Mark is also vice president–
technical at Energia Potior Limited, a new company set up to
commercialize the Shell Heat Exchanger technology developed at
the University of Auckland.

Cast Shop Technology

Cast Shop Technology: Recycling and Sustainability Joint Session

David Gildemeister received a B.S. in metallurgical engineer-

ing at South Dakota School of Mines and Technology in 1993
and a Ph.D. in materials science and engineering from Carnegie
Mellon University in 2016. He has worked for Arconic
(formerly Alcoa, Inc.) for more than 24 years. Thirteen years
in four different production facilities as a process and product
metallurgist have exposed him to numerous billet, ingot, and
continuous casting processes, as well as hot rolling. For the past
eleven years, he has conducted research and development in
aluminum casting and solidification at the Arconic Technology
Center in New Kensington, Pennsylvania.

Electrode Technology

Houshang Alamdari received his M.Sc. degree in 1996 and

Ph.D. degree in 2000 from Université Laval, Canada. He
pursued research activities at the Hydro-Quebé c Research
Institute, Canada, on the synthesis of nanocrystalline materials
for hydrogen storage. He held the process director position at
Nanox Inc, Canada, and was involved in the development and
scale up of a production process for nanostructured
perovskite-type materials for automotive catalysts. In 2006, he
joined Laval University as professor at the Department of
Mining, Metallurgy, and Materials Engineering, Université
Laval, Canada. He is currently director of the Regal-Laval
Research Center, where his research activities are focused on
the anode manufacturing process for aluminum production.
Program Organizers xxv

The Science of Melt Refining: An LMD Symposium in Honor of Christian

Simensen and Thorvald Engh

John Grandfield is the director of Grandfield Technology Pty

Ltd, a consulting and technology firm, and adjunct professor at
Swinburne University of Technology in the High Temperature
Processing Group. John has a Bachelor of Applied Science
degree in metallurgy (RMIT), an M.Sc. in mathematical
modelling (Monash University), and a Ph.D. in materials
science (University of Queensland).
John has 30 years’ experience in light metals research and
technology in smelting, continuous casting, and metal refining
(Rio Tinto Alcan, CASTcrc and CSIRO). He has conducted
plant benchmarking audits, technology reviews, optimised
existing technology, managed technology transfer, and devel-
oped and commercialised new cast house technologies. He
remains active in research with a current focus on ingot cavity
control and inclusion removal.
His work on direct chill and ingot casting of aluminium and
magnesium has been awarded both internationally and within
Australia. John is regularly invited to give training courses,
participate in in-house innovation workshops, and conduct
R&D program reviews around the world.
John has four patents, has published two book chapters,
more than 50 conference, and journal papers, and has
co-authored a book on DC casting of light metals. He is a
member of the TMS Aluminum Committee and was editor of
Light Metals 2014.

Anne Kvithyld is a senior scientist at SINTEF in Trondheim,

Norway. She earned her Ph.D. from the Norwegian University
of Science and Technology (NTNU) in 2003. She has been a
visiting scholar at the Colorado School of Mines, USA. Her
research interests are on production of metals, in particular
refining and recycling. She is an active member of The
Minerals, Metals & Materials Society (TMS).
Aluminum Committee 2016–2020

Chairperson
Edward McRae Williams
Alcoa Inc
Pennsylvania, USA
Vice Chairperson
Arne P. Ratvik
SINTEF
Trondheim, Norway
Past Chairperson
Margaret M. Hyland
University of Auckland
Auckland, New Zealand
Light Metals Division Chair
Alan A. Luo
Ohio State University
Ohio, USA
Secretary
Stephen Broek
Hatch Ltd
Ontario, Canada
JOM Advisor
Pascal Lavoie
Light Metals Research Centre
Quebec, Canada
Member-At-Large
Stephen Broek
Hatch Ltd
Ontario, Canada

Members Through 2017

Thomas P. Clement, II
Alcoa US Primary Products
Texas, USA
Mark A. Cooksey
CSIRO
Victoria, Australia

xxvii
xxviii Aluminum Committee 2016–2020

Les C. Edwards
Rain CII Carbon LLC
Louisiana, USA
Gyan Jha
Kentucky, USA
Barry A. Sadler
Net Carbon Consulting Pty Ltd
Victoria, Australia

Members Through 2018

John F. Grandfield
Grandfield Technology Pty Ltd
Victoria, Australia
Kai F. Karhausen
Hydro Aluminium
Bonn, Germany
Edward McRae Williams
Alcoa Inc
Pennsylvania, USA

Members Through 2019

Pete Forakis
STAS Middle East Ltd FZE
Sharjah, United Arab Emirates
John V. Griffin
ACT LLC
New Jersey, USA
Margaret M. Hyland
University of Auckland
Auckland, New Zealand
Pascal Lavoie
Light Metals Research Centre
Quebec, Canada
Arne P. Ratvik
SINTEF
Trondheim, Norway
Hans-Werner Schmidt
Outotec GmbH
Oberursel, Germany
Alan David Tomsett
Pacific Aluminium
Queensland, Australia
Aluminum Committee 2016–2020 xxix

Members Through 2020

Phil Black
Regain Materials
Melbourne, Australia
Kathie McGregor
CSIRO
Victoria, Australia
 Part I
Alumina and Bauxite: Digestion and Calcination
 CFB Alumina Calciners—New and Future
Generation Opportunities for Green Field
Refineries

Linus Perander, Alessio Scarsella, Edgar Gasafi,

and Hans-Werner Schmidt

Abstract
The latest CFB Calciners were installed in green field Alumina Refineries. Because of the
pressure of cost reduction, a low capital expenditure needs to be achieved. At the same
time, an outstanding performance is expected regarding energy consumption, product
quality and availability. It is obvious that these contradictory demands are running into a
conflict, if the conventional technology is only reproduced. New developments are required
to achieve these challenging market demands. This paper describes how solutions were
developed, proven and tested and expands on possible future improvements. Examples of
new developments are described. Further, it is shown how these targets are achieved with
new large calciners installed in a new green field alumina refinery. These new features are
considering a steady continuous operation. At the same time product quality and energy
consumption are improved.

Keywords
Calcination Alumina CFB Product quality

Introduction of the good efficiency of the cyclones in front [4]. With

Given the commercial success of the Circulating Fluidised
Bed in the power plant industry [1], a fact often overlooked
is that the development of this technology originated in the
alumina industry [2, 3]. The first CFB calciner was from its
concept and arrangement very similar to the original pilot
plant [2]. The hydrate was introduced at the venturi on the
top of the plant and the alumina discharge entered the
cooling system by gravity hence the final discharge was the
lowest level in the calcination plant.
For capacities of 500 tpd the investment was not a
problem regarding capex and feasibility. At capacities over
800 tpd, it became necessary to rearrange the plant concept
to a horizontal arrangement in order to save investment cost.
The original calciners had two cyclones in front of the
ESP. This concept resulted in a relative small ESP because
L. Perander
A. Scarsella
E. Gasafi
H.-W. Schmidt (&)
Outotec GmbH & Co. KG, 21 Ludwig-Erhard Strasse, 61440
Oberursel, Germany
e-mail: hans-werner.schmidt@outotec.com
larger capacity and by introducing the horizontal plant
arrangement the cyclones were replaced by a mechanical pre
separator integrated in the front-end of the ESP [5].
Description of Calciner Development
Reduction of Capex
Calcination of alumina using the CFB technology was
introduced to the industry in 1970. The origin of this tech-
nology was a joint development between the alumina
industry (VAW) and Outotec(Lurgi). The result was the first
successful industrial unit with a capacity of 500 MTPD of
alumina which was commissioned in 1970 [2]. Since then
there are more than 60 units installed world-wide. The
design capacities of these units are varying in a range
between 800 up to 3500 MTPD Al2O3. When one compares
the first commercial unit (started up in 1970) with the plant
design of today, many improvements become apparent [6].

© The Minerals, Metals & Materials Society 2017 3

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_1
4 L. Perander et al.
The design of the first calciners was heavily influenced by
the pilot plant and the results obtained with the pilot plant. In
order to minimize risks, well-known features and their pro-
ven performance were transferred to the first industrial unit.
That concept was applied in particular for the calciner at the
AOS refinery were for the first time the CFB technology was
introduced in a green field refinery (Figs. 1 and 2).
Naturally, capex played an important role for these cal-
ciners even if at the time the customer was the development
partner for the CFB alumina calciners. The AOS calciners
had a capacity of 650 tpd each.
It became obvious that with increasing capacities the
tower arrangement was not competitive. At a capacity of
650 tpd the tower arrangement had already a height of 70 m.
Going from the tower design to a horizontal arrangement
of the equipment saved approx. 38% of the structural steel
needed for the support of the vessels. Although this saving
contributed significantly to reduce the capital cost and made
the calciner more competitive in the market an additional
pneumatic transport was needed to carry the product from
the first to the second preheating stage. This was realized
with a so called airlift, a vessel designed to provide a
Fig. 1 650 MTPD alumina calciners—tower arrangement upgraded to
750 MTPD and 840 MTPD
Fig. 2 1,850 MTPD alumina calciners—flat arrangement
pressure seal and allow the pneumatic transport of the pre
dried hydrate back to the process. The target of the imple-
mentation of this transport was to operate the calciner with
the same reliability as when the product flow was driven
only by gravity.
Besides the obvious difference of saving structural steel,
there are many other features that have been developed with
the evolution of the calciners over the last 40 years:
• Higher specific gas throughput
• Easier control and improved safety
• Higher availability
• Lower specific investment cost
• Improved product quality (through optimisation of
velocity profile, fluidisation technologies and nozzle
design).
Especially for the further scale up from 2000 MTPD up to
3500 MTPD it became necessary to introduce further
improvements in order to minimise capital cost.
This reduction is not only the result of the increased
capacities but also of the more efficient use of construction
materials. Figure 3 shows how over the last 40 years the
specific weight of equipment, refractory and structural steel
was reduced.
Reduction of Energy Consumption
Further to the reduction of capital cost increasing energy
prices were demanding a reduction of the energy cost. Thus
many of the new technologies introduced in the CFB alu-
mina calciner were developed in order to reduce the specific
fuel requirement [7]. The most important resulted in the
following developments:
CFB Alumina Calciners—New and Future Generation Opportunities …
Fig. 3 Specific weight/tpd Al2O3 versus time
• Hydratebypass [8]. A substream of pre-calcined
hydratebypasses the furnace and is reacted to SGA uti-
lizing the heat with the hot alumina discharged from the
furnace in a purpose designed mixing pot.
• More cooling stages. In order to improve the heat
recovery from the product alumina an additional cooling
stage was included in the flowsheet [8]. This design
change defined the 3nd generation of alumina CFB
calciners.
• Hydrate dryer. The hydrate dryer utilizes heat from the
fluid bed cooler (otherwise often wasted over the cooling
Fig. 4 Energy efficiency at
different installations. *Note that
the theoretical energy
consumption does include 6%
surface moisture but does not
include any heat losses and
assumes all energy is used for the
calcination reactions
5
tower) to pre-dry a substream of wet hydrate before
feeding this to the first pre-heating stage in the calciner [6].
As a result of these changes Outotec has progressively
reduced the specific fuel energy requirement (see Fig. 4) and
recently set the current benchmark of 2.7 GJ per ton alumina
[6]. It should be pointed out that this record low specific fuel
consumption is achieved on a continuous basis (long term
average). It should also be noted that this was achieved in a
40 year old plant by retrofitting and upgrading the plant to a
more modern configuration including both a hydratebypass
and a hydrate dryer [6].
Product Quality
With regard to today’s alumina production the following
three issues are most important:
• Particle size/particle breakdown
• Loss on ignition, LOI
• Specific surface area, BET (m2/g).
Particle breakdown was always a major issue during the
development of the CFB technology in the alumina industry
[references]. Although the particle strength of the hydrate
has a significant impact on the breakdown, the calciner
design still plays an important role both in terms of
mechanical breakage as well as temperature effects (thermal
stress and attrition, material brittleness).
6 L. Perander et al.
As reported earlier [9–12], the velocity in certain areas
(Venturis, cyclone inlet etc.) has to be limited. Also sharp
edges and sharp bends need to be avoided in areas where gas
solid flow is in transportation mode. It has clearly been
found from investigation of operating calciners, that attrition
mainly takes place in the areas mentioned above and not in
the CFB itself, where the solid velocities are relatively low
[12]. It should be pointed out, that the solids concentration in
the CFB is in a highly expanded fluid bed [3], which is
significantly less than in a standard fluid bed [13].
In order to reduce attrition under influence of high
velocities in critical areas, a Computational Fluid Dynamic
(CFD) model of the gas/solid flows in segments of the cal-
ciner was developed in co-operation with CSIRO/Australia
[14]. The results of the CFD modelling provided a solution
in a three-dimensional flow field on several critical areas
such as cyclone inlets, solid feeding point, venturi nozzles
and ducts, which was considered in the further design iter-
ations. With support of these results these areas were opti-
mised to ensure a minimum differential velocity between gas
and solid, resulting in a reduction of particle breakdown. The
afore mentioned split of primary air to secondary air was
also helpful in reducing the particle breakdown by lowering
the velocities in the primary air nozzles. Particle breakage of
<3% are achieved today in large calciners by applying these
features [12], as also shown in Fig. 5.
By implementing these improvements, the overriding
importance was always to maintain the reliability of the
calciner. This applies for operation as well as for product
quality.
Fig. 5 Particle Breakage of CFB Calciners compared to rotary kilns
Discussion
Figure 6 shows the current CFB alumina calcination flow-
sheet and Fig. 7 the same in a 3D model. This flowsheet
incorporates a mechanical preseparation before the ESP, this
allows to use gravity to feed the predried hydrate to pre-
heating stage II. Furthermore, this flowsheet includes a
hydratebypass from the first preheating stage to the mixing
pot as well as an ESP dust transport to the first cooling stage.
The hydratebypass has been discussed elsewhere [15], and is
a practical mean to enable further fuel energy savings by
utilizing the available heat with the discharged alumina to
calcined the bypassed hydrate in the mixing pot. As shown
in Fig. 8 this can be achieved without compromising the
product quality in terms of LOI, BET or alpha alumina.
Recent plant experience have shown that the hydrate
fraction in the ESP dust is fully calcined in the liftduct of the
first cooling stage [12, 16]. This ensures that no hydrate is
carried over to the product alumina and that the LOI is
maintained below common standard (1.0 wt%).
Demands from Customer and Impact
on Supplier
When considering a greenfield refinery or capacity expan-
sion requiring a new calcination plant, the customer is driven
by a limited budget but also must have certain expectations
on the supplier/technology. These expectations are typically
expressed in terms of performance guarantees, such as:
• Throughput
• Fuel and electrical energy consumption
• Product quality.
In addition, local environmental requirements have to be
met.
In order for the alumina refinery to achieve the production
targets in an economically sustainable way, a high reliability
is demanded from each process facility. Where practical, this
is achieved by having a certain redundancy, however this
often comes at higher investment cost. For example in cal-
cination a few large calciners is more feasible then several
smaller units, but this reduces the flexibility in production.
CFB Alumina Calciners—New and Future Generation Opportunities … 7

Fig. 6 Current CFB calcination

flowsheet (generation 5)

Fig. 7 3D model of the latest 2  3500 tpd alumina CFB calciners (in
construction)
Fig. 8 Effect of hydrate bypass flow and calcination temperature on
LOI and BET
The highly competitive situation requests sometime signif-
icant changes in the technology. The target is always to main-
tain the basic performance and reliability of the calciner. The With this procedure in place, it can be ensured that the
challenge for the supplier is to win the order in a competitive performance is achieved and the project is executed to
situation and to maintain quality and performance. This can be budget and schedule.
achieved by the following measures when considering to
introduce new solutions to increase the competiveness:
Conclusion
• Rigorous test or modelling at representative conditions to
Over the more than 40 years evolution of the CFB calcina-
ensure 100% performance
tion technology several new developments were introduced.
• Selection of solutions with proven references
This was always done with the Customers best interests in
• Risk analysis of the process design parameters prior to
mind and resulted in significant reduction of specific
project execution.
investment cost, reduced specific fuel and electrical energy
8 L. Perander et al.
Fig. 9 Evolution of Fuel and
Electrical energy consumption
and particle breakage throughout
the >40 year history of the CFB
alumina calciner
consumption and improved product quality. As the possible
gains in terms of performance improvements are becoming
smaller and smaller the technical demand on the required
changes increases. Therefore, the risks have to be considered
early on in the design stage, prior to execution, and mitigated
through selection of proven solutions, supported by testwork
or modelling (Fig. 9).
References
1. L. Reh, H.W. Schmidt, G. Daradimos, V. Petersen, Preprints
Institute of Energy Conference, Fluidized Combustion: Systems
and Applications (1980), VI-2
2. L. Reh, J. Ernst, H.W. Schmidt, K.H. Rosenthal, Aluminium 47
(11), 681–685
3. A. Squires, Origins of the fast fluid bed, Advances in Chemical
Engineering, vol 20 Fast Fluidization ed. by M. Kwauk (Academic
Press, 1994), p 4–35
4. E. Hugi, L. Reh, Design of Cyclones with High Solids Loadings
for Circulating Fludized Bed Reactors (Research Activities,
Institute of Process Engineering ETH Zürich, 1997), p. 39
5. H.W. Schmidt, H. Beisswenger, F. Kaempf, Feasibility of fluid bed
calciner process in view of changing demands in the alumina
market. J. Met. 32(2) (1980)
6. L. Perander, A. Lalla, C. Klett, B. Reeb, B. Petersen, M. Missalla,
E. Guhl, Application of optimized energy efficient calcination
configuration to AOS Stade CFB calciners, in Proceedings of the
9th Alumina Quality Workshop (2012)
7. A. Scarsella, S. Noack, E. Gasafi, C. Klett, A. Koschnick, Energy
in alumina refining, setting new limits, in TMS Light Metals
Proceedings, 2015, pp. 131–136
8. H.-W. Schmidt, W. Stockhausen, A. Silberberg, Alumina Calci-
nation with the Advanced Circulating Fluid Bed Technology: A
Design with Increased Efficiency Combined with Operating
Flexibility (TMS Light Metals, Warrendale, Pennsylvania, 1996),
pp. 81–87
9. M. Missalla, R. Bligh, M. Stroeder, C. Klett, Design Developments
for Fast Ramp-Up and Easy Operation of New Large Calciners
(TMS Light Metals, Warrendale, Pennsylvania, 2007), pp. 79–86
10. M. Missalla, J. Jarzembowski, R. Bligh, H.-W. Schmidt, Increased
Availability and Optimization Of Calciner Performance Due To
Automation (TMS Light Metals, Warrendale, Pennsylvania, 2009),
pp. 241–246
11. P. Hiltunen, R. Bligh, C. Klett, M. Missalla, H.-W. Schmidt, How
to Achieve High Availability with Large Calciners and Avoid
Unforeseen Downtime (TMS Light Metals, Warrendale, Pennsyl-
vania, 2008), pp. 63–68
12. C. Klett, M. Missalla, R. Bligh, Improvement of Product Quality in
Circulating Fluidized Bed (TMS Light Metals, 2010)
13. L. Reh, Fluidized bed processing. Chem. Eng. Prog. 67(2), 58–63
(1971)
14. D.J. Brodie, H.-W. Schmidt, Custom design fluid BEd calciner for
Nabalco Pty. Ltd, in Proceedings of the 5th International Alumina
Quality Workshop, Bunbury, Australia (1999)
15. Y. Yetmen, H.-W. Schmidt, Large units for calcination plants with
improved technology, in International Conference on New Devel-
opment in Metallurgical Process Technology Proceedings VDEM
(1999), pp. 369–375
16. H.W. Schmidt, Advanced circulating fluid bed technology for
alumina calcination, in Proceedings of 6th International Confer-
ence Circulating Fluidized Beds (1999), pp. 587–592
17. C. Klett, L. Perander, Alumina Calcination—A Mature Technology
under Review from Supplier Perspective (TMS Light Metals,
2015)
 Evolutional Development of Alkaline
Aluminosilicates Processing Technology

Andrey Panov, Sergey Vinogradov, and Svyatoslav Engalychev

Abstract
Alkaline aluminosilicates are of significant interest for metallurgical and chemical
industries. They are widespread in countries like Russia, USA, China, Canada, Venezuela,
Mexico, Iran, etc. and can present a viable alternative to bauxites. Complex and waste-free
alkaline aluminoslilcates processing technology into alumina, soda ash and cement was
developed in VAMI institute in 20th century from idea till successful realization at several
industrial facilities in Russia, operating till now with competitive production cost of
alumina. Russian Alumina refineries are using feedstock with unique high alumina content
(Al2O3 26–28%) whereas there are other nepheline sources in Russia and in other counties
of lower quality (Al2O319–22%) and their processing results in more cement produced per
tonne of alumina. An economical beneficiation technology has been developed that opens
the possibility for more efficient industrial processing of comparatively poor aluminosil-
icate raw materials in Russia and the rest of the world.

Keywords
Alkaline aluminosilicates Processing properties Quality Beneficiation

Introduction pioneered the processing of this raw material into alumina.

Alkaline aluminosilicates (nepheline syenites, leucites,
anorthosites, dawsonites) being widespread in the world are
a promising but underestimated raw material source for
aluminium production. Nepheline ores are the second most
significant raw material for alumina production after baux-
ites. To date, alumina is produced from nepheline ores at
industrial scale only in Russia using two major sources
(Kiya-Shaltyr in the Kemerovo Region in Siberia;
Kukisvumchor, Yukspor, Rasvumchor in the Murmansk
Region). The industrial value of alkaline aluminosilicates is
defined by the possibility to produce multiple products (soda
ash, potash, cement, Ga, Cs, Rb), assuring the profitability of
processing the raw material where the silica content is
1.5–2.5 times higher than that of alumina. Russia has
A. Panov (&)
S. Vinogradov
S. Engalychev
UC Rusal Engineering and Technology Centre (VAMI),
Saint Petersburg, 199106, Russian Federation
e-mail: Andrey.Panov@rusal.com
Continuous improvement of the technology by RUSAL is
creating the possibility to widen the existing raw material
base by including aluminosilicate raw materials with lower
alumina content of which there are huge resources globally.
Nepheline Syenite Raw Material Base Review
Igneous Nepheline rocks vary greatly in structural features,
the presence of secondary elements, and quantitative inter-
relation between coloured and colourless components
(theralites, nepheline syenite, miaskites, mariupolites etc.).
The most industrially important are the nepheline syenite,
ijolite and urtite ores.
Nepheline syenites are the most common type of
nepheline rocks, and form a quite abundant group of igneous
alkali minerals comprising 20–45% of nepheline Na3K
[Al2Si4O16], 20–60% of alkali feldspar (K, Na)[AlSi3O8]
(these two minerals generally making 80–90% of the rock),

© The Minerals, Metals & Materials Society 2017 9

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_2
10 A. Panov et al.

orthoclase or microcline K[AlSi3O8], and auxiliary minerals the Sengilen mountain range (South-Eastern Tuva), the
of biotite, alkali pyroxene, amphibole, apatite, augite and Urals (Ilmen and Vishnev Mountains). In Canada about 10
others. The chemical composition of the rock is typically: large nepheline deposits are located in the south of Ontario
50–56% SiO2, 19–24% Al2O3, 12–17% К and Na, some Ca and Quebec provinces [2]. The reserves of each deposit
and Mg. amount to approximately 100 Mt. Third in commercial
Igneous rocks of this group form often large, isometric, importance is the Stjernøy deposit located in Norway, which
intrusive deposits that stretch over dozens of kilometers. Due has resources of about 300 Mt. There is the possibility for
to their formation, such deposits often have pillar like other big deposits to be explored provided the consumption
structures and penetrate up to hundreds of meters deep. This of nepheline increases.
ensures their potential for long life open cast mining. The Nepheline ores are used for 2 main purposes:
majority of such masses develop within crystalline shields
(such as Canadian, Baltic, Ukrainian, Zimbabwe, Malagasy (a) as raw material for alumina and by-products at Achinsk
etc.), and in folded mountain regions (Kuznetsk Alatau, Alumina Refinery (AGK) (Kiya-Shaltyr) and in Pika-
Andes, Urals etc.). levo (Khibin concentrate);
Nepheline syenites are widely distributed in Russia (Kola (b) for glass and ceramic uses in Canada, China, Norway,
peninsula and Siberia), Canada (Ontario, British Columbia), Turkey, Russia, South Africa.
USA (Arkansas, New Jersey/Beemerville, Massachusetts,
Texas), South Greenland, Mexico, Norway (Northern Nor- For many years two large nepheline syenite deposits have
way, Oslo district), Sweden, Finland, Italy, Germany been mined in Canada (Blue Mountain) and Norway
(Dresden district), Czech Republic, the Ukraine, Kazakhstan (Stjernøy) producing high-purity potassium nepheline-
(Priishimye), China, Iran (Razgah deposit), Pakistan, India, enriched feldspathic concentrates. The composition of the
South Africa (Kenya, Uganda etc.), Madagascar, Chile, Blue Mountain nepheline ore is 23% A12O3, 60% SiO2, and
Bulgaria, Brazil, etc. [1, 2] The mines and deposits of 4% K2O. Due to presence of alumina and alkali, nepheline
nepheline ores are shown at Fig. 1. concentrates are used as raw material for production of:
Total world nepheline resources are estimated to be in the (1) Glass (flux to reduce fusion temperature, ensures resis-
range of 12-15 billion tonnes. Russia possesses the biggest tance to scratches and cracks, improved heat resistance,
nepheline resources: apatite-nepheline deposits in the Kola chemical recovery); (2) Ceramics (flux to reduce fusion
Peninsula are up to 4 billion tonnes of nepheline, and temperature); (3) Filler in adhesives, paint, plastics, and
resources of up to 3 billion tonnes in Siberia—Kuznetsk sealants; (4) Mineral wool (thermal insulation); (5) Building
Alatau, Northern Baikal region, Eastern Sayan Mountains, stone, etc.

Fig. 1 Nepheline mines and deposits of the world. Adapted from [1]
Evolutional Development of Alkaline Aluminosilicates … 11

Table 1 Typical quality of Country Region A12O3 SiO2 Na2O K2O Fe2O3 CaO
major nepheline ores
Russia Kiya-Shaltyr 26.5 40.0 7.2 4.8 4.5 7.0
Kolsky concentrate 28.5 44.5 10.7 7.1 2.5 1.7
China Guangzhou 22.5 55.2 0.4 0.3 2.9 –
Heilongjiang 23.1 55 5.2 3.5 2.5 –
Iran Razgah 20.0 54.9 6.0 3.9 3.7 2.0
Pakistan Kota 22–24 48–48 6.5–8.7 4.3–5.7 2–3 –
North Korea Sackshu ore concentrate 18.0–22.8 42.0–49.9 6.6–7.8 4.4–5.1 9.9–4.3 7.7–3.8
Mexico Arroy Grande 19.81 47.33 8.27 5.16 4.03 4.71

The typical quality of major nepheline ores studied by
VAMI for alumina extraction in Russia of China, Iran,
Pakistan, North Korea and Mexico is shown in Table 1. The
data shows that the quality of the Russian Raw material is
better with respect to alumina and alkali content compared
with other ores.
Besides ore quality, the commercial value of any deposit
for alumina production depends on a number of other fac-
tors: remoteness, availability of infrastructure, size of
resource, demand for such raw material, etc. Based on the
analysis of current interest in nepheline ores we can draw the
conclusion that only large deposits with high-quality ores
and developed infrastructure have commercial significance.
Results of the geological investigation of many large
alkaline magmatic provinces having deposits with variable
quality, type and structure, give grounds to expect the dis-
covery of new large and high quality deposits suitable for
alumina production. Provided that enough investment in
new geological exploration will be available, such deposits
can be found in the areas like: 1. Kuznetsk Alatau (Russia),
2. South—Eastern Ukraine; 3. Iran, Razgah deposit etc.; 4.
Southern part of the Canadian shield—Ontario and Quebec
provinces; 5. Pakistan, 6. China; 7. Mexico. It is arguable
that there has generally not been enough systematic geo-
logical investigations of such raw materials for alumina
extraction in the world.
Alkaline Aluminosilcates Soda-Limestone
Sintering Technology
Development of the technology for processing of alkaline
aluminosilicate ores started in the USSR early last century to
utilize the nepheline rich residues after beneficiation of
apatite-nepheline ores from the Kola Peninsula. Develop-
ment of the basic technology was conducted by the VAMI
and GIPCH institutes under the guidance of F. Strokov,
P. Vlodavetz, I. Lileev and others. In the middle of the 1930s
it was decided to retrofit Volkhov aluminum plant for
processing of Kola nepheline concentrates, but the works
were interrupted by WWII. Volkhov was converted to the
process only in the early 1950s. After mastering at Volkhov,
the technology was further improved by VAMI and used for
construction of the Pikalevo and Achinsk alumina refineries,
which remain in good operating condition today. The prin-
ciple process flowsheet is presented at Fig. 2.
The complex processing of nephelines involves sintering
of the ore or concentrate with limestone in rotary furnaces at
temperatures of 1200–1300 ºС. The chemical process of this
stage can be summarized by the following reaction:
ðNa; KÞ2 O
Al2 O3
2SiO2 þ 4CaCO3
¼ ðNa; KÞ2 O
Al2 O3 þ 2ð2CaO
SiO2 Þ þ 4CO2 ð1Þ
The sinter is then leached with spent liquor. In this case,
sodium aluminate goes into the liquid phase, and solids, i.e.
belite mud (2CaO
SiO2) is directed to cement production.
Sodium aluminate is decomposed and alumina trihydrate
precipitates with liquor carbonation by the following reaction:
NaAlO2 þ CO2 þ 3H2 O ¼ Al2 O3
3H2 O þ Na2 CO3 ð2Þ
For aluminate liquor decomposition (precipitation),
dust-free flue gases from the sintering kilns containing 10–
16% CO2 are used.
Soda liquors are evaporated for soda ash, and belite mud
is further sintered with limestone to produce cement. Other
valuable components of the ore (K, Rb, Cs, Ga, etc.) can also
be extracted.
Over the more than 70-year period of development and
operation of nepheline technology, a variety of problems
have been solved and a huge number of improvements and
modernizations implemented by our experts, allowing the
process to be competitive with the Bayer process. For
example, the new method of pregnant liquor deep desilica-
tion using a synthesized active ion-exchange additive based
on carbo-aluminate developed by VAMI and St. Petersburg
State Mining institute, gave the opportunity to achieve the
required purity of hydrate and metallurgical alumina, while
12 A. Panov et al.

Fig. 2 Principle flowsheet of

VAMI sintering technology for
processing alkaline
aluminosilicates

Table 2 Technical parameters Parameter UoM Process

compared to the Bayer process
Sintering Bayer
Content of Al2O3 in the ore mass% 25–28 40–55
Raw material consumption t/t 4.5 nepheline 1.8–2.5
6.5 limestone
Commercial total Al2O3 recovery % 75–80 87–90
Electricity Kwh/t 1100 250–400
Fuel GJ/t 42–47 3–4
Steam GJ/t 5 4–12
Total energy consumption GJ/t 50–55 7–16
Typical production cost US$/t 190 230

reducing lime consumption for this process step. Deep
desilication and reduced carbonation temperature have
improved the coarseness and strength of alumina hydrate.
Physical characteristics of this hydrate and alumina are close
to reference sandy alumina.
In spite of relatively high energy consumption (Table 2),
the technology of alumina production from nephelines using
complex processing can be as commercially attractive as
processing high grade bauxites in the Bayer process.
The economic efficiency of sintering alkaline alumi-
nosilicates is achieved due to its complex nature and waste
free production. Along with each ton of alumina 0.8 t of
soda, 0.3 t of potash (Table 3) and 10 t of cement are pro-
duced. These products are highly-profitable and are in
demand. The balance of products is determined by the
composition of raw materials.
The production efficiency of this technology is mostly
dependent on demand for cement products. Often, the
cement market in the region can define the volume of alu-
mina production at a specific plant. In case of the inability to
sell the full volume of cement produced, other applications
of belite mud need to be explored.
Processing of Belite Mud
The efficiency of using nepheline sinter mud for cement
production is explained by the following:
Evolutional Development of Alkaline Aluminosilicates …
Table 3 By-products: Product Quality
characteristics, quality and yield
Soda Ash Superior
Na2CO3 and 1st
grade
Potassium 1 grade
sulphate
К2SO4
Potash Superior
K2CO3 and 1st
grade
Potassium Superior
chloride KCl and 1st
grade
Gallium Ga Purity
99.99%
• It is principally prepared for making clinker (2CaO
SiO2
content is *70–80%);
• Clinker yield from a mix containing mud is *10–15%
more than from an ordinary mix;
• Cement kiln productivity increases by 25–30%;
• Reduction of specific fuel consumption for clinker
burning by 5–7% due to the absence of decarbonation.
The process to obtain Portland cement using nepheline
sinter mud as part of the raw mix is industrially applied at
the Pikalevo and Achinsk cement plants. The composition of
belite muds from Achinsk Alumina Plant (AGK) and Pika-
levo Alumina Refinery (PGZ) are presented below in
Table 4.
Cement production using a two-component mix (lime-
stone and belite mud) without corrective mineral additives
can significantly simplify the technology of mix preparation
(compared to the classic version of the four-component mix
for clinker).
Our industrial experience with nepheline ore processing
can be summarised as follows: at Pikalevo alumina refinery
(Leningrad region) all the produced belite mud is processed
into cement and 100% recovery of waste is achieved. At the
Achinsk alumina complex (Krasnoyarsk region, Siberia), the
complete utilization of belite is not economically viable due
to the high production rate and long distances to potential
consumers. Only about 15% of mud is utilized for cement
production and a small portion for road construction. The
belite is also used in smaller quantities as mine backfill.
Along with the production of high quality cement prod-
ucts, belite mud can be used without additional processing
for medium-strength construction materials. The strength of
belite cement matches 150 grade concrete, so it can be used
for both the bedding of paved roads and for backfilling of
13
Yield, t/t Application
alumina
0.5–0.8 Chemical, pulp and paper, textile industry, oil treating
industries, washing substance and glass production
0.05–0.3 Fertilizers
0.04–0.1 Electronic and radio electronic industry, glass and crystal
production
0.003– Fertilizers
0.005
0.0000015 Radio electronics, defense
mines and drill holes after extraction of raw materials. Tests
have shown that belite mud can be used directly for mine
backfill, however the pure belite material requires long
periods for solidification and cementing (about 3 months for
the minimum strength of 20 MPa). The hydraulic activity of
nepheline ore and potential for its application as binding
material for backfilling depend on the alpha, beta or gamma
modification of belite. Selection and dosing of special
additives is required to control solidification and cementa-
tion. Calcium aluminate and gypsum can be used as such
additives are components of cement. By reducing the
required strength of the resulting belite stone, it is possible to
completely eliminate using thermal processes for transfor-
mation of belite (2CaO
SiO2) to alite (3CaO
SiO2). In this
case, materials with the physical and mechanical properties
listed in Table 5 can be obtained. The process can be
adapted to the specific conditions of the mine to select the
backfilling method with the minimum investment cost.
Heat treatment of belite hydration products can increase
the strength of the resulting materials (Table 6). It is worth
noting that there are other ways of producing binding
components using belite slurry, feasibility and cost-
effectiveness should be considered in each case for each
type of ore.
Based on research, industrial tests and industrial practice,
the following are opportunities for belite mud utilization:
• Cement production:
– Raw material component for clinker formation;
– Active mineral additive to the ground clinker.
• Road construction:
– Monolithic carry and frost protected foundations for
roads,
– Road cover;
14 A. Panov et al.

Table 4 Composition of Plant Commodity Al2O3 Fe2O3 SiO2 CaO MgO R2Oa
nepheline ore and belite mud
from Russian Alumina Refineries, Achinsk Nepheline 25.85 4.46 40.55 9.22 1.78 12.21
mass% Belite mud 3.70 3.71 29.57 54.25 1.85 2.65
Pikalevo Nepheline 28.35 2.65 45.09 0.95 17.76
Belite mud 2.44 2.18 31.14 58.40 1.35 1.60
a
Sum of Na2O and K2O

Table 5 Influence of additives Composition, % Normal initial density Setting time, Compressive strength
on properties of binder made of h-min (kg/cm2)/solution of 1:3,
belite mud storage (day)
Belite Additive Start End Wet-air Water
7 28 28
Mixed with gypsum
99 1 18.5 0–42 1–09 34.5 58.5 79.5
98 3 18.5 0–39 1–05 36.0 72.6 85.1
95 5 19.0 0–41 1–13 38.5 80.2 96.6
90 10 22.0 0–57 1–38 53.0 97.0 107.2
85 15 21.0 1–16 3–50 62.1 118.0 114.2
Mixed with lime
95 5 21.0 0–42 1–28 64.6 119.8 123.2
90 10 22.0 1–17 1–52 64.4 118.4 123.8
85 15 23.0 1–21 1–59 42.8 148.7 78.9
80 20 26.0 1–21 2–11 44.8 61.5 65.3
75 25 30.0 1–20 2–30 35.0 54.7 57.1

Table 6 Influence of Processing temperature, Associated Normal initial Setting time, Compressive strength
temperature on properties of °C water density h-min (kg/cm2)/solution of
binder made of belite mud 1:3, storage (day)
Start End Start End
7 28 28
– 1.34 Not able to concrete (bind)
300 0.97 33.5 4–15 6–15 26.1 73.1 51.9
400 0.88 38.0 3–10 5–05 37.5 73.0 61.9
500 0.85 35.0 3–18 5–33 44.0 76.9 74.3
600 0.66 34.6 4–22 6–32 52.3 65.0 36.9
700 0.62 34.6 1–20 4–45 74.9 46.1 33.2

–
Reinforcing poor soils for road construction; – Added for soil amelioration as microelement rich
–
Reinforcement of banks; component.
–
Foundations of ducts for water drainage • Manufacturing of construction materials:
–
Road service life increased 1.5 times, decrease of road – Binding material
construction costs by 4–5 USD/m2. – Grade M200
• Agriculture Filling of mined areas in underground mining
– Normalises acid-alkali balance and assures phospor- Increasing strength of normal and wet soils
ous retention in the soil; – Grade M300
Evolutional Development of Alkaline Aluminosilicates …
Manufacture of iron concrete blocks based on B15
concrete
Manufacture of commodity concrete B15 for foun-
dations, walls, ceilings etc.
– Density 400, 500, 600 kg/m3
Load carrying wall material in domestic construction
(up to 4 stories);
Internal wall construction;
Highly efficient thermal insulator (heat transfer coef-
ficient 0,1 W/(m °C))
– Cost of material reduction by 25–30 USD/m3
• Other applications
– Fillers;
– Sorbents;
– Glass materials;
– Slag stone casting;
– Refractory products;
– Construction ceramics;
– Synthetic zeolites, hydrosilicates,
– White silicate bricks (autoclave process);
– Asbestos-cement materials for roofs, etc.
– Specialty concretes (acid and alkali proof, heat proof,
water proof, etc.)
Integration of Beneficiation Technology
Under conditions of limited demand for soda ash and
cement/belite mud binder products, to allow industrial scale
low grade ore processing, the beneficiation of alkaline alu-
minosilicates can increase alumina and alkali content in the
alumina refinery feed while reducing silica and thus reducing
the cement produced per tonne of alumina. Russia and other
countries have abundant but predominantly low alumina
(19–23%) nephelines, consequently our specialists have
developed beneficiation processes for these low grade ores.
Depending on the mineral composition and grain struc-
ture of ores, the most suitable beneficiation technology can
be selected involving steps of gravimetric separation, mag-
netic separation, floatation, X-ray sorting and chemical
beneficiation. This opens the possibility to process ores of
any quality. For example, processing of a Russian raw
material with alumina content about 22% leads to a con-
centrate with 27% alumina. A variety of available benefici-
ation technologies allow regulation of the alumina vs cement
production ratio, depending on market scenarios.
The main target of beneficiation is increased aluminium
oxide and alkalis in nepheline concentrate, regardless of the
mineral form of the initial materials and to regulate output of
highly profitable by-products. The possibility to apply dif-
ferent beneficiation processes and the yield of products
recovered from the concentrate produced is defined
15
experimentally by laboratory studies of the ore and con-
centrate properties. A detailed model of production and the
local market should be made allowing selection of most
profitable way to develop a new plant.
Conclusions
1. Technology for alkaline alumina silicate processing into
alumina and by-products using a sintering process was
developed and only used industrially in Russia. This
technology has enormous application potential for many
other deposits globally.
2. The main features of the technology are:
• Relatively high consumption of raw materials com-
pared to the Bayer process. Processing of 4–4.5 tons
of nepheline/concentrate with limestone gives 1 tonne
of alumina, up to 0.8 t of soda ash, 0.3 t of potash and
10 t of cement; The main economic and environ-
mental advantage of nepheline technology is the
possibility for full utilization of all raw material
components for different products, leading to
waste-free production;
• The consumptions of fuel, steam and electricity are
significantly higher than for bauxite processing tech-
nologies, however those are compensated by absence
of soda consumption and the income from
by-products or intermediate by-products (alkali
liquors for soda ash and belite mud for cement
production);
• Even taking into account higher costs for repair and
maintenance of the main equipment, the production
cost of alumina from nepheline ores may be compa-
rable (or even lower), to that of high grade bauxite;
• The location of nepheline syenite deposits close to
aluminium smelters in areas without high quality
bauxites (like Canada, USA, China, Iran, etc.), has the
potential to significantly reduce the aluminium pro-
duction cost by lowering transportation costs com-
pared with imported alumina.
3. Conditions for successful implementation of a new pro-
ject are:
• Availability of local deposits of good quality nephe-
line ores and limestone which can be mined and
furnished to the plant at reasonable prices;
• Availability of an alumina refinery site with sufficient
access to appropriate quality fuel (gas/coal/oil), elec-
tricity and water, which may be supplied to the plant
at reasonable prices;
• A market for all the products which may be produced
(including alumina, soda ash, potash, aluminum sul-
fate, cement and belite mud) in the vicinity of the
plant.
16 A. Panov et al.

To develop nepheline technology based on available References

nepheline deposits, it is necessary to continue
research and development and evaluation studies to 1. V.T. McLemore, N. Syenite, Industrial Minerals and Rocks:
identify the right conditions to support new industrial Commodities, Markets and Users, 7th edn. (Society for Mining,
operations. Metallurgy, and Exploration, Inc. (SME), 2006), 653–670
2. World Nonbauxite Aluminum Resources Excluding Alunite, U.S.
4. Depending on local belite mud/cement market, technol-
Geological Survey Professional Paper 1076-C (1990)
ogy can be optimized by adjusting cement vs alumina
production ratio by applying beneficiation technologies.
 Characterization and Ore Dressing of Bauxite
from Brazil

Karoline K. Ferreira, Bruna L. Novo, Danielle C. Castro, Daniel Barcellos,

Luiz C. Bertolino, Antônio C.O. Guerra, Carla N. Barbato,
Adriana A.S. Felix, Marta E. Medeiros, Francisco M.S. Garrido,
and Fernanda A.N.G. Silva

Abstract
The Bauxite from North Brazil is characterized by a geological profile with different layers.
The differences among these layers are percentage of bauxite constituents (gibbsite,
kaolinite and hematite). Nowadays, only one layer is used for alumina production by Bayer
process, the commercial or crystallized bauxite. This work intended to characterize and to
ore dress crystallized bauxite (CB), amorphous crystallized (MB) and nodular bauxite
(MNB) from Pará to make them usable in the Bayer process. The ore dressing was
developed by mechanochemical activation with an alkaline reagent in different concen-
trations and conditioning time. After ore dressing, the samples were submitted to
characterization by X-ray diffraction (XRD), X-ray fluorescence (XFR) and rheological
characterization. CB and MB ore dressing products were characterized by an increase of
mass ratio Al2O3available/SiO2reactive and it was observed that the total silica of MNB, after
ore dressing, decreased around 13%. These results were a strong indication that these
bauxites could be used in the Bayer process.

Keywords
Bauxite Mechanochemical activation Ore dressing

Introduction

Bauxite rock is formed under subtropical to tropical condi-

K.K. Ferreira
Escola de Química, Universidade Federal do Rio de Janeiro,
Av. Horácio Macedo, 2030 Bloco E, Cidade Universitária, Rio de
Janeiro, RJ 21941-909, Brazil
B.L. Novo
D.C. Castro
D. Barcellos
A.C.O. Guerra

M.E. Medeiros
F.M.S. Garrido
F.A.N.G. Silva (&)
Instituto de Química, Universidade Federal do Rio de Janeiro,
Av. Athos da Silveira Ramos, 149 Bloco A, sala 630, Cidade
Universitária, Rio de Janeiro, RJ 21941-909, Brazil
e-mail: fnogueira@iq.ufrj.br
B.L. Novo
L.C. Bertolino
Centro de Tecnologia Mineral/CETEM-MCTI, Av. Pedro Calmon
900, Cidade Universitária, Rio de Janeiro, RJ 21941-908, Brazil
C.N. Barbato
Unidade Duque de Caxias, Instituto Federal de Educação, Ciência
e Tecnologia do Rio de Janeiro, Av. República do Paraguai, 120,
Sarapui, Duque de Caxias, Rio de Janeiro, 25050-100, Brazil
A.A.S. Felix
Unidade Maracanã, Instituto Federal de Educação, Ciência e
Tecnologia do Rio de Janeiro, Rua Senador Furtado 121/125,
Maracanã, Rio de Janeiro, 20270-021, Brazil
tions for prolonged weathering, which promotes the leaching
of the silica in rocks containing aluminum [1]. Bauxite is
characterized by a chemical composition of aluminum
oxy-hydroxides, such as gibbsite (c-Al(OH)3), diaspore
(c-AlO(OH)) and boehmite (a-AlO(OH)). Kaolinite
(Al4(Si4O10)(OH)8), quartz (SiO2), hematite (Fe2O3), goe-
thite (FeO(OH)), ilmenite (FeTiO3), rutile and anatase
(TiO2) are the most common impurities present in bauxite.
The proportions and types of minerals that compound this
rock vary from one deposit to another [2].
In the state of Pará (Brazil) three big companies get
together account for over 90% of Brazilian production [3]. In
this state, the most important deposits are characterized by
horizontal layers that it can be classified in six different layers
from top to bottom: saprolite, lower bauxitic, ferruginous, top
bauxitic, gravel or pisolitic and clayey capstone [4]. Nowa-
days, only ferruginous layer, known as crystallized bauxite
(CB), is commercially exploited [5]. This layer is

© The Minerals, Metals & Materials Society 2017 17

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_3
18
characterized mainly by gibbsite (high crystallinity index),
low content of kaolinite, oxy-hydroxy of iron and anatase [5].
In Brazil about 95% of bauxite reserves are metallurgical
grade, i.e., are considered as raw material for alumina pro-
duction. The rock suffers a digestion process, forming
sodium aluminate (Na2OAl2O3). Kaolinite, main mineral
related to reactive silica in the case of bauxites in north-
eastern Pará, is also dissolved by NaOH to form sodium
silicate, Na2SiO3. During the dissolution, it also reacts with
Na2OAl2O3 and precipitates as sodium silicoaluminate
(Na2O
Al2O3
2SiO2), which is disposed in the process with
other impurities. This waste is known as red mud [7]. It is
estimated that 1.0 tons of silica consumes approximately
1.2 t of NaOH. However, it is necessary attention to ratio
between Al2O3available (gibbsite) and SiO2reactive, (silicate
minerals, mainly kaolinite). This ratio is known in the lit-
erature as (A/S). The A/S value should be greater than 6.25
to consider a bauxite as economically profitable. The iron
oxide content should be between 8 and 10%, not to com-
promise the Bayer process [6].
The others horizontal layers are not commercially
exploited, due to the high content of impurities, and low
concentration of alumina. Brazilian’s alumina production, in
2015, was 10.4 Mt and the red mud production estimated
was 12.5 Mt. The red mud production could be reached
about 20 Mt, depending on the quality of bauxite [7].
It is necessary and important to develop a processing route
that reduce the content of impurities, and thereby increase the
ratio A/S of marginal bauxites (MB). This way, we could
have a better use of current Brazilian bauxite reserves, which
as well as being important from the economic point of view
also imply lower environmental impacts [8].
Within this context, the purpose of this work was a study
of characterization and ore dressing of marginal (MB) and
commercial (CB) bauxites from Pará, based in
mechanochemical activation. It could allow reactive silica
reduction of bauxites, making them more suitable for the
Bayer process and enabling a reduction in the amount of red
mud produced.
Materials and Methods
In this study, bauxite samples from two different horizons of
Pará State were characterized and ore dressed. These sam-
ples correspond to the ferruginous horizons, lower bauxitic
and pisolitic, industrially known as crystallized bauxite
(commercial), amorphous crystallized (marginal) and nodu-
lar bauxite (marginal) from geological profile of Miltônia
Plateau and Rondon, respectively.
Three barrels of 300 kg each, containing samples of
commercial bauxite (CB), marginal (MB) and nodular
bauxite (MNB) with a particle size less than 100 mm, were
K.K. Ferreira et al.
prepared according to the specifications of the Bayer process
following stages of crushing, classification, wet sieving for
removal of the fine fraction (less than 37 µm), homoge-
nization and quartering.
CB and MB Samples
The CB and MB samples were characterized by X-ray
diffraction (XRD), chemical analysis, scanning electron
microscopy (SEM), Zeta potential, determination of vis-
cosity and ore dressing through mechanochemical
activation.
The mechanochemical activation tests were carried out in
a stainless steel reactor. In reactor, it was added 1 L of
deionized water and an alkaline reagent, which was varied in
weight percentage in relation to the pulp, 0.5 to 4.5% w/w,
the reacting time, 5 and 20 min, according to design of
experiments, 22, with three replicates at the center point. The
particle size of product was carried out at wet size classifi-
cation, according to the damp method. A vibratory sieve
(684.5 rpm), equipped with some sieves with openings of 75.
37 and 20 µm, where the fraction above 37 and 20 µm was
filtered and dried in an oven at, approximately, 80 °C.
The samples, mechanically activated, were characterized
by X-ray diffraction (XRD) and chemical analysis in order
to determination of the available alumina content
(Al2O3available), and reactive silica (SiO2reactive). The deter-
mination of the Al2O3available and SiO2reactive followed the
procedure described in Silva et al. [8].
In order to compare the viscosity of bauxite samples (CB
and MB) before and (CB4520 and MB0520) after
mechanochemical activation process, pulps with 50% wt. of
solids were prepared. The rheological tests were carried out
at AR-G2 from TA Instruments. The sample was loaded into
the rheometer using a syringe. A geometry cross-hatched
parallel plates (D = 60 mm) was used. The tests to deter-
mine the viscosity of the bauxite pulps were carried out in
the following condition: experiments length of time was
100 s and shear rate of 100 s−1.
MNB Sample
The particle size of MNB sample was classified using size wet
classification according to the damp method. Thus, a vibra-
tory sieve (684.5 rpm), equipped with some sieves with
openings from 1200 to 37 µm according to series Tyler.
These samples were filtered and dried in an oven at,
approximately, 80 °C. The MNB sample and its granulo-
metric fractions were characterized by X-ray diffraction
(XRD) and X-ray fluorescence (XRF) in order to determine
the chemical content.
Characterization and Ore Dressing of Bauxite from Brazil
The MNB sample was submitted to mechanochemical
activation. The process was the same developed to CB and
MB samples, however the reaction parameters were differ-
ent. The concentration of alkaline reagent ranged from 1 to
4%wt., and the conditioning time ranged from 10 to 20 min,
following the design of experiments, 22.
Results and Discussions
CB and MB Samples
The results obtained from XRD, the CB (commercial) and
MB (marginal), Table 1, which allows to observe that both
bauxites are composed by kaolinite, gibbsite, hematite and
Al-goethite. Furthermore, the diffractogram of marginal
bauxite (MB) was characterized by kaolinite peak (5400 a.u.)
more intense when compared to the peak of same mineral
(4560 a.u.) present at CB’s diffractogram. These results
indicated that MB contains higher content of impurities when
compared to CB. This is explained at Kotschoubey et al.
where the geological section of Miltônia Plateau is detailed.
Amorphous crystallized bauxite (ACB) is located in a bottom
horizon (lower bauxitic), where minerals with finer granu-
lometry as kaolinite are concentrated.
Table 2 shows the chemical analysis (SiO2reactive and
Al2O3available) determined to CB, MB and standard BXMG-6
samples. It was observed that only CB sample obtained
A/S  6.25, parameter required in Bayer Process. The
chemical analysis corroborates with XRD results, once the
%SiO2reactive of MB is higher than %SiO2reactive of CB and
Al2O3available of MB is lower than Al2O3available of CB.
The zeta potential performed to the samples before the
ore dressing showed a sign inversion (from positive to
negative) of the total particles charges, close to pH 10.5. As
gibbsite characterized by positive zeta potential at pH 9 and
kaolinite characterized by negative zeta potential across pH
Table 1 Minerals identified in Mineral
X-ray diffractions for CB and MB
samples Kaolinite
Gibbsite
Hematite
Al-goethite
Table 2 Chemical analysis Samples
(SiO2reactive and Al2O3available)
determined to CB, MB and CB
standard BXMG-6 samples Al2O3avaiable (%) 48.8
SiO2reactive (%) 7.01
A/S 6.96
19
extension [9], it is a strong evidence that at pH 10.5 there is
repulsion between these particles. In this condition, the ore
dressing by mechanochemical activation could be carried out
with an alkaline reagent.
CB and MB Samples After Ore Dressing
by Mechanochemical Activation
The mechanochemical activation experiments were per-
formed with bauxite samples, varying the alkaline reagent
concentration of alkaline reagent in relation to the pulp, and
the stirring time, as described. The metallurgical balance
according to the results of XRF and wet sieving in relation to
the main oxides, i.e., Al2O3, Fe2O3 SiO2, present in CB and
MB are shown in Table 3.
According to the metallurgical balance (Table 3) and a
study of the influence of the established parameters (95%
confidence interval, estimated effect p = 0.05) for fractions
above 37 µm, the best results are observed for the samples
CB 4520 and MB 0520 samples, i.e., conditioned with 4.5%
w/w of alkaline reagent for 20 min and 0.5% w/w of alkaline
reagent for 20 min, respectively. It shows a decrease of
about 12% of total SiO2, and about 2% of total Fe2O3 at
coarse fractions when compared to untreated samples.
The results of X-ray diffraction after mechanochemical
activation, Fig. 1, was characterized by an increase of
kaolinite peaks intensity at fractions below 37 lm, mainly
20 lm. These results are an indication that there is
higher kaolinite concentration in the finer fractions. More-
over, it is observed the formation of mineral katoite
[Ca2,93Al1,97(Si0,64O2,56)(OH)9,44)] with peaks at 20.06 (2h)
to the experiment CB 4520.
Table 4 shows the chemical analysis (SiO2reactive and
Al2O3available) determined to CB4520, MB0520 and standard
BXMG-6 samples. It was verified that after ore dressing the
values of SiO2reactive decreased and the values of
2h (degree)
14.34
23.6
28.99
24.72
Standard BXMG-6
MB Measured value (%) Certified value (%) Uncertainty (%)
46.2 43.6 41.8 0.3
9.66 1.07 1.06 0.06
4.78 – – –
20 K.K. Ferreira et al.

Table 3 Metallurgical balance according to the results of XRF and the mass percentages of the oxides retained by wet sieving
Commercial Bauxite (CB)
CB CB055 CB0520 CB455 CB4520
Oxides retained (%)
Al2O3 SiO2 Fe2O3 Al2O3 SiO2 Fe2O3 Al2O3 SiO2 Fe2O3 Al2O3 SiO2 Fe2O3 Al2O3 SiO2 Fe2O3
+37 µm 83.6 55.1 72.9 81.1 48.8 71.2 77.9 47.4 61.7 79.3 44.3 71.7 79.5 43.9 70.5
Marginal Bauxite (MB)
MB MB055 MB0520 MB455 MB4520
Oxides retained (%)
Al2O3 SiO2 Fe2O3 Al2O3 SiO2 Fe2O3 Al2O3 SiO2 Fe2O3 Al2O3 SiO2 Fe2O3 Al2O3 SiO2 Fe2O3
+37 µm 81.4 54.3 66.6 79.9 49.2 65.7 76.03 42.1 64.2 81.2 49.6 69.2 76.5 44 63.4

MB 0520 +37 μm

Co Kα
Intensity (u.a)
MB 0520 +20 μm

MB 0520 -20 μm

10 20 30 40 50 60 70 80
2θ (degree)

Kaolinite Gibbsite Hematite

Fig. 1 X-ray diffractions patterns for CB and MB samples after the ore dressing

Table 4 Chemical analysis (SiO2reactive and Al2O3available) determined to CB4520, MB0520 and standard BXMG-6 samples
Samples Standard BXMG-6
CB—4520 MB—0520 Measured value (wt%) Certified value (wt%) Uncertainty (%)
Al2O3avaiable (wt%) 55.2 52.9 43.6 41.8 0.3
SiO2reactive (wt%) 3.8 3.4 1.07 1.06 0.06
A/S 14.5 15.6 – – –

Al2O3available increased for both samples (CB4520 and
MB0520). These results were corroborated to diffractions for
CB and MB after the ore dressing. After ore dressing by
mechanochemical activation, both bauxites (CB and MB)
obey mass ratio A/S  6.25 required at the industrial
process.
Figure 2 shows the viscosity of CB and MB pulps with
50% (wt) of solids (CB and MB) before and (CB4520 and
MB 0520) after mechanochemical process. It was verified
that CB and MB pulps were characterized by lower viscosity
than CB4520 and MB0520 pulps. These results indicated the
strong influence of SiO2reactive (silicate minerals, mainly
Characterization and Ore Dressing of Bauxite from Brazil 21

Fig. 2 a Viscosity of CB and CB4520 bauxite pulps. b Viscosity of MB and MB0520 bauxite pulps

kaolinite) on viscosity of bauxite pulps. Kaolinite is char-

acterized by small particles (lower than 37 µm). However,
the clusters are greater in pulps with high SiO2reactive, since
kaolinite have a bigger surface area, favoring van der Walls
interactions among them. The clusters hold water inside (that
is not available for the flow) causing the suspension to
behave as if the solids’ volumetric fraction were bigger,
which increases its viscosity [10].

Nodular Bauxite (MNB)

The diffractogram of MNB can be seen in Fig. 3. It was

observed that gibbsite is the main bauxite mineral and it was
associated with mineral kaolinite, goethite and hematite. The
results obtained by XRF, Table 5, for sample MNB show
that the contents of mass percentage related to Al2O3, SiO2,
Fe2O3 and TiO2 are respectively 49.1; 4.1; 22.6 and 1.6%.
This result indicates the relationship Al2O3total/SiO2total is
compatible with the expected A/S relationship for applica-
tion of the sample MNB in the Bayer Process. However, the
characterization by means of wet chemical analysis for the
determination of available alumina and reactive silica is
necessary to assess the optimal ratio in the process. On the
other hand, regarding the iron content, the amount is higher
than expected, i.e., 8.0%, and in this case the sample can not
be used for the production of alumina. The analysis of the
results of Table 5 show an increase in total SiO2 concen-
tration between fractions 37 and 212 µm characteristic of
kaolinite and Fe2O3 in finer fractions, between 45 and
65 µm indicating a possible interaction between these
Fig. 3 X-ray diffractions patterns for NMB sample
minerals. The results also showed that the concentration of
titanium in the sample remains constant through the different
granulometric fractions.
According to the results shown in Table 6, it can be seen
that the mechanochemical activation was effective according
to the percentage of material retained in the fraction above
37 µm, and therefore, the best result was verified to the con-
ditions where it was used 4%wt. of alkaline reagent and stir-
ring for 10 min. For this experiment, a decrease was observed
of approximately 13% percentage retained, when compared
with the test without reagent. However, these values relate
only to the mass percentage of the sample, requiring a quan-
titative analysis of the levels of oxides retained in each
fraction.
22 K.K. Ferreira et al.

Table 5 Chemical analysis of Opening (µm) Al2O3 SiO2 Fe2O3 TiO2

MNB sample determined by XRF
(wt%)
MNB—total 49.1 4.1 22.6 1.6
1200 54.5 4.2 12.5 1.3
850 52.7 4.8 14.2 1.2
600 53.7 4.6 13.5 1.2
425 52.3 5.0 15.0 1.2
300 51.8 5.7 15.2 1.2
212 49.7 7.3 16.3 1.3
150 48.0 7.6 18.1 1.5
104 45.7 7.2 20.0 1.8
74 48.4 8.2 17.7 1.4
53 49.1 5.8 18.5 1.7
45 48.1 5.6 19.5 1.7
37 45.6 6.0 22.1 1.8
−37 39.5 5.4 31.3 1.7

Table 6 Metallurgical balance MNB Granulometry (µm) Retained %

before and after
mechanochemical activation to 37 90.54
MNB sample −37 9.46
Mechanochemical activation
4% 10 min 37 77.61
−37 22.39
1% 10 min 37 83.75
−37 16.25
1% 20 min 37 80.63
−37 19.37

Conclusions References

The ore dressing used by mechanochemical activation of
commercial, marginal and nodular bauxites was efficient to
increase the value of Al2O3Available and to decrease the value of
SiO2Reactive of these samples. Consequently, it was happened
increased the ratio A/S, important parameter of Bayer Process,
for CB, MB and MNB. These results are very important to the
industry and to the environment, once bauxite reserve increase
with the ore dressing of MB and MNB.
The chemical analysis and XRF to determine the content
of Al2O3available and SiO2reactive and the levels of oxides,
respectively, are being developed to NMB in order to
quantify the efficiency of mechanochemical activation for
this bauxite.
Acknowledgements The authors would like to thanks João Alves
Sampaio (in memorian) for their technical support; to IQ/UFRJ and
COAM/CETEM for analysis and lab infrastructure; CNPq for their
financial support (Process: Universal—480668/2013-2).
1. J.D. Dana, C.S. Hurlbut, C.S. Manual de Mineralogia, 1ª edn.
(Brasil, Livros Técnicos e Científicos Editora S.A., Rio de Janeiro,
1978), pp. 341
2. F.A.N.G. Silva, C.N. Barbato, R.D. Santos, D.S.G. Almeida, J.A.
Sampaio, M.E. Medeiros, F.M.S. Garrido, Mechanochemical
activation of bauxite. Light Met. 27–32 (2012)
3. A.L. Santana, Alumínio. Balanço Mineral Brasileiro, 2014.
Departamento nacional de produção mineral (DNPM). https://
sistemas.dnpm.gov.br/publicacao/mostra_imagem.asp?
IDBancoArquivoArquivo=8964. Access May, 2016
4. B. Kotschoubey, J.M. Calaf, A.C.C. Lobato, A.S. Leite, C.H.D.
Azevedo, Caracterização e Gênese dos Depósitos de bauxita da
Província Bauxitífera de Paragominas, Noroeste da bacia do
Grajaú, Nordeste do Pará/Oeste do Maranhão. In: Marini, O. J.,
Queiroz, E. T., Ramos, B. W. (Eds) Caracterização de Depósitos
Minerais em Distritos Mineiros da Amazônia. (Cap. 11, Brasília,
2005), pp. 691–782
5. K.-Y. Ling, X.-Q. Zhu, H.-S. Tang, Z.-G. Wang, H.-W. Yan, T.
Han, W.-Y. Chen, Mineralogical characteristics of the karstic
bauxite deposits in the Xiuwen ore belt, Central Guizhou Province,
Southwest China. Ore GeologyReviews (vol. 565, 2015), pp. 84–96
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6. P. Smith, The processing of high silica bauxites—review of
existing and potential processes. Hydrometallurgy 98, 162–176
(2009)
7. Industrial Minerals, Alumina/Bauxite. Disponível em: http://www.
indmin.com, Acesso em: agosto de 2016
8. F.A.N.G Silva, M.E. Medeiros, J.A. Sampaio, R.D. Santos, M.C.
Carneiro, L.S. Costa, F.M.S. Garrido, Technological characteriza-
tion of Bauxite from Pará-Brazil. Light Met. 139–144 (2009)
23
9. T. Hou et al., Interaction between electric double layers of
kaolinite and Fe/Al oxides in suspensions. Colloids and Surfaces
A: Physicochemical and Engineering Aspects (vol. 297, 2007),
pp. 91–94
10. C.N. Barbato, S.C.A. França, M.N. Souza, Study on rheological
behavior of crystallized and crystallized amorphous bauxites. Light
Met. 87–91 (2010)
 Process Optimization for Diaspore Digestion
Equilibrium Using Response Surface
Methodology

Zhengyong Zhang

Abstract
The high-temperature digestion process is well applied in china for alumina production
from diaspore, and digestion is the critical process for alumina plant. The present study
attempts to extract alumina from diaspore using a synthetic caustic liquor. The effect of
important parameters such as digestion temperature and caustic concentration were
investigated and the process conditions were optimized using surface response method-
ology (RSM) based on central composite design (CCD). The different influence of
digestion parameters on equilibrium molar ratio was compared, and the optimum condition
for extraction of alumina from diaspore was identified. The model equation developed
using RSM software shows good agreement with the experimental data, with a correlation
coefficient (R2)
0.96. The characterization of sample before and after digestion was
determined by X-ray diffraction (XRD).

  
Keywords
Alumina extraction Equilibrium molar ratio Response surface methodology
Optimization

Introduction performs many useful functions. It can improve the digestion

The most important steps involved in Bayer process are
digestion and precipitation. The parameters for digestion
depend on the nature of bauxite. For gibbsite, low temper-
ature (140–150 °C) is required, when the digestion can be
carried out at high-temperature (240–250 °C) for boehmitic
(Boehmite concentration exceeding 8%) [1–3]. Several
published articles have cited the kinetics and parameters
applications of digestion process for gibbsite and boehmite
[4–6]. However, most of Chinese bauxite resources are
diasporic bauxite, which need high digestion temperature
and caustic concentration during alumina production by the
Bayer process. As a common additive, lime is widely used in
the alumina production by the Bayer process, where it
Z. Zhang (&)
Shenyang Aluminium and Magnesium Engineering and Research
Institute Co. Ltd, Shenyang, 110001, China
e-mail: yongmcc@163.com
property of diasporic to increase the extraction of alumina.
The equilibrium molar ratio (MR) is a very important
parameter for alumina production. some factors such as
temperature, caustic concentration and lime addition can
affect the digestion MR. The traditional experiment methods
can only study the single factor influence, but not the
synergy effect.
RSM is one of the relevant multivariate techniques which
can deal with multivariant experimental design strategy,
statistical modeling and process optimization [7–9]. It is
used to examine the relationship between one or more
response variables and a set of quantitative experimental
variables or factors. This method is often employed after the
vital controllable factors are identified and to find the factor
settings that optimize the response. Hence the present work
intends to assess the effects of variables such as digestion
temperature and caustic concentration using a central com-
posite design (CCD). The characteristics of sample before

© The Minerals, Metals & Materials Society 2017 25

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_4
26
and after digestion are assessed using X-ray diffraction
(XRD).
Materials and Methods
Materials and Apparatus
The diaspore was obtained from a Chinese alumina refinery
and XRD using Cu Ka radiation) analysis was performed to
assess the changes in the diaspore and residue samples.
Experimental Methods
The digestion tests were carried out in oil digester with small
autoclave, the caustic liquor was synthetized by chemical
reagent in the laboratory. The screening tests were done to
obtain the equilibrium molar ratio (MR) before the opti-
mization tests. Then the bauxite was weight and mixed with
caustic liquor to meet the target MR. A total of 13 experi-
ments were conducted with the sample in a batch mode
using a glass reactor of volume 150 ml. the exit liquor was
titrated to measure Nk, Nt and Alumina.
Experimental Design
RSM helps to optimize the process, influenced by number of
operating parameters with a minimum number of experi-
ments as well as to analyze the interaction between the
parameters. Digestion temperature (v1 ), caustic concentra-
tion (v2 ) were chosen as the independent variables with their
levels and ranges shown in Table 1.
It shows the actual values of the independent variables at
which the experiments were conducted to estimate the
equilibrium MR (Y). The chosen independent variables used
in process optimization were coded according to Eq. (1).
vi  v0
vi ¼ ð1Þ
Dv
where vi was the dimensionless coded value of the i th
independent variable, v0 was the value of vi at the center
point and Dv was the step change value. The equilibrium
MR was the response variable of the experimental conditions
in the design of experiments. The digestion temperature was
Table 1 Independent variables Variables
and their levels used for CCD
Digestion temperature (°C)
Caustic concentration (gNa2O/l)
Z. Zhang
varied from 220 to 280 °C, the caustic concentration was
varied from 140gNa2O/l to 240 gNa2O/l. A total of 13
experiments consisting of 4 factorial points, 4 axial points
and 5 replicates at the central points were performed [10].
Experimental results obtained from the CCD model were
described in the form as given in Eq. (2).
X
n X
n X
Y ¼ b0 þ bi vi þ bii vi2 þ bij vi vj ð2Þ
i¼1 i¼1 i\j
where b0 was the value for the fixed response at the central
point of the experiment; and bi, bj and bij were the linear,
quadratic and cross product coefficients, respectively. The
analyses of variance (ANOVA) and response surfaces were
performed using the design expert software (version 8.0)
from Stat-Ease Inc, USA. The optimized equilibrium MR for
diaspore were estimated using the software’s numerical and
graphical optimization tools.
Results and Discussion
Response Analysis and Interpretation
The results of experiments were shown in Table 2 and the
equilibrium MR was found to range from 1.26 to 1.74 in
response to the variation in the experimental conditions.
According to the sequential model sum of squares were
selected based on the highest order polynomials, where the
additional terms were significant.
The ANOVA of quadratic model is presented in Table 3
which proves the validity of the model.
The digestion temperature has the greatest effect on equi-
librium MR with the highest F value of 773.7 whereas caustic
concentration was found to be less significant. The model
F-value of 192.10 implies the significance of the model [11].
For the fixed model, adequate precision can be ensured with a
signal to noise ratio greater than 4. An adequate precision
ratio of 47 indicates the ability of model to precisely navigate
through the design space. While values of Prob > F less than
0.05 indicate that the model terms were significant. In this
case, v1 , v2 and the interaction terms v21 , v22 , v1 v2 were sig-
nificant model terms were all insignificant. In order to
enhance the effect of significant parameters. The final equa-
tion in terms of coded factors was shown in Eq. (3) as,
Symbol Range and levels
−1 0 +1
v1 220 250 280
v2 140 190 240
Process Optimization for Diaspore Digestion Equilibrium … 27

Table 2 Experimental design Run Digestion variables Equilibrium MR

matrix and results
Digestion temperature (°C) Caustic concentration (gNa2O/l)
1 250 240 1.38
2 250 190 1.47
3 250 140 1.48
4 280 190 1.31
5 250 190 1.47
6 280 240 1.26
7 220 140 1.74
8 250 190 1.47
9 220 240 1.49
10 220 190 1.67
11 250 190 1.46
12 250 190 1.46
13 280 140 1.32

Table 3 Analysis of variance Source Sum of squares Degree of freedom Mean square F-value Prob > F
(ANOVA) for response surface
quadratic model Model 0.21 5 0.042 192.10 <0.0001
v1 0.17 1 0.17 773.7 <0.0001
v2 0.028 1 0.028 127.5 <0.0001
v1v2 9.025E-003 1 9.025E-003 41.07 0.0004
v21 1.496E-003 1 1.496E-003 6.81 0.0349
v22 3.725E-003 1 3.725E-003 16.95 0.0045
Residual 1.538E-003 7 2.197E-004 – –
R2 = 0.96; R2adj ¼ 0:95; Adequate precision = 47 (>4)

Y ¼ 1:47  0:17v1  0:068v2 þ 0:047v1 v2 þ 0:023v21
 0:037v22 ð3Þ
The R2 value for Eq. (4) was found to be 0.96 close to
unity, indicating the good agreement between the experi-
mental and the predicted equilibrium MR, which don’t show
any significant non-linear pattern (S-shaped curve) indicat-
ing non-normality in the error term. Figure 1 shows an
approximate linearity confirming normality of the data.
Process Optimization
The experimental and predicted equilibrium MR is shown in
Fig. 2. Figure show a close proximity of the model predic-
tion with the experimental data signifying the validity of the
regression model. Figure 3 shows three-dimensional plot of
the digestion temperature and caustic concentration on
equilibrium MR. It shows that the equilibrium MR decreases
significantly with increase in the digestion temperature. An
increase digestion temperature from 220 to 280 °C decreases
the equilibrium MR remarkably from 1.74 to 1.26.
The main chemical reaction of extraction alumina from
diaspore can be defined as follows:
Al2 O3 :H2 O þ 2NaOH þ aq ! 2NaAl(OH)4 þ aq ð4Þ
In the above reaction as the digestion temperature
increases, the drive force becomes strong to dissolve more
diaspore. An increase in the concentration of caustic on one
hand would increase the rate of reaction and on the other
hand reduce the mass transfer resistance aiding diffusion of
caustic to the surface of diaspore, facilitating higher %
extraction.
28 Z. Zhang

Fig. 1 Normal % probability

versus internally studentized
residuals

1.80
yield. It is economical to choose high temperature and a
lower caustic concentration liquor during to the energy
1.70 saving in evaporation process.
In order to verify the accuracy of the model, a compar-
Predicted MR

1.60
ative experiment was carried out, the results of experiments
1.50 were shown in Table 4 and the predicted equilibrium MR
23
was 1.334 while the experimental data was 1.345. The
1.40
characterization of sample before and after digestion was
1.30
determined by X-ray diffraction as shown in Fig. 4 and
Fig. 5. The characteristic diffraction peaks of diaspore were
1.20 disappearing and new hematite and desilication product
1.20 1.30 1.40 1.50 1.60 1.70 1.80
(Na-DSP) showing up after digestion.

Experimental MR
Conclusions
Fig. 2 Comparison of model prediction with the experimental data

The present study was aimed to explore the effects of

Figure 3 shows a decrease in equilibrium MR with
increase in the digestion temperature. However, the effect of
caustic concentration on the equilibrium MR was varied,
with lower digestion temperature, shows a significant effect
while higher digestion temperature shows only a marginal
effect. As the temperature increases to 280 °C, the effect of
caustic concentration becomes very small. As we know, the
lower MR of pregnant liquor can get higher precipitation
digestion temperature and caustic concentration on the
equilibrium MR of diaspore in China and to optimize the
process conditions using RSM. The proposed quadratic
model agrees well with the experimental data, with corre-
lation coefficients (R2) of 0.96. The digestion temperature
was found to have significant effect on the equilibrium MR
while other parameters showed little effect. The predicted
model was verified by experimental test.
Process Optimization for Diaspore Digestion Equilibrium … 29

Fig. 3 Effect of temperature and

caustic concentration on
equilibrium MR 1.8
1.7
1.6

Equilibrium MR
1.5
1.4
1.3
1.2

140.00
165.00
232226220
190.00 238
250244
Caustic concentration 215.00 256
268262
240.00 280274 Temperature

Table 4 Predicted versus Digestion temperature (°C) Caustic concentration (gNa2O/l) Equilibrum MR
experimental results
Predicted Experimental
260 235 1.334 1.345

6500
7000 1 1 AlO(OH) 1-Fe2O3
2 Fe2O3
3
6000 2 2 2- Na8Al6Si6O24(OH)2(H2O)2
3 FeO(OH) 1 3-1.08Na2O·Al2O3·1.68SiO2·1.8H2O
6000 4 Al2O3·2SiO2·2H2O
5500 2
5 TiO2
5000 1
5000 3
Intensity

1 2 1
Intensity

4500 2
4000 11
1
4000 2 3
3000 1 1 22
3 3 1
4 5 2 2 1 1 1 2 1
13 1
4 2 1 2 1 3500 1
2000
3 2 3 2 1
3000
3
20 40 60 80
2θ(°) 2500
20 40 2θ(°) 60 80
Fig. 4 X diffraction pattern of diaspore
Fig. 5 X diffraction pattern after digestion

References
1. N.K. Kshairlya, Bauxite digestion studies for optimization of
operating parameters, Int. Conf. Non-ferrous Met. 1–7 (2006)
2. G.I.D. Roach, The influence of mineralogy on the dissolution
kinetics of gibbsite. Light Met. 183–196 (1985)
3. N.S. Raghavan, G.D. Fulford, Mathematical modeling of the
kinetics of gibbsite extraction and kaolinite dissolution/desilication
in the Bayer process. Light Met. 29–36 (1998)
4. L.Ü. Guo-zhi, Effects of intense magnetic field on digestion and
settling performances of bauxite. J. Cent. S Univ. 21, 2168–2175
(2014)
5. W.E. Wahnsiedler, The kinetics of bauxite digestion in the Bayer
process. Light Met. 145–179 (1985)
6. M.A. Bezerra et al., Response surface methodology (RSM) as a
tool for optimization in analytical chemistry. Talanta 76, 965–977
(2008)
7. M.S. Secula et al., Response surface optimization of the photo-
catalytic decolorization of a simulated dyestuff effluent. Chem.
Eng. J. 141, 18–26 (2008)
8. F. Gonen, Z. Aksu, Use of response surface methodology
(RSM) in the evaluation of growth and copper (II) bioaccumulation
properties of Candida utilis in molasses medium. J. Hazard. Mater.
154, 731–738 (2008)
30 Z. Zhang

9. J.F. Fu, Y.Q. Zhao, Q.L. Wu, Optimising photoelectrocatalytic 11. B.K. Körbahti, M.A. Rauf, Determination of optimum operating
oxidation of fulvic acid using response surface methodology. conditions of carmine decoloration by UV/H2O2 using response
J. Hazard. Mater. 144, 499–505 (2007) surface methodology. J. Hazard. Mater. 161, 281–286 (2009)
10. I.A.W. Tan, A.L. Ahmad, B.H. Hameed, Optimization of prepa-
ration conditions for activated carbons from coconut husk using
response surface methodology. Chem. Eng. J. 137, 462–470
(2008)
 Thermodynamic Analysis and Formation Law
of Q Phase of Calcium Aluminate Clinker

Long Lu, Dongdong Ma, Di Zhang, Tianxu Zhang, and Bo Wang

Abstract
The research on lime sintering process to treat low grade bauxite becomes the hotspot,
because it can realize dry sintering and decrease the energy consumption. But during the
sintering process the existence of MgO, which is trace element and contained in lime, will
lead to the phase formation from 12CaO
7Al2O3 (C12A7) to 20CaO
13Al2O3
3MgO
3SiO2
(Q phase) whose alumina leaching property is worse than the former. The alumina leaching
ratio decreases obviously. The double parameter model is used to calculate the
thermodynamic data of the quaternary compound, and the formation law of
alumina-containing phases is obtained by Factsage software. The results indicate that
low temperature and high lime addition are benefit to the formation of C12A7. The Q phase
is found in clinker when sintering temperature is 1325 °C. The content of Q phase increases
obviously when the temperature is higher than 1400 °C.

Keywords
Thermodynamic analysis Q phase Alumina leaching Lime-sintering process

Introduction remarkably. MgO is a major impurity of the calcium alu-

Calcium aluminates play an important role in the alumina
industry as alumina-containing mineral in the sintered clin-
ker from the low-grade alumina-containing resources, such
as high-iron bauxite, red mud and high-alumina fly ash. The
minerals in the sintered clinker by the lime sinter process
consist of 12CaO
7Al2O3 (C12A7) and c-Ca2SiO4 (c-C2S),
and C12A7 is of interest because of its good alumina leaching
property in sodium carbonate solution [1–4]. The sodium
carbonate solution circulation only exists in the alumina
leaching process. The lime sinter process has the advantages
of dry sintering and clinker self-pulverization as compared
with the soda-lime sinter process. It also can reduce the
sodium carbonate and sintering energy consumption
L. Lu
D. Ma
D. Zhang
B. Wang (&)
School of Materials Science and Engineering, Hebei University
of Science and Technology, Shijiazhuang, 050018, China
e-mail: wangbo1996@gmail.com
T. Zhang
Chengde Petroleum College, Chengde, 067000, China
minate clinker, which is about 0.5–2.0% and from lime
dosage. MgO can reacts with CaO, SiO2 and Al2O3 to form
20CaO
13Al2O3
3MgO
3SiO2 (Q phase) in the sintering
process [5]. The Q phase dissolves difficulty in the sodium
carbonate solution, which then deteriorates the alumina
leaching property of the sintered clinker.
Eremin [6] found the alumina leaching property of cal-
cium aluminate clinker decreases with the increase of MgO
content, which decreases sharply especially in low lime
dosage. There is no effect when the molar ratio of CaO to
Al2O3 is higher than 1.8, and the MgO containing mineral is
similar to C6A4MS.
Wang Bo [7, 8] found Mg2+ could diffuse into the lattice
of C12A7 first, and the maximum content is lower than 1.0%.
C12A7 transforms into 20CaO
13Al2O3
3MgO
3SiO2 grad-
ually with the increase of MgO content. The major
alumina-containing mineral is 20CaO
13Al2O3
3MgO

3SiO2 when the MgO content is 3.0%.
The formation of 20CaO
13Al2O3
3MgO
3SiO2 will
deteriorate the alumina leaching property of calcium

© The Minerals, Metals & Materials Society 2017 31

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_5
32 L. Lu et al.

aluminate clinker obviously. The aim of this paper is to Importing the Tables 1 and 2 into Formulas (1) and (2),
study the 20CaO
13Al2O3
3MgO
3SiO2 formation mecha- the results are as follow:
nism in the CaO–Al2O3–SiO2–MgO thermodynamics data
aðb þ c þ dÞ 0 bða þ c þ dÞ 0
with the Factsage software and the transition process from Dr H0 ¼ aA þ bB þ cC þ dD þ A þ B
aþbþcþd aþbþcþd
C12A7 to 20CaO
13Al2O3
3MgO
3SiO2. It will control the cða þ b þ dÞ 0 dða þ b þ cÞ 0
formation content of 20CaO
13Al2O3
3MgO
3SiO2, and þ C þ D
aþbþcþd aþbþcþd
then improve the alumina leaching property of calcium ¼ 20ð0:74Þ þ 13ð37:44Þ þ 3ð56:44Þ þ 3ð31:59Þ
aluminate clinker. þ ½ð111:35Þ20  19 þ 78:8613  26 þ ð45:81Þ3  36
þ ð67:22Þ3  36=39
¼ 1141:470 kJ mol1
Calculation of Thermodynamic Data
Df H0m ¼ aDf H0Mm Ox þ bDf H0Nn Oy þ cDf H0Ll Oz þ dDf H0Pp Ok þ Dr H0
In the CaO–Al2O3–SiO2–MgO quaternary system, the ther-
modynamic data of most of aluminate and silicate can be ¼ 20  ð634:294Þ þ 13  ð1675:274Þ
retrieved except 20CaO
13Al2O3
3MgO
3SiO2. þ 3  ð910:857Þ þ 3  ð601:241Þ þ ð1141:47Þ
Guo Peimin presents that the standard Gibbs free energy ¼ 40142:206 kJ mol1
and Enthalpy of composite oxide could be calculated by the
two-parameter fracture model method, and the calculation The standard enthalpy calculation of Q phase is
error is less than 2% [9, 10]. The Gibbs free energy and −40142.206 kJ mol−1 at 298 K with two-parameter fracture
Enthalpy of Q phase was calculated in the two-parameter model method.
fracture model method.

Calculation of Gibbs Free Energy

Calculation of Enthalpy
The computational formula of molar Entropy with quater-
If a Quaternary Compounds aMmOx
bNnOy
cLlOz
dPpOk nary Compounds aMmOx
bNnOy
cLlOz
dPpOk was shown
could generate, the computational formula of molar in Formula (3):
Enthalpy was shown in Formula (1). aðb þ c þ dÞ 0 bða þ c þ dÞ 0
Dr S0 ¼ aA þ bB þ cC þ dD þ A þ B
aþbþcþd aþbþcþd
Dr H0 ¼ aA þ bB þ cC þ dD cða þ b þ dÞ 0 dða þ b þ cÞ 0
aðb þ c þ dÞ 0 bða þ c þ dÞ 0 þ C þ D þD
aþbþcþd aþbþcþd
þ A þ B ð1Þ
aþbþcþd aþbþcþd ð3Þ
cða þ b þ dÞ 0 dða þ b þ cÞ 0
þ C þ D And the computational formula of standard molar
aþbþcþd aþbþcþd
Entropy with quaternary Compounds aMmOx
bNnOy
cL-
lOz
dPpOk was shown in Formula (4):
And the computational formula of standard molar
Enthalpy was shown in Formula (2):
Df S0m ¼ aDf S0Mm Ox þ bDf S0Nn Oy þ cDf S0Ll Oz þ dDf S0Pp Ok þ Dr S0
Df H0m ¼ aDf H0Mm Ox þ bDf H0Nn Oy þ cDf H0Ll Oz
ð2Þ ð4Þ
þ dDf H0Pp Ok þ Dr H0
where, A, A′, B, B′, C, C′ and D′ are the parameters of MmOx,
In the Formula (1), A, A′, B, B′, C, C′, D and D′ are the NnOy, LlOz and PpOk. D is −8.932 J/(mol K). Oxides char-
parameters of MmOx, NnOy, LlOz and PpOk. Oxides charac- acteristic parameters of 20CaO
13Al2O3
3MgO
3SiO2 is
teristic parameters of 20CaO
13Al2O3
3MgO
3SiO2 is shown shown in Table 3. The Entropy of oxides is shown in
in Table 1. The Enthalpy of oxides is shown in Table 2. Table 4.

Table 1 A, A′, B, B′, C, C′, Oxide A, B, C and D/(kJ mol−1) A′, B′, C′ and D′/(kJ mol−1)
D and D′ of oxides at 298 K
CaO −0.74 −111.35
Al2O3 −37.44 78.86
MgO 56.44 −45.81
SiO2 −31.59 −67.22
Thermodynamic Analysis and Formation Law of Q Phase … 33

Table 2 Enthalpy calculation of oxides at 298 K Table 5 Thermodynamics calculation of Gibbs free energy, enthalpy
and entropy
Oxide CaO Al2O3 MgO SiO2
Enthalpy/ −634.294 −1675.274 −601.241 −910.857 DH h298 ðkJ mol1 Þ DGh298 ðkJ mol1 Þ DSh298 ðJ mol1 K1 Þ
(kJ mol−1) −40142.206 −41329.240 3983.335

-34000
Table 3 A, A′, B, B′, C, C′, D and D′ of oxides at 298 K
Oxides A, B, C and D/ A′, B′, C′ and D′/ -36000
(J mol−1 K−1) (J mol−1 K−1)
CaO 40.282 113.967 -38000

Al2O3 52.414 31.285

-1
MgO 27.861 8.106 -40000 ΔH Tθ
ΔGTθ
SiO2 36.089 11.159
-42000

-44000
Table 4 Enthalpy calculation of oxides at 298 K
-46000
Oxides CaO Al2O3 MgO SiO2 1100 1200 1300 1400 1500
−1 −1
Enthalpy/(J mol K ) 39.75 50.99 26.94 104.71 Temperature/K

Fig. 1 Gibbs free energy and Enthalpy calculation of Q phase with

different sintering temperature
Importing the Tables 3 and 4 into Formulas (3) and (4),
the results are as follow:

Dr S0 ¼ aA þ bB þ cC þ dD
aðb þ c þ dÞ 0 bða þ c þ dÞ 0
þ A þ B
aþbþcþd aþbþcþd
cða þ b þ dÞ 0 dða þ b þ cÞ 0
þ C þ D þD
aþbþcþd aþbþcþd
¼ 20  ð40:282Þ þ 13  ð52:414Þ þ 3  ð27:861Þ
þ 3  ð36:089Þ þ ½ð13:967Þ  20  19 þ 31:285  13
 26 þ 8:106  3  36 þ ð11:159Þ  3  36=39
þ ð8:932Þ ¼ 2130:515 J mol1 K1

Df S0m ¼ aDf S0Mm Ox þ bDf S0Nn Oy þ cDf S0Ll Oz þ dDf S0Pp Ok þ Dr S0

¼ 20ð39:75Þ þ 13ð50:99Þ þ 3ð26:94Þ þ 3ð104:71Þ
þ ð2130:51462Þ
¼ 3983:335 J mol1 K1 Fig. 2 Entropy calculation of Q phase with different sintering
temperature
Therefore,

Df G0m ¼ Df H0m  TDf S0m

¼ 40142:206  298  3983:33462=1000 Thermodynamics Calculation
¼ 41329:240 kJ mol 1 of the Formation Law of Q Phase and C12A7

The molar Gibbs free energy, molar Enthalpy and molar
Entropy calculations of Q phase at 298 K and 101 kPa were
shown in Table 5.
The molar Gibbs free energy and Enthalpy of Q phase at
high sintering temperature were shown in Fig. 1, and the
molar Entropy of Q phase was shown in Fig. 2.
Importing the thermodynamics data of Q phase into the
Compound module of Factsage software, and the reaction
process of Q phase formation could be calculated based on
the minimization principle in the Gibbs free energy. The
mass balance was calculated with different sintering tem-
perature in the CaO–Al2O3–SiO2–MgO quaternary system
34 L. Lu et al.

50
Q phase 50
45 C12A7
C2S
40 40
Content /%

Content /%
35 30 Q phase
C12A7
30
C2S
20
25

10
20

15 0
1300 1350 1400 1450 1500 1300 1350 1400 1450 1500
Temperature /°C Temperature /°C

Fig. 3 Minerals variation in quaternary system when the A/S is 1.3 Fig. 5 Minerals variation in quaternary system when the A/S is 3.0

in favor of Q formation, and then deteriorates the alumina

45
leaching property of calcium aluminate clinker. The content
40
of C12A7 increases gradually and then decreases. The con-
tent of C12A7 has the highest percentage with different mass
35 ratio of Al2O3 to SiO2 when the sintering temperature is
Content /%

1350 °C. The raw materials cannot react completely when

30 Q phase the sintering temperature is lower than 1350 °C, and parts of
C12A7
alumina cannot form C12A7. C12A7 could transform into Q
25
C2S
phase when the sintering temperature is higher than 1350 °C.
Therefore, controlling sintering temperature at 1350 °C is in
20
favor of the stability of C12A7. The content of C2S decreases
15 gradually with the increase of sintering temperature, which
then deteriorates the pulverization property of calcium alu-
1300 1350 1400 1450 1500
minate clinker.
Temperature /°C Controlling the sintering temperature could prevent Q
Fig. 4 Minerals variation in quaternary system when the A/S is 2.0
phase formation, but the content of Q phase is all higher than
20%. It also deteriorates the alumina leaching property of
calcium aluminate clinker obviously. Therefore, the C/A of
when the MgO content is 4.0%, the molar ratio of CaO to the clinker is increased to 1.71, and its mass balance is
Al2O3 is 1.4 and the mass ratio of Al2O3 to SiO2 is 1.3–3.0, calculated, as shown in Table 6.
as shown in Figs. 3, 4 and 5. Table 6 shows, the content of Q phase is 0.46–0.71%, the
Figures 3, 4 and 5 show the content of Q phase all content of C12A7 is 44.44–44.79%, and the content of C2S is
increases as the sintering temperature increases when the 3.88–3.94% when the sintering temperature changes from
molar ratio of CaO to Al2O3 is 1.4, the mass ratio of Al2O3 1300 to 1450 °C. Increasing the molar ratio of CaO to Al2O3
to SiO2 is 1.3–3.0 and the content of MgO is 4.0%. Based on and decreasing the sintering temperature could prevent the
the Enthalpy calculation of Q phase formation, it is an formation of Q phase, which then improve the alumina
endothermic process. So increasing sintering temperature is leaching and pulverization property of calcium aluminate.

Table 6 Mineral percentage Temperature/°C Q phase C12A7 C2S MgO

with C/A in1.71, A/S in 1.3 and
MgO in 4% (%) 1300 0.46 44.79 50.81 3.94
1350 0.55 44.76 50.76 3.93
1400 0.71 44.69 50.68 3.92
1450 1.28 44.44 50.40 3.88
1500 49.63 26.62 23.75 0
Thermodynamic Analysis and Formation Law of Q Phase …
The content of Q phase increases sharply and the content of
C12A7 and C2S decreases when the sintering temperature is
higher than 1500 °C. So controlling the sintering tempera-
ture lower than 1450 °C could prevent the formation of Q
phase, which then promotes the alumina leaching and pul-
verization property of calcium aluminate clinker.
Conclusions
The thermodynamics data of Q phase under different sin-
tering temperature could be calculated in the two-parameter
fracture model method. The mass balance was calculated in
the CaO–Al2O3–SiO2–MgO quaternary system with the
Equilib module of the Factsage software. Controlling the
sintering temperature at 1350 °C could promote the forma-
tion of C12A7. Increasing the sintering temperature higher
than 1350 °C will promote C12A7 transform into Q phase,
and then deteriorate the alumina leaching property of cal-
cium aluminate clinker. Increasing the molar ratio of CaO to
Al2O3 could prevent the formation of Q phase, and MgO
exist in the form of periclase of calcium aluminate clinker.
Changing the mass ratio of Al2O3 to SiO2 has no effect on
inhibiting the formation of Q phase.
Acknowledgements The authors greatly acknowledge the financial
support of the Science and Technology Foundation of higher education
institution of Hebei Province (No: BJ2016023, QN2015002), and the
Nature Science Foundation of Hebei Province (No: E2016208107).
35
References
1. J. Grzymek, Complex production of aluminium oxide and iron
from laterite raw materials applying the calcium aluminates
polymorphism. TMS Annual Meeting and Exhibition, Light Met.
87–99 (1985)
2. B. Wang, H.-Y. Yu, H.-L. SUN, S.-W. Bi, Effect of material ratio
on leaching and self-disintegrating property of calcium aluminate
slag. J. Northeast. Univ.: Nat. Sci. 29(11), 1593–1596 (2008)
3. Z.-F. Tong, S.-W. Bi, H.-Y. Yu, Y.-S. Wu, Leaching kinetics of
non-constant temperature process of calcium aluminate slag under
microwave radiation. Chin. J. Nonferrous Met. 16(2), 357–362
(2006)
4. D.J. Connor, Aluminium Extraction from Non Bauxitic Materials
(Aluminium-Verlag Gmbh, Sydney, 1988), pp. 230–250
5. B. Wang, H.-Y. Yu, Y. Miao, H.-L. Sun, S.-W. Bi, G.-F. Tu,
Effect of MgO on leaching and self-disintegrating property of
calcium aluminate slag. Light Met. 4, 11–13 (2008)
6. N.I. Eremin, Investgations on the complex processing of bauxites
(Bauxite-Alumina-Aluminum, Symposium of ICSOBA.Budapest:
Research Institute for Non-Ferrous Metals, 1971), 329–335
7. B. Wang, H.-Y. Yu, H.-L. Sun, S.-W. Bi, G.-F. Tu, H.-J. Geng,
Effect of MgO on crystal and leaching property of 12CaO
7Al2O3.
Minning Metall. Eng. 28(05), 68–71 (2008)
8. B. Wang, H.-Y. Yu, H.-L. Sun, S.-W. Bi, G.-F. TU, Synthesis and
Al2O3 leaching property of 20CaO
13Al2O3
3MgO
3SiO2. Chin.
J. Nonferrous Met. 19(2), 378–382 (2009)
9. Chen Chao-Hsia, A method of estimation of standard free energies
of formation of silicate minerals at 298.15 degrees K. Am. J. Sci.
275(7), 801–817 (1975)
10. P.-M. Guo, P. Zhao, Estimation of heat capacity of complex oxide
using two-parameter model. J. Iron Steel Res. 18(9), 17 (2006)
 Leaching Behavior of Alumina from Smelting
Reduction Calcium Aluminate Slag
with Sodium Carbonate Solution

Zhifang Tong and Yingjie Li

Abstract
Leaching behavior of alumina of smelting reduction calcium aluminate slag based on
high-iron red mud composition was investigated. Alumina of calcium aluminate slag was
leached using sodium carbonate solutions (Na2CO3 abbr., Na2Oc). The effects of Na2Oc
concentration, reaction temperature, reaction time, liquid-solid ratio on the leaching rate of
alumina were investigated and its leaching kinetics was studied as well. The results show
that the optimum conditions of leaching is reaction temperature of 75 °C, Na2Oc
concentration of 100 g L−1, reaction time of 100 min, liquid-solid ratio of 4.5:1. The
leaching rate of alumina is 83.7% under the optimum conditions. It is found that the
leaching process can be satisfactorily represented by fitting with Avrami equation. The
apparent activation energy of leaching pro cess and the feature parameter of Avrami
equation are determined to be 11,844 kJ mol−1 and 0.0983, respectively, the leaching
process is inner-difussion controlled.

Keywords
Calcium aluminate slag Alumina Leaching Kinetics

Introduction
In recent years, with high-grade mineral resources decreas-
ing, the development and utilization of the low-grade ore and
metallurgical secondary resources (metallurgical slag con-
taining high-iron) have achieved increasing attention. The
Bayer red mud of Guangxi Pingguo Aluminum plant in
China is a high-iron red mud, whose elemental analysis is
shown in Table 1. It is a kind of wealthy and valuable
secondary resource [1–3].
Currently, many studies on the utilization of high-iron red
mud have been carried out such as the direct reduction iron
[4–6] and directly selected iron [7, 8], but all of which have
Z. Tong (&)
Y. Li
School of Metallurgy and Chemical Engineering, JiangXi
University of Science and Technology, Gan Zhou, 341000, China
e-mail: tongzhifang1998@126.com
Y. Li
e-mail: 2691958837@qq.com
not been widely used in the practice due to some defects in
the process.
The red mud could be dealt by smelting reduction
iron-making process with calcium aluminate slag by slag-
ging system. Firstly, the elements of Fe, V, Ta will be
reduced and go into molten iron, and Na, Al, Sc in the red
mud will not be reduced and go into the molten slag, then the
slag is cooled in the certain cooling process and become
self-power calcium aluminate slag, in which the main alu-
minum component is 12CaO.7Al2O3 that is suitable for
leaching alumina; secondly, the Na, Al in reduction slag are
leached by sodium carbonate solution using wet grinding
process, then the scandium enriched in residues is extracted
by extracting process. Based on all of above, the compre-
hensive utilization of red mud could be realized eventually
by reduction smelting, slag leaching and extraction separa-
tion process. In the whole process, the leaching properties of
alumina in smelting reduction calcium aluminate slag is the
key part for aluminum in red mud recovering utilization.
However, the studies on leaching behavior of alumina in

© The Minerals, Metals & Materials Society 2017 37

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_6
38 Z. Tong and Y. Li

Table 1 Chemical composition Fe2O3 Al2O3 SiO2 CaO TiO2 V2O5 ZrO2 Sc2O3 Na2O Re2O3 Others
of red mud (mass%)
32.47 17.47 11.93 14.13 5.45 0.128 0.36 0.015 4.0 0.11 13.48

calcium aluminate slag based on the red mud composition

has not been reported so far. 1
In this work, the alumina in the slag was leached using 3
12
sodium carbonate solution, the effects of concentration of
sodium carbonate solution (Na2Oc), leaching temperature, 1
13
leaching time and liquid to solid ratio on the leaching rate of 4
alumina in slag were investigated, and the suitable leaching 2
conditions was determined. By studying the alumina leach- 1 3
ing kinetics of slag, the control step of the leaching process
2 1
was found out, and it provided an important theoretical basis 2 1
for leaching process optimization. 2 1 1
1 4

Experimental

Material
The experimental slags were prepared by mixing analytically
pure oxides (CaO, SiO2, Al2O3, MgO, TiO2), and adding
Na2CO3 as a source of Na2O according to the material
balance calculation of smelting reduction iron-making pro-
cess of COREX. These oxides are roasted prior to the
pre-mixed powder compositions for removal of carbonate
and water in oxide. The roasting temperature of the analyt-
ically pure oxides are listed in Table 2. The blended powders
was heated to melt in molybdenum crucibles in a MoSi2
resistance furnace at 1773 K for one hour under 0.5 L/min of
Argon atmosphere. After one hour, the molten slag was
cooled to 1200 °C at the cooling rate of 4 * 5 °C min−1 in
the furnace, then taken out from furnace and cooled in air.
During the slag cooling, dicalcium silicate in the slag had
crystalline transformation from b type to c type, which made
the volume of dicalcium silicate expanded 12% and made
the slag powder. The self-powder slag is collected for
leaching experiments. The chemical composition and XRD
pattern of slag are shown in Table 3 and Fig. 1, respectively.
It can be seen from Fig. 1 that the main phase of slag are
2CaO.SiO2, 12CaO.7Al2O3, CaTiO3.
Fig. 1 XRD pattern of calcium aluminate slag
The sodium carbonate solution was prepared with AR
NaOH, AR Na2CO3 and industrial Al(OH)3. The solution
composition is caustic alkali (Na2OK) 7 g L−1, A12O3
7 g L−1, carbon alkali (Na2Oc) 60 * 120 g L−1.
Experimental Method
The leaching experiment was performed in a water bath
heating apparatus with electromagnetic agitating, the leach-
ing container was a 500 mL three-necked flask. First, a
certain amount of sodium carbonate solution was added into
the flask and heated to a predetermined reaction temperature
with a certain stirring rate, and then the slag was put into the
solution according to experimental liquid-solid ratio. This
time was taken as the starting point for leaching. The
leaching was carried out according to predetermined time. At
the end of the leaching, making the liquid-solid separation
rapidly, the alumina content in the filtrate was analyzed

Table 2 Reagent purities and Brand CaO Al2O3 SiO2 MgO TiO2 Na2CO3
roasting temperatures
Chemical purity (%) >98 >98 >98 >98 >98 >98
Roasting temperature (K) 1273 1273 1273 1273 1273 573
Roasting time (h) 2 2 2 2 2 1

Table 3 Chemical compositions CaO SiO2 Al2O3 MgO TiO2 Na2O

of slag (mass%)
53.08 19.66 16.22 5.08 3.48 2.48
Leaching Behavior of Alumina from Smelting Reduction Calcium … 39

using chemical analysis method, and the leaching rate of
alumina was calculated.
The phase of slag was analyzed using X-ray diffraction
(Philips PW 3071 diffractometer with Cu Ka radiation), the
particle size distribution of slag using LS800 laser particle
size analyzer.
Results and Discussion
Leaching Experiment
Based on preliminary exploratory experiments, the stirring
rate was chosen to be 400 rpm and the orthogonal experi-
ment was designed with the alumina leaching rate as the
main reference index. The concentration of sodium carbon-
ate solution (Na2Oc), leaching temperature, leaching time,
liquid-solid ratio were identified as factors, the four levels of
each factor were chosen, and orthogonal experiment factor
level is shown in Table 4, the results of orthogonal experi-
ment and range analysis are shown in Table 5.
It can be seen in Table 5 that the influence order of factors
on the alumina leaching is temperature, carbon alkali con-
centration, time, liquid-solid ratio. In addition, for the same
factor, the larger Ki value means that the relative index of i
level is the better. So A3 was selected from A factor, B3 was
selected from B factor, D3 was selected from D factor.
Because the values of C3 is close to that of C4, taking
consideration for liquid-solid separation in the actual pro-
duction process, C3 was selected.
Therefore, the optimum leaching conditions of slag is
A3B3C3D3, that is to say, which is the leaching temperature
of 75 °C, carbon alkali concentration 100 g L−1, liquid to
solid ratio of 4.5, the leaching time 100 min.

Table 4 Orthogonal Temperature (°C) (A) Na2Oc (g L−1) (B) L/S (mL g−1) (C) Leaching time (min) (D)
experiments factor level design
1 95 140 6.5 140
2 85 120 5.5 120
3 75 100 4.5 100
4 65 80 3.5 80

Table 5 Results of orthogonal Number Temperature Na2Oc L/S Leaching time; Leaching rate
experiments and range analysis (°C) (A) (g L−1) (B) (C) (min) (D) of alumina (%)
1 95 140 6.5 140 69.09
2 95 120 5.5 120 73.15
3 95 100 4.5 100 79.66
4 95 80 3.5 80 81.23
5 85 140 5.5 80 73.72
6 85 120 6.5 100 83.03
7 85 100 3.5 120 81.45
8 85 80 4.5 140 78.94
9 75 140 4.5 120 83.86
10 75 120 3.5 140 84.01
11 75 100 6.5 80 82.86
12 75 80 5.5 100 83.21
13 65 140 3.5 100 82.31
14 65 120 4.5 80 81.52
15 65 100 5.5 140 83.28
16 65 80 6.5 120 82.69
k1 75.78 77.25 79.42 78.83
k2 79.29 80.43 78.34 80.29
k3 83.49 81.81 81.00 82.05
k4 82.45 81.52 82.25 79.83
R 7.70 4.57 2.83 3.22
40 Z. Tong and Y. Li

Effect of the Leaching Factors on the Leaching 90

Rate of Alumina 89

Leaching rate of alumina/ %

88
The effect of leaching temperature, Na2Oc concentration,
liquid to solid ratio and the leaching time on the leaching 87
behavior of slag was investigated, respectively. The results 86
are shown in Figs. 2, 3, 4 and 5. 85
It can be seen from Figs. 2, 3, 4 and 5 that when the 84
Na2Oc concentration is greater than 100 g L−1, the leaching
83
rates of slag change little. The leaching rate of alumina
increase firstly with leaching time increase, when the 82
leaching time is greater than 100 min, the leaching rate of 81
alumina change hardly. Within the experimental range, 80
liquid-solid ratio has little effect on the leaching rate. The 3 4 5 6 7

90 Fig. 4 Effect of L/S on leaching rate of alumina

88
Leaching rate of alumina/ %

90
86 88
Leaching rate of alumina/ %
84 86 Leaching time 100min
84
82
82
80 80

78 78
76
76
74
50 60 70 80 90 100 110 120 130 140 150
72
70
40 50 60 70 80 90 100
Fig. 2 Effect of Na2Oc concentration on leaching rate of alumina

Fig. 5 Effect of temperature on leaching rate of alumina

90

88
leaching rate increase firstly and then decrease with tem-
Leaching rate of alumina/ %

86 perature increase. The leaching rate reach a maximum value

at 75 °C, then decrease obviously with temperature increase.
84 In order to explore the reason of effect of temperature on
leaching rate, the XRD analysis of leaching residues under
82
different leaching temperatures are carried out and the results
80 are shown in Fig. 6.
As shown in Figs. 5 and 6, when the temperature is
78 greater than 75 °C, the secondary reaction between calcium
76
silicate in the slag and the sodium aluminate solution
improves, the alumina dissolved in the solution take part in
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
the reaction again to produce the compound of Na12Al12-
Time/min Si12O48 as shown the temperature of 95 °C, which lead to
the alumina leaching rate decrease.
Fig. 3 Effect of leaching time on leaching rate of alumina
Leaching Behavior of Alumina from Smelting Reduction Calcium … 41

12

12

12
12
2
12 12
2 2 11 1 2
1 1 2
1 2 1
1

10 20 30 40 50 60 70 80 90 100 10 20 30 40 50 60 70 80 90 100

12
1 13

12 3 13
1
2 2 22 2
1 121 2 1 3 3 3
1

10 20 30 40 50 60 70 80 90 100 10 20 30 40 50 60 70 80 90 100

Fig. 6 XRD patterns of residue at different leaching temperatures

Leaching Kinetics Effect of Temperature on the Leaching Rate

For understanding deeply the leaching behavior of slag and
leaching rate-controlled step, the leaching kinetics of cal-
cium aluminate slag was studied. In order to ensure reagent
concentrations as same as possible before and after the
experiments, the liquid-solid ratio of 20 is adopted, the
volume of sodium carbonate solution is 200 mL, and the
amount of slag is 10 g. By particle size analysis, the particle
size of calcium aluminate slag is fine, and the proportion of
less than 74 lm particles, is greater than 94%, so this
research did not consider the effect of particle sizes on the
dynamics. By preliminary experiments, the leaching ratio of
alumina in slag increased, firstly with the stirring rate
increase. When the stirring speed increased from 300 to
400 rpm, the change of the leaching rate was not obvious.
Therefore, the stirring rate was chosen to be 400 rpm.
of Alumina
Based on the leaching experiments, when the leaching
temperature is higher than 75 °C, the effect of the secondary
reaction on the decrease of the leaching rate is obvious,
which make the reactions of the slag leaching complex.
Therefore, this research focuses on the leaching behavior of
the slag below the temperature of 75 °C. Under the leaching
conditions of Na2Oc concentration 100 g L−1, liquid to solid
ratio of 20, stirring rate of 400 rpm, the relationship between
alumina leaching rate and time at different temperatures is
shown in Fig. 7.
As shown in Fig. 7, the leaching rate increases with the
temperature increasing at the same time. The leaching laws
of slag are basically the same at different temperatures.
Initial leaching rate of slag is very quickly, then the leaching
rate is significantly lower and the curve become smoothly
42 Z. Tong and Y. Li

Fig. 8 Ln[−ln(1 − X)] versus lnt at different reaction temperatures

Fig. 7 Effect of temperature on leaching rate of alumina

natural logarithm at the same time, the equation obtained is

with leaching time increase, the leaching rates change hardly
after 100 min.
Kinetics Model
The reaction between the compound of 12CaO.7Al2O3 in the
slag and Na2CO3 solution belongs to the liquid-solid mul-
tiphase reaction, which occurs at the interface of liquid and
solid, and a solid reaction product of CaCO3 is generated in
the process, the chemical reaction is shown in Eq. 1.
12 CaO:7Al2 O3 ðsÞ þ 12 Na2 CO3 ðsÞ þ 33 H2 OðlÞ
! 12 CaCO3 ðsÞ þ NaAlðOHÞ4 ðaqÞ þ 10 NaOHðaqÞ
As shown in Fig. 7, the initial reaction rate in leaching
process is great, but the reaction rate decreases quickly with
the reaction time increase, for such a type of liquid-solid
multiphase reaction, its kinetics is consistent with Avrami
model [9–15], the dynamics equation is as follows:
lnð1  XÞ ¼ ktn
where k is the apparent reaction rate constant; the charac-
teristic parameters of n can reflect process control mecha-
nism, which is only related with the properties and geometry
of solid grains and does not change with the reaction con-
ditions changing. The both sides of Eq. 2 were taken of the
as follows:
Ln ½lnð1  XÞ ¼ lnk þ nlnt ð3Þ
The data in Fig. 7 were taken into Eq. 3. The relationship
between ln [−ln(1 − X)] and lnt at different temperatures are
shown in Fig. 8. Figure 8 shows that there is a good linear
relationship between ln[−ln(1 − X)] and lnt, and it is
determined that leaching process is satisfactorily represented
by fitting with Avrami equation. The value of n and lnk at
different temperatures are shown in Table 6. As shown in
Table 6, the value of n at different temperatures do not
ð1Þ change obviously, the average value of n is 0.0983. So, the
feature parameter of n of Avrami equation is determined
0.0983.
Calculation of Activation Energy
In the chemical reaction, the reaction rate constant K is the
function of the temperature. The effect of temperature on K
could be expressed with the Arrhenius equation (Eq. 4).
ð2Þ
K ¼ K0 expðEa=RTÞ ð4Þ
where K0 is the frequency factor and Ea is the apparent
activation energy. Natural logarithm representation of Eq. 4
is in Eq. 5.

Table 6 Values of n and lnk at Temperature (°C) n lnk Ra

different reaction temperatures
75 0.0956 0.2194 0.9974
65 0.0941 0.1247 0.9992
55 0.1002 −0.0334 0.9975
45 0.1032 −0.1567 0.9962
a
R is correlation coefficient
Leaching Behavior of Alumina from Smelting Reduction Calcium …
Fig. 9 Arrhenius plot for leaching of alumina
lnk ¼ lnk0 þ ðEa=RTÞ ð5Þ
The relationship between lnk and 1000/T based on the
data in Table 6 is shown in Fig. 9. It can be obtained in
Fig. 9 that the apparent activation energy (Ea) and the fre-
quency factor (K0) can be calculated to be 11,844 kJ mol−1
and 75,368 kJ mol−1 according to Arrhenius equation,
respectively. Therefore, the dynamics equation is in Eq. 6.
lnð1  XÞ ¼ 75:368exp½11:844=ðRTÞt0:0983 ð6Þ
When the hydrometallurgical process is controlled by
inner-diffusion, the apparent activation energy is about
8–20 kJ mol−1 in general [16]. Therefore, the kinetics
rate-controlling step of the leaching process of slag in
sodium carbonate solution is inner-diffusion controlled. It is
reasonable to conclude that the reaction rate decrease is due
to the reaction product of CaCO3 wrapping up the surface of
slag particles and preventing the leached product diffusion.
Therefore, according to the results of kinetic studying, the
leaching rate of aluminum in slag can be improved by
adopting wet milling leaching process to remove the bad
effect of the CaCO3 wrapping up the surface of slag.
Conclusion
Alumina of smelting reduction slag based on red mud
composition could be leached out by sodium carbonate
solution. The optimum leaching conditions is reaction tem-
perature 75 °C, the Na2Oc concentration 100 g L−1, reaction
time 100 min, and the liquid-solid ratio 4.5:1. The leaching
rate of alumina is 83.7% under the optimum leaching
43
conditions. Leaching process can be satisfactorily repre-
sented by fitting with Avrami equation. The apparent acti-
vation energy of leaching process and the feature parameter
of Avrami equation are determined to be 11,844 kJ mol−1
and 0.0983, respectively, the leaching process is inner-
diffusion controlled.
Acknowledgements The financial support of National Natural Sci-
ence Foundation of China (number: 50974064) and Jiangxi Provincial
Association of Science and Technology funded projects (No. [2015]
141) are gratefully acknowledged.
References
1. Q.H. Xue, Y.W. Chen, Thought and exploration on the compre-
hensive utilization of red mud from Guangxi Pingguo aluminium
Co., Light Met. 10, 11–14 (2011)
2. Y.F. Zhang, et al., Comprehensive utilization status of red mud
from Pingguo and its development and expectation. Light Met. 12,
13–17 (2004)
3. S.J. Yang, The study of phase indentitification of red mud of
pingguo alumina plant. J. Cent. South Univ. Tech. 27(5), 569–573
(1996)
4. H. Wang et al., Experimental research on comprehensive utiliza-
tion of the high iron red mud based on direct reduction and melting
by RHF iron bead technology. Light Met. 1, 19–22 (2013)
5. P.H. Liand, G.W. Li, Study on direct reduction of iron red mud
digestion of Pingguo aluminum mine. Light Met. 10, 20–24 (1997)
6. D.C. Lou et al., New process of utilizing red mud from alumina
treating plant to produce high quality direct-reduction iron. China
Min. Mag. 11(5), 50–54 (2002)
7. P.B. He, Y.F. Zhou, Y.H. Hu, Reseach of pingguo bayer process
red mud with using magnetic separation of selective hydrophobic
flocculation. Nonferrous Met. 6, 1–4 (2008)
8. J.Z. Lu, X.J. Yu, L.P. Zhang, Development condition of recov-
ering iron from red mud. Shandong Metall. 29(4), 10–14 (2007)
9. Y.F. Chang et al., Sulphuric acid leaching kinetics of pre-reduced
laterite ores. J. Mol. Sci. 24(4), 241–245 (2008)
10. C.F. Dickinson, G.R. Heal, Solid-liquid diffusion controlled rate
equations. Thermochim. Acta 340, 89–103 (1999)
11. N. Demirkiran, A. Kunkul, Dissolution kinetics of ulexite in
perchloric acid solutions. Int. J. Mineral Process. 83(1), 76–80
(2007)
12. H. Okur et al., Effect of ultrasound on the dissolution of colemanite
in H2SO4. Hydrometallurgy 67(1), 79–86 (2002)
13. Q. Li et al., Acid leaching kinetics of zinc plant purification
residue. Trans. Nonferrous Met. Soc. China 23, 2786–2791 (2013)
14. Y.J. Zheng, K.K. Chen, Selective leaching Se from selenium
residue by Na2SO3 solutions and leaching kinetics. Chinese J. Non-
ferrous Met. 22(2), 585–589 (2012)
15. X.Y. Guo et al., Atmospheric leaching of nickel laterite by
hydrochloride acid and its kinetics. Min. Metall. Eng. 31(4), 69–74
(2011)
16. D.C. Mo, Metallurgy Kinetics (Central South University of
Technology Press, Changsha, NY, 1987), p. 295
 Part II
Alumina and Bauxite: Bauxite Residues Technology
 Security Disposal and Comprehensive
Utilization of Bauxite Residues

Songqing Gu, Zhonglin Yin, and Lijuan Qi

Abstract
Security disposal and comprehensive utilization of bauxite residues are of great significance
to the world alumina industry due to environmental protection requirement and waste
materials recovery. The security disposal and utilization technologies for bauxite residue
will be shown and discussed in this paper. The dry stacking technology for Bayer residues
by the drum or pressure filters has been applied widely in the Chinese refineries from
10 years ago. Magnetic separation dressing of high iron content red mud for iron ore
concentrates has been put into industrial operations in China for more than 5 years. The
residue from sintering process is able to be used for red mud pool dam construction and
Soil Modifiers for high acidic soil areas for neutralizing and adsorbing the harmful heavy
metal compounds in the soil. The high caustic Bayer residues could be applied for such
construction materials as foamed ceramics and glass ceramics etc. The further utilization
possibilities and potentials in the future are outlined in the steelmaking, construction,
agriculture and environmental industry etc.

Keywords
Bauxite residues Disposal Stacking Comprehensive utilization

Introduction applied in almost all the Chinese refineries 10 years ago,

China has become the biggest alumina production country
since 2007. About 59 million dons of alumina was produced
in China in 2015 with over 100 million tons of solid residue
to be disposed. It becomes a very important issue for envi-
ronmental protection and circular economy to safely dispose
and utilize the bauxite residue since the most of alumina
refineries are set up in the areas with a large population in
China.
Security stacking and disposal of the residues is the first
technical problem to be solved. The wet stacking was
S. Gu (&)
China Aluminum Corporation Limited, No.62 Xizhimenbei Street,
Beijing, 100082, China
e-mail: s.q.gu@163.com
Z. Yin
L. Qi
Zhengzhou Light Metals Research Institute, Zhengzhou, Henan
450041, China
even just piling up in situ so that there was a great risk of
disposal security and caustic leakage to pollute underground
water for the Chinese refineries at that time.
Meanwhile a great effort of R&D for comprehensive
utilizations of bauxite residues has been made to reduce
treatment cost of the residues, to increase stack area lifetime
and mitigate pollution risk in China in the past 30 years
including making cement as one of raw materials by deal-
kalizing process, using residues as the main component for
roadbed, extracting valuable elements from the residues etc.
However, most of early study results were not applied in a
large industrial scale due to their engineering imperfections
or no economical benefits.
In the past 10 years the security disposal and utilization
of the bauxite residues have become a serious and urgent
issue with the great growth of alumina production in China,
which prompts Chinese government to introduce a series of
polices for encouraging Chinese refineries to increase

© The Minerals, Metals & Materials Society 2017 47

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_7
48 S. Gu et al.

technical input and to develop extensive cooperation. As a

result, a series of key technologies have been developed and
applied in the industry [1]. The dry stacking and utilization
rate of the residues have been greatly improved.
The technology achievements in the residue disposal and
comprehensive utilization in China will be summarized and
the technology development trend in the future in this field
will be outlined in this paper.

Technical Achievements of Residue Disposal

and Utilization

Red Mud Dry Disposal Fig. 2 Bauxite residue piling up field

Almost all the bauxite residues in Chinese refineries were

wet stacked 10 years ago except Pingguo refinery. The wet
stack technology is shown in the Fig. 1. Wash Settler Recovered Liquor

In this process the bauxite residue slurry is pumped and

discharged from washing tanks into red mud pools on the
undersurface of which the impermeable layer is set up for
preventing the caustic liquor to pollute underground water
and the caustic liquor is collected in the pools and pumped
back to the refineries. The height of the pool dams can be
increased for enhancing the stacking area lifetime when the
red mud pools are filled up (Fig. 2).
However the caustic pollution to the environment by the
liquor leakage to underground water system is the major risk
of the wet disposal of red mud slurry. And the disasters will
happen to downstream areas if the dams are collapsed or the
caustic liquor is effused just like what happened in Hun-
garian refinery in 2010.
So called semi-dry stacking technology for the bauxite
residue was put into operation by Chinese refinery 22 years
ago. The semi-dry stacking process is shown in Fig. 3.
In this process a rotary filter is set up after the last wash
settler to reduce the liquor content in the discharged residue
Bayer Process
Semi-Dried Residue
Rotary Filter
High Pressure Pump
Fig. 3 Schematic diagram of semi-dry stacking Process
to about 40%, which is stirred strongly in the storage tanks
for reducing the shear force of the high density slurry to send
it to the residue stacking areas by high pressure pump.
The dry disposal technology for the bauxite residues [2,
3] has been developed in recent 10 years in China as shown
in Fig. 4.
The pressure filters are set up near the residue stacking
areas to reduce the liquor content in the discharged residues

Recovered Liquor
High Settler

Pressure Filter
Bayer Process

High Pressure Pump Dried Residue

Stacking area
Stacking Areas

Fig. 1 Bauxite residue wet stacking Fig. 4 Schematic diagram of dry stacking Process
Security Disposal and Comprehensive Utilization of Bauxite … 49

to about 30% and put the dried residue into disposal areas.
The liquor after filtration is pumped back into refineries for
recovery.
The liquor quantity into storage areas is reduced by more
than 50% by using the dry disposal technology. The bull-
dozers are applied to push and compact the residues for
further reducing the liquor content in the residues, as the
result of which the risk of caustic pollution and the dam
collapse is greatly reduced.
However the productivity of press filters for dried resi-
dues is respectively low due to the bench process of the
filters. Especially in the winter season in the north China a
great amount of steam will be eliminated when discharging
the dried residue at higher temperatures for the difficult
operation so that it becomes an important optimization
project to improve filtration equipment.

Making Iron Concentrates by Magnetic

Separation Dressing from the Residues

The high iron content bauxite residues are produced in

Guangxi and Shandong refineries using high iron content
bauxite in China. Meanwhile a large quantity of iron ore has
to be imported to China for Chinese iron and steel industry.
The iron concentrates can be obtained by processing the
high iron content bauxite residue and be used as supplement Fig. 5 Magnetic separation equipment in China
of iron making and for reducing residue disposal as well.
A systematic study is carried out by Chalco for com-
prehensive utilization of the high iron residues in Guangxi suitable for the construction and strengthening of red mud
and Shandong refineries. The major chemical composition of pool dams. So the sintering residue is often given priority for
the Bayer residue tested is listed in the Table 1. construction, packing and mending of the Bayer residue
It is revealed by the study that the metal iron content in dams, owing to which the sintering residue is consumed and
the iron concentrates can be increased to more than 55% and the dam security is much better ensured.
the iron recovery rate reaches more than 40% by the newly
developed magnetic separation technology as shown in
Fig. 5. Making Construction Materials from the Residues
The concentrates can be used for making iron as a sup-
plement material in iron and steel plants [4] and the iron The bauxite residues are similar to the construction raw
recovery rate from the residue can be improved to more than materials in the chemical and mineral compositions. Calcium
40%. This technology is applied in China already. silicates, hydrogarnet and hematite can be found in the
common construction raw materials. R&D of bauxite residue
utilizations focuses on making the construction materials due
Red Mud Pool Dam Construction by Sintering to their great utilization quantity and wide application areas.
Residue
Road construction materials
There are both Bayer and Sintering processes in some Chi-
nese refineries such as Shanxi refinery of Chalco. Due to its The tests to use the bauxite residues for filling materials
better adhesive property the residue from sintering process is during road construction have been completed by Chalco

Table 1 Chemical composition TFe FeO Fe2O3 SiO2 Al2O3 CaO Na2O TiO2
of the residue sample, %
25.3 0.7 35.4 8.6 15.5 13.9 3.2 6.3
50 S. Gu et al.

refineries. The test results show that the compressive

strength, permeability and stability of the road by using
bauxite residue filling material are similar to the common
road construction materials, which has proved that it is
possible to use bauxite residues for the road construction.

Building bricks

It is also tested in Chalco that the bricks for building

construction can be made by mixing fly ash with less content
of bauxite residue instead of clay. Both waste materials are
used and consumed to make usable construction bricks, the
properties of which are qualified up to the brick standard.

Foam ceramics

The foam ceramics become a kind of new construction

materials owing to their excellent properties such as good
strength, high porosity, less density, resistance to oxidation
etc., which makes it suitable to the light construction
materials used as sound and heat insulation walls.
The results of the tests made in Chalco show that a kind
of foam ceramics bricks as shown in Fig. 6 can be made by
using bauxite residue as part of raw materials and the caustic
in the residues can play some role to modify the property of Fig. 7 Ceramite balls from the residues
the bricks.

Glass ceramics and ceramite balls
Glass ceramics are a new kind of construction materials,
which have an excellent toughness, smooth surface and dura-
bility. The properties of glass ceramics are much better than
such natural stones as marble, granite and ceramic tiles etc.
The glass ceramics bricks can be made partly from
bauxite residues, the caustic in which could be reacted to
glass component in glass ceramics.
The bauxite residues can be used to make the ceramite
balls as shown in Fig. 7 for building construction owing to
their light density and excellent heat resistance, which are
suitable to be laid on the building roof.

Making Soil Modifiers for High Acidic Soil Areas

Fig. 6 Foam ceramics bricks from the residues
There are large acid soil areas in the south China and even
with the heavy metals pollution in some places.
The joint efforts have been made to solve the serious
problems by Chalco and a few Chinese universities together.
The soil modifiers have been developed by processing the
caustic residue by some additives and a large scale experi-
ments have been carried out in China.
The utilization of the soil modifiers is not only able to
neutralize the acidic soil for improving farm output but also
to retard the detriment to crops by the heavy metals in the
soil based on the excellent adsorption characteristics of the
heavy metal ions on the soil modifiers.
Security Disposal and Comprehensive Utilization of Bauxite …
Outlook of Utilization Potentials of Bauxite
Residue
Utilizations of the bauxite residues are very important for
environment protection and reducing the residue stacking
pressure, which closely deals with the development goals of
the world alumina industry. The major utilization potentials
of the bauxite residues in the future are studied and shown as
follows:
Utilization Potentials in the Iron and Steel
Industry
The iron concentrates from high iron content bauxite residue
contain about 55% of metal iron and can be an ingredient for
iron making in iron smelting blast furnaces, which has been
applied in Chinese iron industry already and can be
extended.
There is some possibility to further use the bauxite resi-
dues in the iron and steel industry as additives for reducing Summary
the slag viscosity and iron loss.
The most important technical problem for using the
residue in iron and steel industry is to develop the addition
recipes for the residues from the different sources.
Utilization Potentials in the Environmental
Industry
It is well known that the acidic wastes could be neutralized
by caustic bauxite residues. Based on this principle the
bauxite residues can be used for treatment of acidic wastes
such as acidic flotation effluents in the heavy metals dressing
plants, surface water with acidic or heavy metals pollution,
acidic waste water in the slag disposal areas etc.
The major technical problem to be solved in this field is
to develop the approaches to add the residues into the wastes
and to reach the best results.
Utilization Potentials in the Construction
Industry
As mentioned above the bauxite residues can be used for
various kinds of construction materials of road, public places
and building construction instead of the common tabia,
cement and bricks in a big batch. And it is also revealed in
some papers that the residues would be the good filling
materials in the plastics devices for the excellent anti-aging
and fire resistant properties. This field is a major utilization
potential.
The process technology is essential to the construction
material properties because all the residues have the different
51
compositions and it is needed to mix many other different
materials. A series of up to date process technologies have to
be developed to make the construction materials from the
bauxite residues to have the better properties.
Utilization Potentials in the Agriculture
The bauxite residues have some excellent properties espe-
cially excellent adsorption to heavy metal ions, containing
some elements important to plant growth, neutralizing the
acidified soils etc. so that the wide applications of bauxite
residues should be found in the agriculture field [5].
The soil modifiers and silicon-calcium-fertilizers will be
the major products to be used in the agriculture field.
Nevertheless a great deal of tests should be further carried
out for the security application since the agriculture products
are closely related to human health.
1) Security disposal and comprehensive utilization of
bauxite residues become the significant R&D projects for
the Chinese alumina industry. Some research achieve-
ments have been realized and commercialized in China.
2) The dry stacking of the bauxite residues is widely applied
in China for the disposal security. The magnetic sepa-
ration dressing concentrates from high iron content
residues are used for iron and steel industry. And the
residues from sintering process are used for Bayer resi-
due disposal dam construction.
3) A great number of technologies to utilize bauxite resi-
dues are studied or have been developed such as the new
kinds of construction materials, soil modifiers etc.
4) The development trend of the bauxite residue utilizations
are analyzed and the major potentials will be found in
such fields as iron and steel making, environment pro-
tection, construction material production and agriculture.
References
1. H. Li, S. Gu, et al., Technology Handbook of Aluminum Production
(in Chinese). (Metallurgical Industry Press, Beijing, 2011)
2. M.M. de Castro et al. A new technology for dry disposal of
alunorte’s bauxite residue. Light Met. pp. 109–112 (2013)
3. K. Evans, E. Nordheim, K. Tsesmelis, Bauxite residue management.
Light Met. pp. 63–66 (2012)
4. Mingjun Rao et al., Iron recovery from red mud by reduction
roasting-magnetic separation. Light Met. pp. 125–130 (2013)
5. G.K. Andrey Panov et al., Directions for large scale utilization of
bauxite residue. Light Met. pp. 93–98 (2012)
 Bauxite Residue Amendment Through
the Addition of Ca and or Mg Followed
by Carbonation

Luis C.A. Venancio, José Antonio Silva Souza,

Emanuel Negrão Macedo, Fernando Aracati Botelho,
Amanda Morais de Oliveira, and Raissa Silva Fonseca

Abstract
The alumina production Bayer process generates 0.7–2.0 ton of Bauxite Residue (BR) and
an average of 1.0 ton of CO2 per ton of alumina produced. The direct use of exhaust gases
to react and reduce the alkalinity of BR may allow a triple gain: improving the storage
conditions, opening a range of new applications for BR and sequester from 16 to 102 kg of
CO2 per ton of alumina. This paper shows a lab scale long term program to measure the
effects of adding different percentages of Ca and Mg salts followed by carbonation in order
to precipitate the alkalinity on stable compounds. The main goal is to decrease the
stabilization pH to facilitate the reuse. The processed material was analyzed periodically to
monitor the appearance of carbonates. The pH of the suspension was monitored for
400 days after the reaction to evaluate the buffer effect. X-ray diffraction and scanning
electron microscopy were used to analyze the reacted material.

Keywords
Bauxite residue Carbonation Carbon dioxide Alkalinity precipitation

Introduction The alumina is mainly produced from the refining of

Aluminum is the most used non-ferrous metal in the world
due to its excellent physical and chemical characteristics,
which is worth noting the low specific weight, corrosion
resistance, high thermal and electrical conductivity. It is used
extensively in transportation, electrical transmission, pack-
aging, construction and many other industries.
Despite being a metal abundant in the earth’s crust, it is
not found in its pure state. Metallic aluminum is obtained by
electrolysis of aluminum oxide (Al2O3), also known as
alumina extracted from bauxite by a combination of chem-
ical processes.
L.C.A. Venancio (&)
A.M. de Oliveira
R.S. Fonseca
Interdisciplinary Bachelor of Science and Technology, UFMA—
Federal University of Maranhão, Av. Dos Portugueses, 1966,
Bacanga, São Luís, MA CEP 65080-805, Brazil
e-mail: luiscvenancio@gmail.com
J.A.S. Souza
E.N. Macedo
F.A. Botelho
Amazon Natural Resources Development Program PRODERNA,
UFPA—Federal University of Pará, Rua Augusto Correia 01,
Guamá, Belém, Pará CEP 66075-110, Brazil
bauxite ore using the Bayer process. The extraction of alu-
minum oxide from the ore is obtained by dissolution in
caustic soda at high temperature followed by separation of
insoluble bauxite residues (BR). The last step is the seed
precipitation and calcination of the alumina. The BR poses
risks to the environment due to its large volume and high
alkalinity. According to the latest technology BR is stacked
in specially constructed sealed deposit areas. To date the
immense majority of the BR that has been produced are
stored. With exception to some efforts in Russia and China
[1, 2] very little is reused or incorporated into other pro-
duction processes. However, a strategic goal was set by the
International Aluminium Institute (formed by most indus-
tries) in 2010 to reuse 20% of BR by 2025 [3].
This paper summarizes the results of lab scale experi-
ments and of the reaction of CO2 diluted on air with a water
suspension of BR with addition of CaO and the preliminary
results of the addition of magnesium carbonate. The alka-
linity of the BR was substantially reduced after reaction with
the CO2. The stabilization pH showed a tendency down-
wards after 400 days of the carbonation.

© The Minerals, Metals & Materials Society 2017 53

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_8
54
These lab scale experiments were designed to enable the
continuation of the pilot scale experiments with flue gas and
BR presented at 2013 [4]. At that experiments it was verified
the possibility of carbonating the BR with flue gas con-
taining around 8% CO2. The pH after carbonation reached
8.5. Although the pH rebuff after 150 days to an average of
10.5. Since we are dealing with a low Ca BR, it was decided
to run a lab scale experiments to measure the impact of
adding different amounts of CaO and or Magnesium Car-
bonate ((MgCO3)4.Mg(OH)2.5H2O).
This work is part of a long term effort to design and test an
efficient new process of reducing the alkalinity of BR, capture
CO2 and SO2 minimizing power consumption and capital costs.
The pH of the BR slurry was measured during the reac-
tion and for up to 400 days after reaction to access the extent
of pH stabilization over time. Lower the alkalinity of BR
reduces the environmental risk with its storage [5] and
potentially facilitates the reuse of this material in different
new applications.
Unlike similar processes available at the literature [6], in
this case the tricalcium aluminate could not be the main
factor due the low Ca content shown in X-ray fluorescence.
This was the main reason to test the addition of CaO on a lab
experiment in order to control the stabilization pH.
Bayer Process for Alumina Production
The Bayer process to obtain alumina from bauxite can be
divided in four steps:
Digestion
The minerals containing aluminum at the bauxite are selec-
tively extracted from the non-soluble components through
the dissolution in sodium hydroxide.
AlðOHÞ3 þ Na þ þ OH ! NaAlO2 þ 2H2 O ð1Þ
Clarification
After the extraction, the insoluble bauxite residue (BR) must
be separated through a settling and filtering process. The
aluminum containing liquor is transferred to the precipitators.
Precipitation
Crystalline aluminum trihydroxide “hydrate” is precipitated
from the liquor.
L.C.A. Venancio et al.
NaAlO2 þ 4H2 O ! Al(OH)3 þ Na þ þ OH ð2Þ
The hydrate is fed into the calcination kiln.
Calcination
The hydrate is calcined to form alumina trough the sep-
aration of the water.
2AlðOHÞ3 ! Al2 O3 þ 3H2 O ð3Þ
Bauxite Residue
Alumina production through Bayer process generates from
0.7 to 2.0 tons of residue per ton of alumina produced. It is
usually called Bauxite Residue (BR) also called red mud.
The BR composition include hematite and e other iron
oxides, quartz and titanium oxides.
On the BR treatment only part of the sodium hydroxide is
removed. The BR has a considerable amount of sodium
hydroxide and several concentrated ores. On the other hand,
the bulk of its alkalinity is in the solids and reacts slowly
after the pH of the liquid is lowered. Contributes to this the
addition of lime and other additives during the Bayer process
with the objective of avoiding silica dissolution, helping the
settling and improving the production. Not integrating BR in
other processes is a waste of mineral resources, but it must
be done in an energetic and economically viable way.
Table 1 shows the chemical analysis of the BR from Alu-
mina do Norte do Brazil S/A (ALUNORTE—
Belém-PA-Brazil).
BR Complex Alkalinity and the Reaction
with Carbon Dioxide
The chemical reactions that control the alkalinity of BR and
its neutralization behavior are complex. The time and the pH
are the two most important variables. The pH is governed by
the presence of alkaline solids. BR solutions pH average is
12.3, with standard deviation of 1.0 and ranges between 9.7
and 12.8. Therefore BR is hazardous due its high alkalinity
[8], and high volume. The pH neutralization process is
affected by the presence of hydroxides, carbonates, alumi-
nates and polyacrylates [8, 9]. These solids that are formed
on the desilication process, on the Bayer process and also by
addition of lime. The buffering action of this multiple
alkaline solids causes the neutralization behavior of BRs to
Bauxite Residue Amendment Through the Addition of Ca and or Mg … 55

Table 1 Dry BR composition Content % Content %

[7]
SiO2 18.3 Na2O 9.31
Al2O3 22.6 V2O5 0.28
Fe2O3 34.9 K2O 0.13
TiO2 5.56 MgO 0.04
CaO 1.32 FL 7.56

be complex with several steps and time dependent. Washing

with water is not a practical way to remove the alkalinity
from BR [9]. This chemistry and alkalinity impact on dif-
ferent aspects of BR. Storage requirements are affected by
the reactivity with sealants. Bulk density, sedimentation
rates, compaction, hydraulic conductivity, drying rates,
dusting behavior, and physical strength are also alkalinity
impacted [10]. The reuse as a raw material other process
requires at least reduced reactivity to facilitate handling,
interaction with other raw materials and transport.
The carbonation neutralizes the alkalinity according to
the following equations:

CO2 ðgÞ þ OH $ HCO

3 ð5Þ

HCO þ 2
3 ðaq) $ H þ CO3 ðaqÞ ð6Þ Fig. 1 pH evolution during carbonation at pilot plant [4]

As pH decreases the following reactions occur:

AlðOHÞ 
4 ðaq) $ AlðOHÞ3 ðsÞ þ OH ðaqÞ ð7Þ
NaAlðOHÞ4 ðaqÞ þ CO2 $ NaAlðOHÞ2 CO3 ðsÞ þ H2 O(l)
ð8Þ
Previous Experiments
Current lab scale experiments were designed to enable the
continuation of the pilot scale experiments with flue gas and
BR presented at 2013 [4]. As we can observe at Figs. 1 and
2, the pilot experiments verified the possibility of carbon-
ating the BR with flue gas containing around 8% CO2.
Although the pH rebuffed after 150 days to an average of
10.5. This fact was attributed to the slow reaction of the
alkalinity contained at the solid phase and the partial
reversion of the carbonation. In order to increase the pre-
cipitation of stable compounds and consequently reducing
the buffer effect on the stabilization pH [11], it was decided
to run a lab scale experiments adding different amounts of
CaO and magnesium carbonate before the carbonation.
Lab Scale Experiment Equipment
The main objective of this experiment is to evaluate the
possibility of the precipitation of the alkalinity of the car-
bonated BR on stable compounds and therefore obtain a
lower long term stabilization pH.
The laboratory experiment consists of the following
steps:
1. Mixture of dried BR, with CaO. The amount of CaO vary
from 2.5% to 50% ww.
2. Addition of water in order to obtain a suspension with
27% BR/CaO and 73% water ww.
3. Carbonation on a bubbling tower with a mixture of CO2
and air 50% vv. The carbonation process duration is
120 min.
4. Monitoring the pH of the reacted material.
The results presented here were monitored for 400 days.
At Fig. 3, can be observed the flowchart for the labora-
tory process.
56 L.C.A. Venancio et al.

Fig. 2 pH evolution of several

experiments after carbonation at
pilot plant [4]

Fig. 3 Flowchart of the

laboratory equipment

The Experiment
Each of the experiments were made in triple
Different weight percentages of CaO from 1 to 50% ww
were added to the BR and mixed for 20 min with 73% ww
of H2O followed by carbonation at the bubbling tower for
120 min. The resultant material were stored on lidded flasks
and the pH is measured every month after 5 min of agitation.
Different weight percentages of Magnesium Carbonate
((MgCO3)4.Mg (OH) 2.5H2O) from 1 to 10% were added to
the BR and mixed for 20 min followed by carbonation at the
bubbling tower for 120 min. The resultant material were
stored on lidded flasks and the pH is measured every month
after 5 min of agitation.
Results and Comparison of Pure Carbonation,
Ca and Mg Addition
At Fig. 4 we can observe the results of the stabilization pH
of different amounts of CaO added BR from 1 to 50%. There
is a trend to stabilize at an average of 9.5.
At Fig. 5, it can be observed a comparison of the aver-
ages of the experiments of pure carbonation, the Ca added
Bauxite Residue Amendment Through the Addition of Ca and or Mg …
Fig. 4 Stabilization pH of
different amounts of CaO added
BR
Fig. 5 Comparing the average
stabilization pH of different
experiments
followed by carbonation and the preliminary results of the
Mg added followed by carbonation.
At Fig. 6, it can observed at the top BR plus 10% CaO,
with the formation of Calcite (CaCO3) at 2h = 26.623° and
29.341°, compared with pure carbonation at the bottom.
At Fig. 7 can be seen the scanning electron microscopy of
a 10% CaO added carbonated BR were can be observed the
CaCO3 slow formed occurrences. Since this is a very slow
reaction most of the material is in amorphous form.
Conclusions
The pure carbonation stabilization pH have an average of
10.5.
57
The BR with CaO added followed by carbonation has a
stabilization average PH of 9.5.
There is no direct correlation with the amount of Ca and
the stabilization pH.
The existing preliminary data of the magnesium carbon-
ate added Br followed by carbonation shows a similar trend
of the CaO added.
Next Steps
Make an experiment with the addition of brine and compare
the results with the presented here.
Develop a pilot scale experiment with addition to validate
the results on a larger scale.
58 L.C.A. Venancio et al.

Fig. 6 X-ray diffraction of pure

carbonation BR at the bottom and
BR with 10% added CaO
followed by carbonation at the top

Fig. 7 Scanning electron

microscopy of a 10% CaO added
carbonated BR

Simulate models of BR deposits submitted to weather and
compare with lab results. Analyze the leached.
References
1. A. Panov, G. Klimentenov, G. Podgorodetskiy, V. Gorbunov,
Directions for large scale utilization of bauxite residue, TMS.
Light Met. pp. 93–98 (2012)
2. W. Liu et al., New progresses on utilization of red mud in China.
Icsoba newsletter, vol. 15, http://www.icsoba.org/newsletters. June
2016
3. Alumina Technology Roadmap, http://www.world-aluminium.org/
media/filer/2012/06/12/fl0000422.pdf 2010
4. L.C. Venancio, J.A.S. Souza et al., Pilot test of bauxite residue
carbonation with flue gas, TMS. Light Met. 2013, 113–118, San
Antonio (2013)
5. H.R. Nikraz, A.J. Bodley, D.J. Cooling, P.Y.L. Kong, M. Soomro,
Comparison of physical properties between treated and untreated
Bauxite Residue Amendment Through the Addition of Ca and or Mg …
bauxite residue mud, J. Mater. Civil Eng. 19(1), 2–9
(ASCE/January 2007)
6. S. Khaitan, D.A. Dzombak, G.V. Lowry, Mechanisms of neutral-
ization of bauxite residue by carbon dioxide. J. Environ. Eng.
ASCE. 135(6), 433–438 (2009)
7. L.C. Venancio, J.A.S. Souza et al., Residues recycling, saving
money and helping the environment. JOM. 62, 41 (September
2010)
8. M. Gräfe, G. Power, C. Klauber, Review of bauxite residue
alkalinity and associated chemistry; DMR-3610; CSIRO-Minerals
(2009)
59
9. M.R. Thornber, D. Binet, Caustic soda adsorption on Bayer
residues, in 5th International Alumina Quality Workshop, Ed by
AQW Inc., Bunbury, pp. 498–507 (1999)
10. D.J. Cooling, P.S. Hay, L. Guilfoyle, Carbonation of bauxite
residue, in Proceedings of the 6th International Alumina Quality
Workshop, ed. by S. Chandrashekar, AQW Inc., Brisbane,
pp. 185–190 (2002)
11. M. Johnston, M.W. Clark, P. McMahon et al., Alkalinity
conversion of bauxite refinery residues by neutralization.
J. Hazard. Mater. 182, Elsevier (2010)
 Application of Tricalcium Aluminate Instead
of Lime for the Recovery of Aluminum
in Middle-Low Grade Bauxite
in Calcification-Carbonization Process

Yanxiu Wang, Ting-an Zhang, Guozhi Lu, Weiguang Zhang,

Xiaofeng Zhu, and Liqun Xie

Abstract
In the process of calcification-carbonization, the alkali and aluminum in the mid-low grade
bauxite and red mud can be recovered. Aluminum is obtained in the form of
low-concentration sodium aluminate solution which is comparatively difficult to reuse. In
this paper, the low-concentration sodium aluminate solution was reused to prepare tricalcium
aluminate and went back to the Calcification-Carbonization process instead of lime. When
processing gibbsite and diasporic bauxite with Calcification-Carbonization method, the
effect of calcium aluminate on dealkalization and dealumination was investigated. The
results show that the alumina-silica ratio of these two ores can be both reduced to 0.70, and
the sodium alkali content can be reduce to less than 0.50%. It indicates that it’s feasible to use
calcium aluminate replacing lime. The proposal well solved the problem that aluminum is
difficult to recycle at low concentrations and enhances the effectiveness and cleanness of
Calcification-Carbonization process which has an extensive prospect.

Keywords
Alumina Calcification-carbonization Calcium aluminate Recovery of aluminum

Introduction realize the efficient and clean production of alumina which

China is flourishing in alumina industry with great quantity
of production and consumption. At present, the alumina
output of China reaches 40% of global total. On one hand,
the rapid development of alumina scale makes the congenital
disadvantage of scarce bauxite resources more apparent. On
the other hand, red mud which is alkaline industrial solid
waste has to stockpile in a large amount for a long time,
resulting in continuous ecological destruction and potential
safety hazard [1, 2]. In face of dual challenges of resources
and environment, it’s particularly essential and urgent to
Y. Wang
T. Zhang (&)
G. Lu
W. Zhang
X. Zhu
L. Xie
Key Laboratory of Ecological Metallurgy of Multi-metal
Intergrown Ores of Education Ministry, Special Metallurgy
and Process Engineering Institute, School of Metallurgy
of Northeastern University, Shenyang, Liaoning, 110819, China
e-mail: zta2000@163.net
Y. Wang
e-mail: 137141750@qq.com
promotes industrial progress and upgrading.
After years of research, the metallurgy and process engi-
neering Institute of Northeastern University proposed
Calcification-Carbonization method which uses middle-low
grade bauxite to produce alumina efficiently and cleanly [3–5].
First, calcium, silicon, aluminum in the digestion system is
combined completely to form calcification transformation
product in the calcification process which is mainly made up of
grossularite. Second, the calcification product is disposed with
CO2 and decomposes to the carbonization product in the
carbonization process which is mainly made up of calcium
carbonate, calcium silicate and aluminum hydroxide Third,
the carbonization product is put into sodium hydroxide solu-
tion to dissolve the alumina and the resultant solid product is
new-typed red mud in which the main composition is calcium
carbonate and calcium silicate [6–8] (Fig. 1).
In the processing of middle-low grade bauxite and red
mud with Calcification-Carbonization method, the relative
content of aluminum is low, and the aluminum content in

© The Minerals, Metals & Materials Society 2017 61

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_9
62
Fig. 1 Process chart of
calcification–carbonization
liquor after leaching is also low which make it difficult to
perform seed precipitation. The way of evaporation to
increase the concentration will consume a lot of energy.
Therefore, the recovery and recycling of aluminum from low
concentration leaching liquor is difficult to realize. In order
to make full use of aluminum resources and reduce the cost
effectively, the low aluminum leaching liquor was proposed
to combine with lime, forming tricalcium hydroaluminate
which returns to the system and completes the calcification
transformation instead of lime.
According to the literature [9, 10], the calcium aluminate
produced in sintering process system can be used in the Bayer
digestion instead of lime in processing diasporic bauxite with
Bay-Sintering combine process. The results show that the use
of calcium aluminate has no adverse effect on Bayer diges-
tion. In regard to the Calcification-Carbonization process for
alumina production, no relevant research has been reported to
study the effect of tricalcium hydroaluminate on the dealka-
lization and dealumination. In this paper, 3CaO
Al2O3
6H2O
was prepared in laboratory to replace lime and investigate the
dealkalization and dealumination effect in processing middle-
low grade diasporic and gibbsite bauxite with Calcification-
Carbonization method.
Y. Wang et al.
Experimental
Raw Materials
The raw ores disposed with Calcification- Carbonization
method can be categorized into diasporic bauxite and
gibbsite bauxite which come from Aluminum Corporation
of China in Henan province and Weiqiao Aluminum
Electric Corporation in Shandong province. As can be
seen from Table 1, the alumina-silica mass ratio (A/S) is
very low.
In the preparation of 3CaO
Al2O3
6H2O, the sodium
aluminate solution (Na2O 240 g/L, Al2O3 197.4 g/L) was
prepared in an autoclave with analytical reagents sodium
hydroxide, aluminum hydroxide and deionized water.
According to chemical formula of 3CaO
Al2O3
6H2O,
a quarter of theoretical CaO addition amount was added at
90 °C for 3 h. Through cooling, filtration, washing and
drying, the purer 3CaO
Al2O3
6H2O can be observed.
The chemical composition and XRD pattern of pre-
pared 3CaO
Al2O3
6H2O can be observed in Table 2 and
Fig. 2.
Application of Tricalcium Aluminate Instead of Lime … 63

Table 1 Chemical composition Bauxite type Al2O3 SiO2 TFe CaO A/S
of diasporic bauxite in Henan and
gibbsite bauxite in Shandong (%) Diasporic 39.75 9.37 12.95 1.10 4.24
Gibbsite 58.11 19.02 2.90 0.10 3.06

Table 2 Chemical composition Composition CaO Al2O3 Else n(CaO)/n(Al2O3)

of prepared 3CaO
Al2O3
6H2O
(%) Content 44.19 26.41 29.40 3.05

5000 1 1−−3CaO⋅Al2O3⋅6H2O at specific temperature and agitation speed. After cooling,

1 1
filtration, washing and dying, the alumina leaching product
4000 1 was obtained. The bauxite was carbonized and digested for 3
times which indicates that the third leaching product is
3000 dealkalized and dealuminized red mud with
1 1
Intensity

1 1
2000 1 The chemical compositions of powder samples were
1
1
1000 1 ZSX100e) and the mineral composition of raw materials and
11
1 1 1 1
0 diffractometer (XRD).
20 40 60
2θ/(°)
Fig. 2 XRD pattern of prepared 3CaO
Al2O3
6H2O
Experimental Method
Calcification transformation was performed in KTFOZ-6.0
high pressure autoclave. CaO was added according to the
theoretical calcium-silicate ratio of calcification product
grossular. The additive CaO, raw ore and sodium aluminate
solution was kept at a specific temperature for 1 h. After
cooling, filtration, washing and dying, the calcification
product was obtained which will be used for subsequent
carbonization.
Calcification transformation was also performed in
KTFOZ-6.0 high pressure autoclave. The deionized water
was added according to the specific liquid-solid ratio. The
autoclave was sealed up and CO2 was bubbled below the
liquid level. All the reactants were kept in specific temper-
ature and pressure. After cooling, filtration, washing and
dying, the carbonization product was obtained which will be
used for subsequent alumina leaching. The first carboniza-
tion product is the carbonization product of calcification
product while the second carbonization product is the car-
bonization product of the first leaching product. The rest
product can be named in the same manner.
The alumina leaching process of carbonization products
was performed in a beaker containing low concentration
NaOH solution. The beaker was put into the DK-10DS
electro-thermostatic water bath. All the reactants were kept
Calcification-Carbonization method.
analyzed by X-ray fluorescence spectrometer (XRF,
1
111 11 1 1
11 1 products were characterized in the Bruker D8 Advance
1
80
Results and Discussion
Processing Diasporic Bauxite
The diasporic bauxite from Henan was disposed with
Calcification-Carbonization method. The calcification tem-
perature is chosen at 245 °C. The concentration of Na2O and
Al2O3 is 240.0 and 127.4 g L−1. The calcium-silicate ratio n
(CaO)/n(SiO2) = 3:0.64. The calcification reaction lasts for
1 h. In the carbonization process, the carbonization tem-
perature is specified at 100 °C. CO2 pressure and
liquid-solid ratio is separately 1.2 MPa and 10:1. The cal-
cification reaction lasts for 3 h. The alumina leaching is
conducted in NaOH (100 g L−1) solution at 60 °C. The
liquid-solid ratio and leaching time is respectively 10:1 and
1.5 h.
From Fig. 3 can be seen, the diaspore and kaolin in raw
bauxite converts to calcification product which is mainly
grossular in the calcification process. The grossular decom-
poses to the carbonization product which is mainly calcium
carbonate through the carbonization of high pressure CO2. In
the third carbonization product, the content of SiO2 and
Al2O3 accounts for 6.66 and 6.17% which shows that some
calcium silicate and aluminum hydroxide is also formed in
addition to calcium carbonate. But because of their amor-
phous state or low content, the diffraction peaks of calcium
silicate and aluminum hydroxide can’t be observed in the
XRD patterns. The total Fe content of the raw ore is only
2.90%. After a series of disposal, the bit of remaining
64 Y. Wang et al.

Fig. 3 XRD patterns of diasporic bauxite and transformation products. a Raw diasporic bauxite; b calcification product; c carbonization products;
d leaching products

Table 3 Chemical compositions Samples Al2O3 SiO2 CaO Na A/S

of diasporic bauxite and
transformation products (%) Diasporic bauxite 58.11 19.02 0.10 – 3.06
Calcification product 24.85 8.94 41.06 <0.01 2.78
First carbonization product 20.97 5.69 32.71 0.010 3.69
First alumina leaching product 11.38 6.41 38.00 2.61 1.78
Second carbonization product 11.41 6.41 40.10 0.035 1.78
Second alumina leaching product 8.30 6.96 43.61 1.14 1.19
Third carbonization product 6.17 6.66 43.55 0.056 0.33
Third alumina leaching product 4.72 6.77 46.67 0.36 0.70

goethite doesn’t appear in the XRD patterns of reaction
products too (Table 3).
After the third carbonization and leaching, Al2O3 content
in the solid product decreases to 4.72% and Na content
reduces to 0.36%. The alumina-silica ratio reduces from 3.06
of raw bauxite to 0.70 of the new-typed red mud. The
experimental results show that the application of tricalcium
aluminate instead of lime can also receive a good effect of
dealkalization and dealumination when processing diasporic
bauxite with Calcification-Carbonization method.
Processing Gibbsite Bauxite
The gibbsite bauxite from Shandong was also processed
with Calcification-Carbonization method. The gibbsite
Application of Tricalcium Aluminate Instead of Lime … 65

Table 4 Chemical compositions Samples Al2O3 SiO2 CaO Na A/S

of gibbsite bauxite and
transformation products (%) Gibbsite bauxite 39.75 9.37 1.10 – 4.24
Calcification product 19.96 8.43 33.77 0.61 2.36
First carbonization product 16.69 7.24 27.78 0.065 2.31
First alumina leaching product 9.93 7.43 35.10 0.082 1.34
Second carbonization product 9.29 7.25 33.18 0.068 1.28
Second alumina leaching product 6.77 7.67 36.72 0.032 0.88
Third carbonization product 6.60 6.99 35.00 0.054 0.94
Third alumina leaching product 4.36 6.66 36.79 0.045 0.65

bauxite is easier to dispose than diasporic bauxite, so a lower
calcification temperature is chosen at 180 °C. The concen-
tration of Na2O and Al2O3 is 140.0 and 74.3 g
L−1. The
calcium-silicate ratio n(CaO)/n(SiO2) = 3:0.64. The calcifi-
cation reaction lasts for 1 h. In the carbonization process, the
carbonization temperature is specified at 100 °C. CO2
pressure and liquid-solid ratio is separately 1.2 MPa and
10:1. The calcification reaction lasts for 3 h. The alumina
leaching is conducted in NaOH (100 g/L) solution at 60 °C.
The liquid-solid ratio and leaching time is respectively 10:1
and 1.5 h (Table 4).

Fig. 4 XRD patterns of diasporic bauxite and transformation products. a Raw gibbsite bauxite; b calcification product; c carbonization products;
d leaching products
66
From Fig. 4 can be seen, the gibbsite and kaolin in raw
bauxite converts to calcification product which is mainly
grossular in the calcification process, but the grossular
doesn’t decompose in the first carbonization. So in the XRD
pattern of first carbonization and leaching product, the main
phase is still grossular and hematite. The grossular decom-
poses to calcium carbonate at the second carbonization. In
the third carbonization product, the content of SiO2 and
Al2O3 accounts for 6.99% and 6.60% which shows that
some calcium silicate and aluminum hydroxide is also
formed in addition to calcium carbonate. But because of
their amorphous state or low content, the diffraction peaks of
calcium silicate and aluminum hydroxide can’t be observed
in the XRD patterns. After the third carbonization and
leaching, Al2O3 content in the solid product decreases to
4.36% and Na content reduces lower than 0.05%. The
alumina-silica ratio reduces from 4.24 of raw bauxite to 0.65
of the new-typed red mud. The experimental results show
that the application of tricalcium aluminate instead of lime
can also receive a good effect of dealkalization and dealu-
mination when processing gibbsite bauxite with
Calcification-Carbonization method.
The experimental results above show that the application
of tricalcium aluminate instead of lime in the processing of
middle-low grade bauxite with Calcification-Carbonization
method is feasible. The problem that low-concentration
aluminum in leaching liquor is difficult to recycle in
Calcification-Carbonization process was solved. The find-
ings help exert the efficiency and cleanliness of
Calcification-Carbonization method for alumina production
which has an extensive prospect.
Conclusion
The diasporic bauxite and gibbsite bauxite was separately
disposed with Calcification-Carbonization method by the
application of prepared tricalcium aluminate instead of lime.
The dealkalization and dealumination effect of the two types
of middle-low grade bauxite was investigated. After the
processing with Calcification-Carbonization method, the
alumina-silica mass ratio of diasporic bauxite reduces from
3.06 to 0.70. The content of Na2O and Al2O3 decreases to
Y. Wang et al.
0.49% and 4.72%. The alumina-silica mass ratio of gibbsite
bauxite reduces from 4.24 to 0.65. The content of Na2O and
Al2O3 decreases to 0.06 and 4.36%. The application of
prepared tricalcium aluminate replacing lime achieved ideal
results. It is feasible to recover the alkaline and aluminum
from middle-low grade bauxite with Calcification-
Carbonization method.
Acknowledgements This research was supported by the National
Natural Science Foundation of China (No.: U1202274, U1402271,
51504059), the Fundamental Research Funds for the Central Univer-
sities of China (No.: N140203005, N140204015), the Postdoctoral
Science Foundation Funded Project of China (No.: 2015M581352) and
the Education Department of Liaoning Province Science and Tech-
nology Research Project (L2014096).
References
1. Q.J. Zhao, Q.F. Yang, Y.F. Zhang, Technological and theoretical
research on alumina production in future. J. Chin. Soc. Rare Earths
30, 982–985 (2012)
2. W.X. Li, Y.X. Liu, Z.L. Yin, Opportunities and challenges facing
China’s alumina industry, in China Nonferrous Metals Society
Proceedings of the Fifth Academic Year (Central South University
Press, Changsha 2003), pp. 42–45
3. T.A. Zhang, G.Z. Lu, Y. Liu et al., A method of consuming Bayer
red mud. China, ZL201110275030.X
4. T.A. Zhang, G.Z. Lu, Y. Liu et al., An alumina leaching method
based on calcification-carbonization transformation processing
middle-low grade bauxite. China, ZL201110275013.6
5. T.A. Zhang, G.Z. Lu, Y. Liu, et al., A method of calcification
transformation by adding ores in alumina production. China,
ZL201410183034.9
6. T.A. Zhang, X.F. Zhu, G.Z. Lv et al., Calcification-carbonation
method for alumina production by using low-grade bauxite, in
Light Metals, San Antonio (TMS, 2013), pp. 233–238
7. G.Z. Lu, T.A. Zhang, X.F. Zhu et al., Calcification-carbonation
method for cleaner alumina production and CO2 utilization. JOM
66(9), 1616–1621 (2014)
8. G.Z. Lu, T.A. Zhang, X.F. Zhu et al., Research on the phase
transformation and separation performance in
calcification-carbonation method for alumina production, in Light
Metals 2013,TMS 2013 Annual Meeting and Exhibition,
pp. 245–250
9. B.I. Whittington, C.M. Cardile, The chemistry of tricalcium
aluminate hexahydrate relating to the Bayer industry. Int. J. Miner.
Process. 48, 21–38 (1996)
10. Z.Z. Qiu, L. Chen, Calcium aluminate replacing lime—solution
proposal in Bayer process. Light Met. (China) 3, 12–14 (1997)
 Low Temperature Reduction of Hematite
in Red-Mud to Magnetite

Sumedh Gostu, Brajendra Mishra, and Gerard P. Martins

Abstract
Red-mud, the residue generated from the Bayers processing of bauxite ore in Jamaica was
subjected to a low temperature reduction process. Hematite (*60 m%) was reduced to
magnetite employing a gas based mixture of CO, CO2 and N2 as a diluent. Extensive
thermodynamic study was conducted to identify the stability region for magnetite. ‘Optimal
conditions’ for the gas-phase reduction were determined to be: a processing temperature of
540 °C ± 10 °C, partial pressures CO(g) and CO2(g) each of 0.070 atm (bar) ± 0.001 atm
(bar)/inert diluent-gas: N2(g), for a conversion-time of 30 min. Mathematical model for
reduction based on unidirectional diffusion is also formulated in this paper.

Keywords
Red-mud Reduction Magnetite Bauxite residue

Introduction The sequence of extraction of the major elements present

Bayer’s process involves Hydrometallurgical caustic diges-
tion of bauxite ore. Selective precipitation of iron is asso-
ciated with the generation of solid by-product referred to as
red-mud. Burgeoning piles of the red-mud have become a
serious environmental concern worldwide owing to its fine
particle size, alkalinity and toxicity. The quantity of
Red-Mud produced in the Bayer’s process is a function of
the bauxite ore type. Typically about 0.8–2.5 tons of
red-mud is produced per ton of Aluminum metal produced in
the Hall Heroult electrolysis process. Estimated accumula-
tion of red-mud globally is approximately 3 billion tons [1].
Most of the red-mud is dry stacked and stockpiled, leaving
large quantities of untapped residue bearing large amounts of
metallic constituents namely Iron, Aluminum, Titanium,
Sodium and Silicon.
S. Gostu (&)
B. Mishra
Department of Material Science and Engineering,
Worcester Polytechnic Institute, Worcester, MA, USA
e-mail: sgostu@wpi.edu
G.P. Martins
Department of Metallurgical and Materials Engineering,
Colorado School of Mines, Golden, CO, USA
in the bauxite residue is crucial for remediation of the
reserve. Removal of Iron in the preliminary process stages
eases extraction of other non-ferrous constituents of
red-mud. Red-Mud slurry was subjected to High-intensity
magnetic separation recovering Fe2O3 in the magnetic por-
tion which would form a feed stock for iron making [2].
Simultaneous soda ash roasting and carbon reduction was
tried on red-mud to obtain metallic iron reduced from
hematite and a water soluble sodium aluminate phase [3–6].
Magnetic separation of the reduced iron was reported to be
not successful due to mineralogical adherence of the various
phases present in red-mud [3, 4]. Carbothermic reduction
was also tried by Staley and Sumedh et al. Iron was believed
to replace Calcium in Pervoskite (CaTiO3) lattice which
eventually caused a decrease in the grade of magnetic pro-
duct [7, 8]. A process similar to producing Direct Reduced
Iron (DRI) employing carbon as a reductant was tried to
obtain metallic iron [9]. The production of pig iron in the
process flowsheet for remediating red-mud was tried by
smelting operation [4, 10]. Aluminum and Titanium were
successfully recovered but the process developed were not
feasible commercially. Carbidization of red-mud to obtain
Hagg’ carbide was tried by Regina et al.

© The Minerals, Metals & Materials Society 2017 67

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_10
68
The research reported in this thesis employs a low tem-
perature gas based reduction to obtain magnetite from
red-mud. The ferromagnetic nature of magnetite makes it
viable for beneficiation method for enriching red-mud. In a
research done by University of Missouri Rolla, three red-muds
were reduced using three carbon based reductants: charcoal,
coal and sawdust in Ar atmosphere to generate magnetite.
A magnetic separation using the Davis tube magnetic separator
yielded high recovery but a lower grade of the magnetically
separated magnetite [11]. Yanyan Liu et al generated mag-
netite from red-mud employing Iron pyrite (FeS2) as reductant
and were successful in generating a low Iron non-magnetic
product used for refractory material manufacture.
Experimental
Jamaican red-mud was used for reduction studies. Hematite
was reduced to magnetite in a tube furnace (1′ quartz tube).
Reduction was carried out in an atmosphere of CO, CO2 and
N2. An online CO/CO2 monitor measured the exit gas
composition. PCO/PCO2 is adjusted to lie in the stability
region of magnetite.
The reduction products are analyzed for its elemental
composition using Inductively Coupled Plasma—Optical
Emission Spectroscopy, X-ray Diffraction for phase
Fig. 1 Experimental set up for reduction experiments Fe2O3
S. Gostu et al.
composition, % conversion to magnetite using Mössbauer
spectroscopy (Fig. 1).
Results and Discussion
Stability Diagram
The thermodynamic equilibrium constant for a reduction
reaction is translated to represent PCO/PCO2 as a function of
temperature. The probable phases of iron chosen for this
thermodynamic analysis include: Fe2O3, Fe3O4, FeO and
Fe3C represented in Eqs. 1–4. The data for the free energy of
formation for the reactions were obtained from the High
School Chemistry (HSC) software. The thermodynamic
stability diagram is shown in Fig. 2.
3Fe2 O3 ðsÞ þ COðgÞ ¼ 2Fe3 O4 ðsÞ þ CO2 ðgÞ ð1Þ
Fe3 O4 ðsÞ þ CO(g) ¼ 3FeOðsÞ þ CO2 ðgÞ ð2Þ
Fe3 O4 ðsÞ þ 6COðgÞ ¼ Fe3 CðsÞ þ 5CO2 ðgÞ ð3Þ
3FeOðsÞ þ 5COðgÞ ¼ Fe3 CðsÞ þ 4CO2 ðgÞ ð4Þ
All the reduction experiments are carried out in the sta-
bility region of magnetite (Fig. 3).
Low Temperature Reduction of Hematite in Red-Mud to Magnetite 69

Fig. 2 Stability diagram for Fe–

C–O system Ptotal=1 atm

10000

100 Fe3C

1 FeO Fe2O3 to Fe3O4

PCO/PCO2
0 200 400 600 800 1000 1200 1400 1600 Fe3O4 to FeO
0.01
Fe3O4 Fe3O4 to Fe3C
0.0001
FeO to Fe3C
0.000001
Carbon solubilizaƟon
1E-08

1E-10
T (oC)

Reduction Experiments U(t) is the (time-dependent) dimensionless posi-

Initial reduction studies were conducted utilizing 0.65 g of
red-mud sample. Optimum conditions for complete reduc-
tion were found by varying Temperature (475, 500, 550,
600 °C). The gas flow rates were maintained at 75–
125 ml/min for CO and 90–140 ml/min for CO2 respec-
tively. Three CO/CO2 ratios: 1:1, 1:1.5 and 1.5:1 for the
durations 10, 20 and 30 min respectively.
The phases of Iron in the reduction product included
Magnetite, unreduced hematite, cementite and some Iron
titanium and Iron Aluminum.
An increase in temperature (from 475 to 600 °C),
CO/CO2 and reduction time increases the conversion of
hematite to magnetite. Optimized parameters for magnetite
reduction were chosen to be: CO/CO2 = 1:1, reduction time:
30 min and Temperature: 540 °C. These parameters were
used to generate large batches of magnetite.
tion of the Fe3O4/Fe2O3 (reaction) interface,
relative to the gas-Fe3O4 interface. The scal-
ing factor is the initial (vertical) height Ho of
the (red-mud) compact; i.e. U(t) = H(t)/Ho
k, K are kinetic-parameters
Deff is the effective diffusion-coefficient of CO2
within the porous Fe3O4 where both ordinary
and Knudsen diffusion can occur in parallel
a1, b2 are stoichiometric coefficients in the gas-solid
conversion-reaction (CO and Fe3O4,
respectively)
eg
CG2 ; CBULK
G2
are, respectively, the concentration of CO2(g) at
the reaction-interface, where equilibrium is
achieved/maintained between Fe2O3(s), Fe3O4(s)
and CO(g) in mutual contact, and in the bulk
gas-phase—i.e. at the gas/Fe3O4 interface,
where it is maintained time-independent
qMoL-S1 is the molar density of Fe2O3.

Mathematical Model for Conversion of Fe2O3 (in The model was verified experimentally by measuring the
Red Mud) to Magnetite length of the magnetite product layer formed. For the veri-
fication of the model, CO and CO2 flow rates at 1:1 (8.5 and
A mathematical model based on unidirectional planar 3%), reduction times (10, 20 and 30 min) and Temperature
(540, 500 and 465 °C) were varied (Figs. 5, 6, 7 and 8).
moving interface (Fe2O3/Fe3O4) was developed such that pffi
diffusion of CO–CO2 occurs within the porous magnetite In developing the model, /(t) is fit with t.
layer. The representation of the basis for the model is shown
/ðtÞ ¼ eðtÞ=e
in Fig. 4.
pffiffiffi where e(t) is the length of the magnetite phase vertically.
k pffi pffi
UðtÞ ¼ t¼K t Ɛ is the total length of the sample.
Ho
pffiffiffi " ! As temperature decreases, k the slope of the linear fit
BULK   #12
k Ceq
G2  CG2 b2 c decreases. This is a characteristic of diffusion controlled
K¼ ¼ 2Deff
Ho ðHo Þ2 a1 qMOLS1 ð1  /Þ reaction.
70 S. Gostu et al.

Fig. 3 Magnetite conversion surface plots v/s time and temperature at a CO:CO2 = 1:1, b CO:CO2 = 1:1.5 and c CO:CO2 = 1.5:1
Low Temperature Reduction of Hematite in Red-Mud to Magnetite 71

γ>1

H(t) H(t) < Ho

Fe3O4 γ =1
Ho ≥ Z(t) ≥ 0
H(t)= Ho
0 < t < t
Fe2O3 Z(t) γ<1
x H(t) > Ho
0
0

Fig. 4 Product profile for mathematical model

Fig. 5 Linear fit for reduction at 8.5% gas, 540 °C

8.5 % 540 oC
0.7
0.65
y = 0.1521x
0.6
R² = 0.998

Ø(t)
0.55
0.5
0.45
0.4
3 3.5 4 4.5 5

Fig. 6 Linear fit for reduction at 8.5% gas, 500 °C

8.5 % 500 oC
0.65

0.6
y = 0.141x
0.55
Ø(t)

R² = 0.9921
0.5

0.45

0.4
3 3.5 4 4.5 5

Fig. 7 Linear fit for reduction at 8.5% gas, 465 °C

8.5 % 465 oC
0.5
y = 0.1012x
0.45
R² = 0.9791
Ø(t)

0.4

0.35

0.3
3 3.5 4 4.5

√
72 S. Gostu et al.

(a)

(b)

(c)

ε
ε(t)

Fig. 8 Reactions at 3% gas concentrations at 540 °C, a 10 min, b 20 min, c 30 min

Low Temperature Reduction of Hematite in Red-Mud to Magnetite
Conclusions
The following are the conclusions of this research focused
on the valorization of the Bauxite residue.
Conversion of hematite to magnetite in red-mud is a
viable conversion process and can be achieved at low partial
pressures of CO2(g)
N2(g) employed ensures that a reducing
atmosphere is maintained.
The solid phase reduction products obtained from the gas
phase reduction of red-mud contained Fe3O4 (56.4–
80.5 wt%), Fe2O3 (0–20 wt%), Fe3C (4.8–6.8 wt%) and
paramagnetic 2+ and 3+ phases (14–22 wt%).
The (preliminary) optimal-conditions for gas-phase re-
duction of the (Jamaican) red-mud investigated in the
research, and reported in this thesis, are: processing tem-
perature of 540 °C ± 10 °C, partial pressures CO(g) and
CO2(g) each of 0.070 atm (bar) ± 0.001 atm (bar)/inert
diluent-gas: N2(g), for a conversion-time of 30 min.
References
1. Bauxite Residue Management: Best Practice, World Aluminum,
European Aluminum Association, April 2013
2. E. Jamieson, A. Jones, D. Cooling, N. Stockton, Magnetic separation
of red sand to produce value. Miner. Eng. 19, 1603–1605 (2006)
3. Y. Li, J. Wang, X. Wang, B. Wang, Z. Luan, Feasibility study of
iron mineral separation from red mud by high gradient supercon-
ducting magnetic separation. Physica C 471(3–4), 91–96 (2011)
4. W.A. Stickney, M.O. Butler, J.E. Mauser, O.C. Fursman, Utiliza-
tion of red mud residues from alumina production (Bureau of
73
Mines. U.S. Dept. of Interior, Bureau of Mines, Washington, D.C.,
1970), 32 pp
5. R. Kumar, J.P. Srivastava, P. Premchand, Utilization of iron values
of red mud for metallurgical applications. Environ. Waste Manag.
108–119 (1998)
6. G. Li, M. Liu, M. Rao, T. Jiang, J. Zhuang, Yuanbo Zhang,
Stepwise extraction of valuable components from red mud based
on reductive roasting with sodium salts. J. Hazard. Mater. 280,
774–780 (2014)
7. A.K. Staley, An investigation into the pyrometallurgical and
electrometallurgical extraction of iron from red mud generated in
the processing of bauxite ores. Ph.D. thesis, Colorado School of
Mines, 2002
8. B. Mishra, S. Gostu, Opportunities for high volume commercial
products conversion from bauxite residue, in Bauxite Residue
Valorisation and Best Practices Conference (2015)
9. W. Liu, J. Yang, B. Xiao, Application of Bayer red mud for iron
recovery and building material production from aluminosilicate
residues. J. Hazard. Mater. 161, 474–478 (2009)
10. K. Jayasankar, P.K. Ray, A.K. Chaubey, A. Padhi, B.K. Satapathy,
P.S. Mukherjee, K. Jayasankar, Production of pig iron from red
mud waste fines using thermal plasma technology. Int. J. Miner.
Metall. Mater. 19(8), 679–684 (2012)
11. R. Caupain, Low-temperature gas-phase carbidization of iron-
bearing constituents in red mud. M.S. thesis, Colorado School of
Mines, 2004
12. Q. Xiang, X. Liang, M. Schlesinger, J. Watson, Low-temperature
reduction of ferric iron in red mud (TMS (The Minerals, Metals
and Materials Society), 2001)
13. Y. Liu, B. Zhao, Y. Tang, P. Wan, Y. Chen, Z. Lv, Recycling of
iron from red mud by magnetic separation after co-roasting with
pyrite. Thermochem. Acta 588, 11–15 (2014)
14. G.P. Martins, Private communication—mathematical-model for-
mulation for conversion of “Fe2O3” (in red-mud) by Fe3O4 by CO
(g); 30 Nov 2015
 Recovery of Iron-, Titanium-Bearing
Constituents from Bauxite Ore Residue
via Magnetic Separation Followed
by Sulfuric Acid Leaching

Guanghui Li, Foquan Gu, Jun Luo, Bona Deng, Zhiwei Peng,
and Tao Jiang

Abstract
Bauxite ore residue is a hazardous byproduct derived from alumina production, containing
iron, titanium, aluminum and other valuable metals. The feasibility of an integrated
technological route for recovering titanium from bauxite ore residue was verified in this
study. Titanium-bearing iron concentrate was first recycled through magnetic separation
process, and titanium was further leached from the non-magnetic material derived from the
upper-stream process by using sulfuric acid. The effects of magnetic intensity on the
recovery of iron, and the effects of H2SO4 concentration, leaching temperature, leaching
time and liquid to solid ratio on the leaching of titanium have been investigated. The results
showed a magnetic concentrate with total iron grade of 56.39% and TiO2 content of 8.66%
was obtained under a two-stage magnetic separation process (intensity: 0.8 and 0.2 T,
respectively), and magnetic recoveries of iron and titanium attained 55.79 and, 17.37%
respectively. 96.36% TiO2 was subsequently leached from the non-magnetic material under
the optimal conditions of sulfuric acid concentration of 8 mol/L, leaching temperature of
70 °C, leaching time of 120 min, and liquid to solid ratio of 8.

Keywords
Bauxite ore residue Titanium Magnetic separation Sulfuric acid leaching

Introduction
Bauxite ore residue is a hazardous byproduct derived from
alumina production, approximately 0.8–1.5 tons of bauxite
ore residue are generated for producing 1 ton of alumina
depending on the properties of bauxite ores and operating
conditions [1]. Currently, there are about 2.7 billion tons
bauxite ore residue accumulated around the world. And this
amount is currently increasing by approximately 120 million
tons per annum [2]. The large quantity and high alkalinity
(pH 10–12.5) of bauxite ore residue result in high costs for
land filling and cause heavy pollution, thus the disposal of
G. Li
F. Gu
J. Luo
B. Deng
Z. Peng
T. Jiang (&)
School of Minerals Processing and Bioengineering, Central South
University, Changsha, 410083, Hunan, China
e-mail: jiangtao@csu.edu.cn
G. Li
e-mail: liguangh@csu.edu.cn
bauxite ore residue had been being a big challenge con-
fronting the whole alumina industry [3].
However, bauxite ore residues also contain valuable
constituents, such as iron, titanium, aluminum, sodium, rare
earths and other trace elements, so it can also be considered
as a secondary resource [4, 5]. Concerning recovery of
valuable components from bauxite ore residue, the recovery
of iron [6, 7] and titanium [4, 8, 9] are greatly focused on.
Pyro-metallurgical process and hydrometallurgical pro-
cess are both used to recovery titanium in bauxite ore residue
[10]. The pyro-metallurgical methods are usually include
extraction of pig iron. The bauxite ore residue was smelted
with additives in an electric furnace to obtain molten iron,
and the slag mainly contains titanium dioxide, alumina and
silica. Then the slag was further treated to produce high-
grade titanium dioxide product [4]. Direct pyro-metallurgical
processes are often limited due to their high energy con-
sumption and large quantity of residues. Hydrometallurgical

© The Minerals, Metals & Materials Society 2017 75

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_11
76 G. Li et al.

methods have often been extensively investigated for The XRD patterns of the bauxite ore and bauxite ore
recovery of titanium from bauxite ore residue. Various acids residue were shown in Figs. 1 and 2, respectively. It was
have been examined, such as dilute sulfuric acid, concen- obviously showed that the primary aluminum-bearing and
trated sulfuric acid and hydrochloric acid, etc. [11, 12]. silicon-bearing minerals such as diaspore (Al2O3
H2O) and
Leonardou et al. [4] proposed a process to recovery titanium kaolinite (Al2O3
2SiO2
2H2O) in the bauxite ore disappeared,
from bauxite ore residue by leaching with diluted sulfuric instead andradite (Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4)
acid at atmospheric pressure, and the titanium recovery emerged. The main titanium-bearing minerals in the bauxite
reached 65.4%. ore residue were titanomagnetite (Fe2.75Ti0.25O4), kassite
In our previous work, it is found that approximately (CaO
2TiO2
H2O), sodium tri-titanate (Na2O
3TiO2).
96.31% alumina was extracted from a bauxite ore in China
via pre-desilication and Bayer digestion process [13].
Thereafter valuable titanium, iron and other components
were enriched in bauxite ore residue. Based on the above
research, an integrated technological route was verified to
make a comprehensive recovery of iron and titanium from
above-mentioned bauxite ore residue. The process mainly
consists of recovery of TiO2-bearing iron concentrate from
bauxite ore residue by direct magnetic separation and sub-
sequent extraction of titanium from non-magnetic fraction
via sulfuric acid leaching.

Experimental

Materials
Fig. 1 XRD pattern of bauxite ore (K kaolinite, D diaspore, A anatase,
H hematite, T titanomagnetite)
Bauxite ore residue The process of pre-desilication
and Bayer digestion of bauxite ore have been intensively
introduced in the literature [13]. The alumina could be
effectively recovered by pre-desilication and Bayer process
under the optimum conditions as followed: pre-desilication
process by leaching with sodium hydroxide concentration of
50 wt%, leaching temperature of 95 °C, leaching time of
30 min, liquid to solid ratio of 5 mL/g. Bayer digestion of
the bauxite concentrate obtained by pre-desilication was
conducted under the conditions of 240 g/L Na2O, 131.6 g/L
Al2O3, ak = 3(ak is the mole ratio of Na2O to Al2O3 in the
liquor), and digestion temperature of 280 °C, digestion time
of 90 min. 96.31% alumina was extracted from the bauxite
concentrate via Bayer process.
The main chemical compositions of the above-mentioned
bauxite ore residue were shown in Table 1. The original
bauxite ore was taken from Yunnan province of China, and
Fig. 2 XRD pattern of bauxite ore residue (A andradite, T titanomag-
its contents were also shown in Table 1.
netite, S sodium tri-titanate, H hematite, K kassite, M magnetite)

Table 1 Main chemical Material TFe Al2O3 SiO2 TiO2 Na2O CaO
compositions of bauxite ore and
bauxite ore residue (wt%) Bauxite ore 19.05 37. 67 12.88 7.24 0.03 0.36
Bauxite ore residue 35.74 6.71 5.80 13.04 5.15 9.28
Recovery of Iron-, Titanium-Bearing Constituents from Bauxite Ore … 77

Reagents Sulfuric acid of analytical grade were used in

the experiments.

Methods

As the main titanium-bearing minerals in the bauxite ore

residue were titanomagnetite, kassite, and sodium tri-titanate
(Fig. 2), magnetic separation process can be conducted to
recover iron and titanium due to the magnetic character of
titanomagnetite, and the remaining titanium could be further
recovered from non-magnetic fraction by sulfuric acid
leaching. Titanium-containing leachate could be used to
prepare titanium pigment via hydrolysis and calcinations
[14].

Preparation of bauxite ore residue The main

steps to obtain bauxite ore residue were depicted in Fig. 3.
The pre-desilication were carried out in a DY-8 autoclave
equipped with eight 150 mL stainless steel pots rotating in a
bath of glycerin. At the beginning of each trail, bauxite ore
was added into the pots and mixed with appropriate concen-
tration sodium hydroxide solution at a given liquid-to-solid Fig. 3 Experimental flow sheet
ratio. Then, the sealed pots were soaked in the bath at specific
temperature and agitated at 60 rpm. After leaching for a given
where e is the recovery of iron and titanium; c is the yield; a,
period of time, the slurry was cooled and separated by filtra-
b are TFe or TiO2 grade of samples before and after mag-
tion. The leaching residue was washed with hot water and
netic separation, respectively.
dried at 105 °C oven. The digestion experiments were carried
out in a DY-4 autoclave which was heated by molten salt. The
slurry (100 mL liquor mixed with 20 g bauxite concentrate
H2SO4 leaching process The non-magnetic fraction
prepared by pre-desilication) was added into the pots and
obtained from magnetic separation was leached with sulfuric
mixed with appropriate concentration of sodium aluminate
acid to extract titanium. All batch experiments were con-
solution (240 g/L Na2O, 131.6 g/L Al2O3, ak = 3). Then, the
ducted in a 200 ml beaker, fitted with a plastic stirrer with a
sealed pots were soaked and rotated in the molten salts bath at
suitable stirring speed. The beaker was placed in a water bath.
given temperature for a given time. The slurry was then
After leaching for a given period of time, the slurry was
cooled and separated by filtration. The Bayer digestion lea-
filtered with a vacuum filter to obtain the residue and filtrate.
chate was used to produce Al2O3, and the digestion residues
The TiO2-rich filtrate was collected for further extract of
(bauxite ore residues), were subjected to magnetic separation
titanium, and the residue was put into a vacuum drying oven
subsequently.
for 4 h consistently at 105 °C. Thereafter, it was collected for
determination of chemical compositions by X-ray fluores-
cence analysis (Axios Max, PANalytical, Netherlands). The
Magnetic separation The bauxite ore residue
leaching of TiO2 (gT ) were determined as follows:
obtained from the Bayer process were ground to 98%
passing 74 lm in particle size for magnetic separation. The  
WðT2 Þ M2
recovery of iron by magnetic separation and TFe and content gT ¼ 1   100% ð2Þ
WðT1 Þ M1
of TiO2 of magnetic fraction and non-magnetic fraction were
analyzed respectively. The recovery of iron and titanium was
calculated as follows: where WðT1 Þ and WðT2 Þ are TiO2 contents of
non-magnetic fraction and sulfuric acid leaching residue,
cb
e¼  100% ð1Þ respectively; M1 and M2 are the mass of non-magnetic
a fraction and sulfuric acid leaching residue, respectively.
78
Results and Discussion
Recovery of TiO2–Bearing Iron Concentrate
from Bauxite Ore Residue by Magnetic
Separation
Effects of magnetic intensity The effects of mag-
netic intensity of two-stage magnetic separation on the
grade of TiO2 and TFe, as well as the recovery of TiO2 and
Fe were investigated, the results was shown in Figs. 4 and
5 respectively. It is observed from Fig. 4, the grade of TiO2
and the total iron grade was subjected to slight change with
the increase of magnetic intensity of the first-stage magnetic
separation, and the recovery of Fe and TiO2 gradually
increased for the increase of the yield of magnetic fraction.
Due to the low total iron grade (42.82–50.44% TFe),
magnetic concentrate of the first-stage magnetic separation
can not meet the iron-making requirements. To obtain the
qualified magnetic concentrate, a two-stage magnetic sepa-
ration process were carried out. Overall, the 0.8 T was
selected as the first-stage magnetic separation intensity, and
its magnetic fraction shifted to the second-stage magnetic
separation. It is shown from Fig. 5, when the second-stage
magnetic separation intensity was 0.2 T, the grade of total
iron grade reached 56.39%, which meets the elementary
requirements of iron-making. With the magnetic intensity
increased, the grade of total iron and TiO2 gradually
reduced, in contrast, the recovery of iron and TiO2
increased.
It can be concluded from the above results, TiO2-bearing
iron concentrate with total iron grade of 56.39% and TiO2
grade of 8.66% was obtained with recoveries of iron and
Fig. 4 Effect of magnetic intensity of first-stage on the recovery of
iron and TiO2
G. Li et al.
Fig. 5 Effect of magnetic intensity of second-stage on the recovery of
iron and TiO2
TiO2 of 55.79, 17.37% respectively by magnetic separation,
and the first-stage and second-stage magnetic separation
intensity of 0.8 and 0.2 T, respectively. The main chemical
composition of TiO2-bearing iron concentrate and
non-magnetic fraction is shown in Table 2. The TiO2-bear-
ing iron concentrate can be used as iron-making burden after
agglomeration.
Leaching TiO2 from Non-magnetic by Sulfuric
Acid Liquor
The non-magnetic fraction was used to further recover tita-
nium through sulfuric acid leaching. The effects of parame-
ters such as sulfuric acid concentration, leaching temperature,
leaching time, liquor to solid ratio and stirring speed on the
leaching of non-magnetic fraction were investigated
intensively.
Effects of sulfuric acid concentration The
effects of sulfuric acid concentration on the leaching of iron,
titanium and calcium were studied under the leaching tem-
perature of 70 °C, leaching time of 120 min, liquid to solid
ratio of 8, stirring speed of 300 rpm. It was shown in Fig. 6
that the leaching ratio of iron, titanium and calcium
increased with the increasing sulfuric acid concentration.
When sulfuric acid concentration increased from 2 to
8 mol/L, the leaching ratio of titanium increased from 76.82
to 96.36%, and thereafter, this value increased slightly. In
the meanwhile, the leaching ratio of calcium had the similar
trends with titanium. In order to obtain higher titanium
leaching ratio, the suitable sulfuric acid concentration is
8–10 mol/L.
Recovery of Iron-, Titanium-Bearing Constituents from Bauxite Ore … 79

Table 2 Main chemical Separation products TFe Al2O3 SiO2 TiO2 Na2O CaO
compositions of iron concentrate
and non-magnetic fraction (wt%) TiO2-beraing iron concentrate 56.3 2.4 2.3 8.7 0.2 3.7
Non-magnetic fraction 21.3 4.8 6.4 21.2 2.1 17.9

Fig. 6 Effect of sulfuric acid concentration on the leaching of iron, Fig. 8 Effect of leaching time on the leaching of iron, titanium and
titanium and calcium of non-magnetic fraction calcium of non-magnetic fraction

from 30 to 70 °C, the leaching ratio of titanium increased

from 74.59 to 96.36%. The leaching of calcium generally kept
about 87.63–90.02%. Thus, the optimal leaching temperature
is recommended as 70–90 °C.

Effects of leaching time The effect of leaching time

Fig. 7 Effect of leaching temperature on the leaching of iron, titanium
and calcium of non-magnetic fraction
on the leaching of iron, titanium and calcium was presented
in Fig. 8. It was indicated that the leaching ratio of titanium
increased from 90.35 to 96.36% as the leaching time
increased from 30 to 120 min at the sulfuric acid concen-
tration of 8 mol/L, leaching temperature of 70 °C, liquid to
solid ratio of 8, and stirring speed of 300 rpm. Meanwhile,
the leaching ratio of calcium generally kept around 91.99–
93.28%. Besides, the leaching of iron increased with the
leaching time elongated. Overall, the suitable leaching time
was 90–120 min.

Effects of leaching liquid to solid ratio The

Effects of leaching temperature The effects of effects of liquid to solid ratio (L/S, mL/g) on the leaching of
leaching temperature on the leaching ratio of iron, titanium iron, titanium and calcium were studied under the sulfuric acid
and calcium were studied under the sulfuric acid concentra- concentration of 8 mol/L, leaching temperature of 70 °C,
tion of 8 mol/L, leaching time of 120 min, liquid to solid ratio leaching time of 120 min, and stirring speed of 300 rpm. It
of 8, stirring speed of 300 rpm. It was shown from Fig. 7 that was observed from Fig. 9 that the leaching ratio of iron, ti-
with the leaching temperature increased, the leaching of iron tanium and calcium increased with the increasing of L/S. As
and titanium increased first, as the leaching temperature raised the L/S increased from 2 to 8, the leaching ratio of titanium
80
Fig. 9 Effect of liquid to solid ratio on the leaching of iron, titanium
and calcium of non-magnetic fraction
Fig. 10 Effect of stirring speed on the leaching of iron, titanium and
calcium of non-magnetic fraction
increased from 88.04 to 96.36%. Thus, the appropriate liquid
to solid ratio is 8–10.
Effects of stirring speed The effects of stirring speed
on the leaching of iron, titanium and calcium were studied
under the sulfuric acid concentration of 8 mol/L, leaching
temperature of 70 °C, leaching time of 120 min, and liquid
to solid ratio of 8. It was observed from Fig. 10, as the
stirring speed increased, the leaching ratio of iron, titanium
increased first, then remained constant when the stirring
speed was over 300 rpm. The suitable stirring speed is rec-
ommended at 300–400 rpm.
G. Li et al.
Fig. 11 XRD patterns of: a non-magnetic fraction, b acidic leaching
residue (A andradite, C anhydrite, G goethite, N nacrite, K kassite,
H hematite, S sodium tri-titanate)
Mechanisms on Sulfuric Leaching Process
The reactions between non-magnetic fractions and sulfuric
acid can be characterized as follows:
CaO
2TiO2
H2 O þ 3H2 SO4 ! CaSO4 þ 2TiOSO4 þ 4H2 O
ð3Þ
Na2 O
3TiO2 þ 3H2 SO4 ! Na2 SO4 þ 3TiOSO4 þ 4H2 O
ð4Þ
Fe2 O3 þ 3H2 SO4 ! Fe2 ðSO4 Þ3 þ 3H2 O ð5Þ
The reactions of kassit (CaO
2TiO2
H2O) with sulfuric acid
generated anhydrite (Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4),
which was slightly soluble in water, resulting in the lower
leaching ratio of calcium than that of titanium.
The XRD analysis of the non-magnetic fraction, and the
leaching residue obtained after sulfuric acid leaching at the
optimum leaching conditions were presented in Fig. 11. It
was observed that in the non-magneitic material, the main
mineral phases were andradite (Ca3(Fe0.87Al0.13)2
(SiO4)1.65(OH)5.4), hematite (Fe2O3) nacrite (Al4(Si4O10)
(OH)8), kassite (CaO
2TiO2
H2O) and sodium tri-titanate
(Na2O
3TiO2). After sulfuric acid leaching, these mineral
phases disappeared, and anhydrite (CaSO4), goethite
(FeOOH) emerged in the acidic leaching residue. The XRD
results confirmed the above-mentioned minerals that andra-
dite, nacrite, kassit and sodium tri-titanate were soluble in
sulfuric acid, but the Ca2+ could react with sulfuric acid to
generate CaSO4, resulting in the production of the above
secondary precipitate.
Recovery of Iron-, Titanium-Bearing Constituents from Bauxite Ore …
Conclusions
The feasibility of an integrated technological route for
recovery titanium from bauxite ore residue was verified, and
the following conclusions were obtained:
(1) TiO2-bearing iron concentrate with 56.39% TFe and
8.66% TiO2 was obtained using magnetic separation
with two-step field intensity of 0.8 and 0.2 T, the
recoveries of iron and TiO2 were 55.79 and 17.37%
respectively. The TiO2-bearing iron concentrate can be
used as iron-making burden after agglomeration.
(2) The leaching ratio of titanium from the non-magnetic
fraction reached 96.36% under the optimal conditions
of sulfuric acid concentration of 8 mol/L, leaching
temperature of 70 °C, leaching time of 120 min, and
liquid to solid ratio of 8.
Acknowledgements The authors wish to express their thanks to the
National Natural Science Foundation of China (Nos. 51234008 and
51174230) for financial support. This work was also financially sup-
ported by the Co-innovation Center for Clean and Efficient Utilization
of Strategic Metal Mineral Resources.
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 Processing Diasporic Red Mud
by the Calcification-Carbonation Method

Xiao-feng Zhu, Ting-an Zhang, Guo-zhi Lv, Fang-fang Guo,

Wei-guang Zhang, Yan-xiu Wang, Li-qun Xie, and Long Wang

Abstract
The novel calcification-carbonation method was proposed to process the diasporic red mud
discharged from Bayer process alumina plant. In this study, Batch experiments were
performed to evaluate the potential effects of important parameters such as temperature,
amount of CaO added, CO2 partial pressure and carbonation cycles on the recovery of
alkali and alumina. The results showed that 78.74% alumina was recovered from the
diasporic red mud with decreases in the mass ratios of Al2O3 to SiO2 (A/S) from 1.27 to
0.27. The Na2O content in the processed red mud was less than 0.3 wt%, and it can be used
as a construction material.

Keywords
Calcification-carbonation method Dasporic red mud Hydrogarnet Alkali Alumina

Introduction At present, Bayer process is the most common method for

The alumina production of China reached 58,979 kt in 2015,
which accounts for 51.2% total output of the world [1].
Depending on the source of bauxite and the digestion
efficiency of alumina, 1.0–1.5 t of red mud was produced
during the production of each ton of alumina [2]. Currently,
it is estimated that 300 million tons of red mud have been
accumulated in China, and the accumulation is accruing at
an annual rate of 50 million tons [3]. More than 90% bauxite
in China is diasporic with the typical character of high
aluminum oxide and silica [4], therefore, most of the red
mud discharged from alumina refinery plant is diasporic red
mud in China.
X. Zhu
School of Materials Science and Engineering, Lanzhou University
of Technology, Lanzhou, 730050, China
X. Zhu
T. Zhang (&)
G. Lv
F. Guo
W. Zhang
Y. Wang
L. Xie
L. Wang
School of Metallurgy, Key Laboratory of Ecological Metallurgy of
Multi-Metal Intergrown Ores of Education Ministry, Special
Metallurgy and Process Engineering Institute, Northeastern
University, Shenyang, 110819, China
e-mail: zta2000@163.net
alumina refinery both in China and abroad [5]. Owing to the
reason that 3(Na2O
Al2 O3
2SiO2)
Na2X
nH2O, which is
known as desilication product (DSP) generated in the
digestion of bauxite, and turned into the red mud, contributes
to the alkalinity, alkali loss, and alumina loss in red mud
produced by the Bayer process [6]. Over about 50 years
research on the subject of red mud disposal, little evidence
shows of any significant utilization of the red mud due to the
great barriers of volume, performance, cost and risk, there-
fore, it has to stack in situ. Because of the red mud generally
exists as a highly alkaline slurry (pH 10–12.5), it may bring
potential risk for storage sites.
We proposed a new method (referred to as the calcifi-
cation–carbonation method) to process red mud derived
from the Bayer alumina refinery plant [7–9]. In this new
method, the DSP is transformed into hydrogarnet through
calcification process firstly. Thereafter, the hydrogarnet is
decomposed by CO2 gas through carbonation process, and
alumina is subsequently extracted with the NaOH solution
at lower temperature, Fig. 1 illustrated the process chart of
calcification- carbonation method. In previous work [10],
the performance of processing gibbsite red mud by the
new method has been investigated in detail. This study

© The Minerals, Metals & Materials Society 2017 83

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_12
84
Fig. 1 Process chart of the calcification-carbonation method
focus on the processing diasporic red mud derived from a
China alumina refinery plant, the potential effects of
important parameters such as temperature, amount of CaO
added, and CO2 partial pressure on this process was
investigated, the reaction mechanism were discussed as
well.
Experimental
Experimental Materials
Red mud used in this study was supplied by an aluminum
Company in Shanxi Province of China, which generated by
the Bayer process for leaching of diasporic. The chemical
compositions of the red mud were shown in Table 1. The
X-ray diffraction (XRD) pattern of the red mud was shown
in Fig. 2. The identified mineral phases were Fe-contain
hydrogarnet, hematite, and cancrinite.
NaOH and CaO used in this study were analytical-grade
chemical reagents, and CO2 with the purity greater than 99%
was supplied from a gas cylinder (40 L)
Table 1 Chemical composition Composition Al2O3
of the red mud
Content (wt%) 24.15
X. Zhu et al.
Experimental Method
The calcification and carbonation experiments were per-
formed in a series 1-L stainless steel autoclave (Fig. 3)
equipped with a magnetic agitator and a
proportional-integral-derivative (PID) temperature con-
troller. In the calcification process, a mixture of distilled
water and 50 g red mud were added to the autoclave, the
temperature of the autoclave was raised to the predetermined
value then holding for 1 h, after reaction, the slurry was
separated. In the carbonation process, the calcified residue
obtain from the calcification process was mixed with dis-
tilled water, after heated to set temperature, CO2 gas was
injected to the autoclave from the gas cylinder for 2 h. The
magnetic agitator was operated at 300 r/min in calcification
and carbonation experiments.
To extract Al2O3 from carbonated red mud and evaluate
the effect of carbonation, parallel experiments were per-
formed in a water bath with a mechanical agitator operated at
300 r/min. The carbonated residue was leached with a
100 g/L NaOH solution with a liquid-to-solid ratio of 5:1 at
60 °C for 1.5 h.
The recovery rate of Al2O3 was expressed as follows:
ðA=SÞO  ðA=SÞr
g¼  100% ð1Þ
ðA=SÞO
where (A/S)o and (A/S)r are the ratio of alumina to silica in
original red mud and the processed red mud, respectively.
Results and Discussion
Effect of Temperature on the Calcification
Process
These experiments were performed at a CaO-to-SiO2 molar
ratio of 3:0.64, liquid-to-solid mass ratio of 4:1, and within
the temperature range of 85–180 °C. As shown in Fig. 4,
temperature substantially affected the calcification of dias-
poric red mud. The Na2O content in calcified residue grad-
ually decreased from 2.41 to 0.23% with increasing
temperature from 85 to 180 °C, indicating that high tem-
perature advantageously affects the calcification process.
Notably, the Na2O content in calcified residue declined
slightly when the temperature was greater than 160 °C,
indicating that the reaction had been completed at 160 °C.
SiO2 Fe2O3 Na2O CaO MgO K2O L.O.I
19.01 16.97 8.44 12.96 0.68 0.64 11.35
Processing Diasporic Red Mud by the Calcification-Carbonation … 85

2.4
Na
Na2O
2.0

1.6

ω(%)
1.2

0.8

0.4

0.0
80 100 120 140 160 180
T(°C)

Fig. 2 XRD pattern of red mud Fig. 4 Effect of temperature on the Na2O (Na) content in the calcified
residue

1--Ca(OH)2 2--Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4
3--Ca3Al2(SiO4)1.53(OH)5.88 4--Na1.82(Al2Si3O10)
5--Na2Al2(Al2Si2)O10(OH)2
1
31 2
2 1 23 2 3 23 31 1
2 1 11 160°C

140°C

120°C

4 4 4 100°C

55 5 5 85°C

20 30 40 50 60 70
Fig. 3 ZRY-K01-0.5/10 high pressure autoclave 2θ/°

Fig. 5 XRD patterns of the calcified residues at various temperatures

Figure 5 shows the XRD patterns of the calcified residues
at various calcification temperatures. The intensity of
diffraction peaks of cancrinite phase decreased with tem-
perature increase, and the hydro- garnet phase increased
instead, the hydrogarnet phase become dominant when the
calcification temperature was increased to 120 °C, which
showed that the cancrinite transformed to hydrogarnet in the
calcification process. In this transformation, the Fe-contain
hydrogarnet was always exist in the calcified residue and not
changed.
residue decreased with increasing CaO-to-RM (red mud)
mass ratio from 30 to 90%, and reached a minimum value of
0.22% at CaO-to-SiO2 mass ratio of 90%. However, when
the CaO-to-SiO2 mass ratio greater than 70%, the Na2O
content declined slightly, indicating that the addition of
excess CaO had little effect on the calcification process.
When the CaO-to-SiO2 mass ratio greater than 50%, the
Na2O content had already reached a desired level of 0.71%
and the high alkalinity of the red mud was reduced signifi-
cantly via the calcification.

Effect of CaO Addition on the Calcification

Process
These experiments were performed at temperature of 160 °C,
liquid-to-solid mass ratio of 4:1, and CaO-to-SiO2 mass ratio
of 30–90%. As shown in Fig. 6, the Na2O content in calcified
Effect of Temperature on the Carbonation
Process
To study the effect of temperature on the carbonation process,
the calcified residue obtained at the conditions of 120 °C,
86 X. Zhu et al.

1.20

1.15

1.10
ω(%)

A/S
1.05

1.00

0.95

0.90
30% 50% 70% 86.9% 90% 0.6 0.7 0.8 0.9 1.0 1.1 1.2
m(CaO)/m(RM) P(CO2)(MPa)

Fig. 6 Effect of CaO addition on the Na2O (Na) content in the Fig. 8 Effect of CO2 pressure on the A/S of carbonated residue
calcified residue

in Fig. 8. The CO2 pressure had no remarkable effect on the

A/S of carbonated residue in the range of 0.8 to 1.2 MPa, the
1.20 A/S just decreased from 1.15 to 1.09 with the CO2 pressure
increased from 0.6 to 0.8 MPa, then increased to 1.14,
indicating that the CO2 pressure was not a determining factor
1.15 for carbonation process.
A/S

Effect of Multi-steps Carbonation

1.10
For the reason once carbonation did not acquired good
results, therefore, the multi-step carbonation were con-
1.05 ducted, the calcified residue were carbonated and alkali
80 90 100 110 120 130 140 soluble 5 time cycles, the results showed in Fig. 9. The A/S
T(°C)
in the carbonated residue decreased from 0.92 to 0.27 with
Fig. 7 Effect of temperature on the A/S of carbonated residue increased of carbonate frequency from 1 to 5, corresponding

CaO-to-SiO2 mass ratio 50%, and liquid-to-solid mass ratio

of 4:1. The carbonation experiments were conducted at CO2 1.4
pressure of 1.2 MPa and liquid-to-solid mass ratio of
10:1. Figure 7 showed the effect of temperature on the 1.2
Al2O3-to-SiO2 mass ratio (A/S) of carbonated residue, the
A/S decreased from 1.2 to 1.1 with increasing of carbonation 1.0
temperature from 80 to 140 °C, corresponding alumina
0.8
recovery rates increased from 5.50 to 13.39%. Overall, the
A/S

recovery rate of alumina did not reached a relative ideal

0.6
effect, this may be related to the kinetics conditions of the
carbonation process.
0.4

0.2
Effect of CO2 Pressure on the Carbonation
Process 0 1 2 3 4 5
Carbonate frequency
These experiments were performed at 120 °C and Fig. 9 Effect of carbonation frequency on the A/S of carbonated
liquid-to-solid mass ratio of 10:1, the results were illustrated residue
Processing Diasporic Red Mud by the Calcification-Carbonation … 87

alumina in red mud can be recovered, with decreases

1--Ca3Al2(SiO4)1.53(OH)5.88 2--Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4
3--Ca2SiO4 4--CaCO3 5--Fe2O3 in the mass ratios of Al2O3 to SiO2 from 1.27 to 0.27,
the Na2O content in the processed red mud was less
4 than 0.3 wt%, and it can be used as a construction
1 5 4
4 4 material.
1 313 51 1 5
13 4 4 44 1 1 (2) The optimal conditions for calcification were observed
to be a CaO-to-SiO2 mass ratio of 50%, a temperature
of 160 °C. The CO2 pressure was not a determining
factor for carbonation process, and multi-step carbon-
ation had significant effect on the carbonation process.
1
1
1
2
1 21 1 2
1 1 1
2 2
Acknowledgements This research was supported by the National
Natural Science Foundation of China (No.: U1202274, U1402271,
51504059), the Fundamental Research Funds for the Central Univer-
20 30 40 50 60 70 sities of China (No.: N140203005, N140204015), the Postdoctoral
2θ/° Science Foundation Funded Project of China (No.: 2015M581352)
and the Education Department of Liaoning Province Science and
Fig. 10 XRD analysis of calcifying, carbonizing and leaching residue Technology Research Project (L2014096).

alumina recovery rates increased from 27.56 to 78.74%.

Previous work indicated that the hydrogarnet had a compact
squamous surface [10], which difficult to be carbonated by
CO2 gas. In the multi-steps carbonation, the hydrogarnet was
decomposed gradually, therefore alumina recovery rate
increased obviously.
X-Ray Diffraction Analysis
Figure 10 showed XRD patterns of residues after different
process. The identified phases of calcified residue were hy-
drogarnet and Fe-contain hydro- garnet, after carbonated, the
main phase became calcium carbonate, hematite, calcium
silicate, which indicating that the hydrogarnet was decom-
posed. In addition, there was unreact hydrogarnet in the
carbonated residue. The aluminum hydroxide phase was not
detected in the XRD patterns, because of the low crys-
tallinity of the generated products.
Conclusions
(1) A calcification–carbonation method was developed
and investigated for the recovery of alkali and alumina
from diasporic red mud. Through this process, 78.74%
References
1. The website of the International Aluminium Institute, http://www.
world-aluminium.org/
2. S. Agatzini-Leonardou et al., Titanium leaching from red mud by
diluted sulfuric acid at atmospheric pressure. J. Hazard. Mater. 157
(2–3), 579–586 (2008)
3. L. Zhong, Y. Zhang, Y. Zhang, Extraction of alumina and sodium
oxide from red mud by a mild hydro-chemical process. J. Hazard.
Mater. 172(2–3), 1629–1634 (2009)
4. R. Zhanga et al., Recovery of alumina and alkali in Bayer red mud
by the formation of andradite-grossular hydrogarnet in hydrother-
mal process. J. Hazard. Mater. 189(3), 827–835 (2011)
5. G. Power, M. Gräfe, C. Klauber, Bauxite residue issues: I. Current
management, disposal and storage practices. Hydrometallurgy 108
(1–2), 33–45 (2011)
6. S. Vishwajeet et al., Sequestration of carbon dioxide (CO2) using
red mud. J. Hazard. Mater. 176(1–3), 1044–1050 (2010)
7. X. Zhu et al., Basic research on calcification transformation
process of low grade bauxite. in Paper presented at the 142nd TMS
Annual Meeting and Exhibition, San Antonio, Texas, 3 March
2013, pp. 239–244
8. T.A. Zhang et al., A method of consuming Bayer red mud. China
Patent, ZL201110275030.X
9. T.A Zhang et al., An alumina leaching method based on
calcification-carbonization transformation processing middle- low
grade bauxite. China Patent, ZL201110275013.6
10. X.-f. Zhu et al., Recovery of alkali and alumina from Bayer red
mud by the calcification–carbonation method. Int. J. Miner. Metall.
Mater. 23(3), 257–268 (2016)
 Research of Flocculants and Dewatering
Additives for Filtration of Red Mud

Cao Wenzhong, Zheng Fuliang, Tian Weiwei, and Zhong Hong

Abstract
The polymer flocculants and dewatering additives have been applied to separation of Red
Mud for thirty years. In recent years, it is pointed out that the additives is related to the
presence of other ions. The experimental results show that the effect of mud dewatering and
mud compaction will affect the production capacity and purity of product. The potential of
using water absorbing polymer or synthetic dispersant to change the rheological property of
the slurry is also summarized in the end. The combination of these effects, with the new bio
polymer to improve the primary pour into the washing bath of the overflow liquid clarity
and recovery of sodium hydroxide is also researched.

Keywords
Dewatering additives Carbonate Causticizing Flocculation

Introduction replace large use of starch. More adsorption place could be

Synthetic macro-molecular polymer as the substitute of
starch and wheat flour has been used in red-mud slurry
flocculation of alumina industry for almost 30 years, but
some alumina plants still holds the traditional starch floc-
culation technology. People believed that synthetic
macro-molecular polymer could get over the interference of
organic impurity and enhance the efficiency of settlement
separation at the same time, but in the red-mud slurry which
contains a great deal of carbonate ions, starch’s use was
helpful to the clarification of the slurry. It was found by
research that the interference of carbonate ions could be
eliminated by slaked lime causticizing and synthetic
macro-molecular polymer could reduce the disturbance of
humic salt and organic impurity. Factory test shows that
small amount of synthetic macro-molecular polymer can
C. Wenzhong (&)
Z. Fuliang
T. Weiwei
Environmental Engineering College of Nanchang University,
Nanchang, 330031, Jiangxi, China
e-mail: w_z_cao@hotmail.com
Z. Hong
College of Chemistry and Chemical Engineering, Central South
University, Changsha, 410083, Hunan, China
set aside on the red-mud ore grain that promote the deeper
adsorption on the surface of ore grain for more humic salt
and organic impurity’s removal.
Experiment
Experiment Reagent
The polymer(HPAM, PAAS) are made in Nanchang
University: Ordinary starch; Soda ash(AR), Hydroxide
sodium(AR), Hydroxide calcium(white lime CP).
Experiment Methods
After crushed and comminuted, bauxite was confected to a
mixture by proportional correction liquor in a blend tank. Put
it into an autoclave and lixiviated under high pressure for
90 min. The digested ore slurry was refrigerated and
decompressed to normal pressure. Then add in solution and
dilute to a certain concentration before settlement separation
experiment.

© The Minerals, Metals & Materials Society 2017 89

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_13
90 C. Wenzhong et al.

Lab settlement experiments were carried out under
aqueous thermostat. The size of settlement tube is
U30 * 220 mm. The turbidity of overflowing liquid or
supernatant was determined by eyes’ observation, filtration
and weighing, and light-electricity turbidimetric method. As
for the low turbidity samples, their turbidity was determined
by checking calibration curve which was drawn according to
the absorbence of turbidity standard solution determined by
spectrophotometer with 1 cm tube at 660 nm.
Experiment Materials
Mineral composition of bauxite in Chinese are diasporic
bauxite. Lime chemical composition (lime mixed with
incompletely burnt limestone): CaO 72.37%; MgO 6.55%.
Chemical composition of bauxite digestion liquor is shown
in Table 1.
Experimental Results and Discussion
Effects of Carbonate Ions on Flocculation
Settlement
The diluted digested ore slurry contained caustic alkali and
the content of carbonate sodium amounted to 31.63 g/L. It
was proved by experiments that if such digested ore slurry
components was carried through settlement separation only
depending on synthetic macro-molecular polymer, the
velocity of settlement separation and the packing charac-
teristics of red-mud were both subjected to disadvantage
affects.
Further research showed that the affects were due to the
ore grain in the mixture which could adsorb carbonate ions
firstly and interfere synthetic macro-molecular flocculant’s
flocculation. When the carbonate sodium in the digested ore
slurry were causticized again by adding white lime, synthetic
macro-molecular flocculant’s flocculation; especially the
velocity of settlement separation and the packing charac-
teristics of red-mud, could be improved. The test dates are
showed in Tables 2, 3 and Figs. 1, 2.
Because of the particularity of alumina production tech-
nology, the digested ore slurry tends to contain a great deal
of carbonate during production process and make the
red-mud’s settlement separation more complex. Until today,
some alumina plants still adopt the traditional most effective
starch as digested ore slurry flocculation. But, experiments
indicated that adding starch for red-mud’s settlement sepa-
ration, carbonate ions still largely affected the settlement
separation’s velocity and clarification of red-mud slurry,
which could be seen in Table 4. So many carbonate’s
remove by adding white lime and causticizing, and use of
synthetic macro-molecular polymer replacing starch, do

Table 1 Bayer diluted digested Composition Al2O3 Na2Ok Na2OT Solids a k

slurry composition
Content (g/l) 133.60 137.40 155.84 51.7 1.69
(Notes Na2Ok Content of caustic alkali, Na2OT Content of all alkali, ak the mole ratio of sodium oxide and
alumina)

Table 2 Effects of hydroxide Test Content of hydroxide calcium Settlement velocity(cm/min) Turbidity
calcium on flocculation settlement number (g/l) (g/l)
Content of polymer (mg/l)
1.0 2.0 3.0 4.0
1 0 3.8 8.1 9.6 11.3 0.24
2 5 24.5 55.7 85.3 119.2 0.13
3 10 31.4 62.5 100.8 136.7 0.11

Table 3 Effects of hydroxide Test number Content of hydroxide calcium (g/l) Mass ratio of liquid-solids of Turbidity (g/l)
calcium on red-mud dehydration compressed red-mud(L/S)
Content of polymer (mg/l)
1.0 2.0 3.0 4.0
A 0 5.88 5.71 5.40 5.12 0.24
B 5 4.08 4.0 3.84 3.77 0.13
C 10 3.39 3.35 3.33 3.30 0.11
Research of Flocculants and Dewatering Additives for Filtration … 91

32 65

30
60

28 HPAM
PAAS
55
26

50
24

22 45

0 g/L Ca(OH)2
20
5.0 g/L Ca(OH)2 40
18 10.0 g/L Ca(OH)2

35
16

14 30
.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 0 2 4 6 8 10 12

flocculant dosage (mg/L)

Fig. 1 Influence of adding hydroxide calcium on red-mud dehydration Fig. 4 Effects of flocculation on light permeance rate
(open square A, filled circle B, filled triangle C)
good not only to settlement separation’s velocity of red-mud
40 slurry, but also to improve the red-mud’s packing.

35

50 mg/L STARCH
Effects of Polymer on Humic Salt Impurity
30 100 mg/L STARCH
150mg/L STARCH
Diasporic bauxite generally contains a little humic salt
25
impurity, which is a disadvantage to alumina production
20 technology. In digested ore slurry, such organic substance
concentrate and to a certain extent adsorbed on the surface of
15 ore grain, which often cause foam spillover in the top of
setting bath, and bring bad effects to normal production.
10
The existence of humic salt and other organic carbon
5
impurity, either alone or mixed together, will affect the
25 30 35 40 45 50 55 60 65 efficiency of red-mud’s settlement separation and the clari-
g/L) fication of supernatant badly. Such bad affects can be
removed by using synthetic macro-molecular polymer
Fig. 2 Effects of carbonate on settlement efficiency of adding starch replacing starch and more adsorption place could be set aside
(open square A, filled circle B, filled triangle C)
on the red-mud ore grain, which also help the organic
impurity’s adsorption and removal. Synthetic polymer floc-
Table 4 Effects of carbonate sodium on settlement efficiency of culants degree of different ions on the upper “clear liquid” in
adding starch the light transmission rate is significant (shown in Fig. 4).
Test Starch Carbonate Settlement Turbidity Figure 4 shows that with the increased use of synthetic
number content sodium velocity (g/l) polymer, the upper “clear liquid” in the transmittance tended
(mg/l) content(g/l) (cm/min) to increase. When the amount of the flocculant reaches a
a 100 31.6 9.3 0.24 certain volume, the upper “clear liquid” and through Light
b 100 40.0 8.6 0.22 rates decline with the volume of the flocculant increasing.
c 100 50.0 7.5 0.41 High degree of synthetic ion polymer to the red mud surface
electrical properties have strong surface charge neutraliza-
tion, small degree of synthetic ion flocculant on the mineral
surface charge have weak neutralization
92
Summary
(1) The disadvantageous effect of carbonate ion in red-mud
slurry on flocculation settlement can be reduced by
hydroxide calcium causticizing.
(2) The carbonate ion, humic salt and organic impurity in
alumina red-mud slurry will be firstly adsorbed on the
surface of slurry ore grains, which will affect floccu-
lation settlement. The effects of carbonate ion on set-
tlement efficiency of adding starch should not be
ignored.
(3) The technology of using synthetic macro-molecular
polymer instead of starch to clarify slurry can make
more place available to adsorb humic salt and organic
impurity, which will be removed from slurry with
red-mud, and the effect of clarification can be further
promoted.
(4) When the sodium carbonate in the digested ore slurry
was causticized by adding white lime the packing
characteristics of red-mud could also be improved.
C. Wenzhong et al.
References
1. Hunt(United Kingdom), Aluminum industry, the progress of
chemical additives, meetings to exchange information (1995) 7
2. Gu Songqing, Physical and chemical properties of synthetic
polymer flocculants and applied technologies. Light Metals 212
(5), 8–13 (1996)
3. Cao Wenzhong, Zhong Hong, Tianwei Wei, Red mud polymer and
electrical properties of mineral surface functional group selected
coagulation. Nonferrous Metals 58(1), 58–61 (2006)
4. D.P. Spitze, A.S. Rothenberg, H.I. Heitner, Development of new
bayer process flocculants. in A Collection of Papers From the TMS
Annual Meeting, ed. by M. Sorlie (Light Metals , US), pp. 167–171
(1991)
5. M. Faneitte, A. Galarraga, T. Foster, Utilization of new polymer in
aluminum industry. in A Collection of Papers From the TMS
Annual Meeting, ed. by E. Phillips (Light Metals, US), pp. 129–131
(1994)
6. R.L. Keendy, Simple reagent techniques to improve aluminu m
oxide processing. in A Collection of Papers From the TMS Annual
Meeting, ed. by M. Sorlie (Light Metals, US), pp. 141–145 (1991)
7. S. Weir, G.M. Moody, The importance of flocculant choice with
consideration to mixing energy to achieve efficient solid-liquid
separation. Miner. Eng. 16(2), 109–113 (2003)
8. A.J. McFarlane, K.E. Bremmell, J. Addai-Mensah, Optimising the
dewatering behaviour of clay tailings through interfacial chemistry,
orthokinetic flocculation and controlled shear. Powder Technol. 160
(1), 27–34 (2005)
9. L.A.D. Chin, Chemical additives in bayer process. in A Collection
of Papers From the TMS Annual Meeting, ed. by M. Sorlie (Light
Metals, US), pp. 155–158 (1991)
 Characterization of Activated Alumina
Production via Spray Pyrolysis

Wang Long, Zhang Ting’an, Lv Guozhi, Zhao Aichun, Ma Sida,

and Zhang Weiguang

Abstract
A novel method was developed to prepare activated alumina via spray pyrolysis of
aluminum chloride solution. In this paper, activated alumina was obtained by spray
pyrolysis in tube furnace with aluminum chloride solution as raw materials in different
temperatures. X-ray diffraction (XRD), scanning electron microscope(SEM) and the
specific surface area analysis were used to characterize the spray pyrolysis products,
respectively. XRD results showed that the crystal phase composition of activated alumina
can be controlled through adjusting pyrolysis temperature. The crystal structure of c-Al2O3
in the products conformed to the requirements of the index of activated alumina. Most of
pyrolysis products were porous structure which the particle size was around 5 lm under
scanning electron microscope. With the activated alumina were examined by specific
surface area analysis, the products existed as inkbottle-shaped and parallel-plate pores.
Pyrolysis products more conformed to the requirements of activated alumina after
examined by XRD, SEM, and the specific surface area.

Keywords
Aluminium chloride Activated alumina Spray pyrolysis Crystallization process
Porous structure

Introduction in production of wear resistant composites [3], and usage as

Activated alumina is a porous aluminum oxide which is one
of the most useful inorganic chemical products and excep-
tionally known for its high surface area among other alu-
minum oxides and possess large pore volume, The material
is also known for other widely used, such as adsorbent in
liquid and gas purification processes [1], usage in plasma
spray coating for production of advanced ceramics [2], usage
W. Long
Z. Ting’an (&)
L. Guozhi
M. Sida
Z. Weiguang
Key Laboratory of Ecological Metallurgy of Multi-Metal
Intergrown Ores of Ministry of Education, Special Metallurgy and
Process Engineering Institute, School of Metallurgy of
Northeastern University, Shenyang, 110819, China
e-mail: zta2000@163.net
Z. Aichun
School of Material Science and Engineering, Taiyuan University
of Science and Technology, Taiyuan, 030024, China
solid electrolytes in batteries for electric vehicles and energy
storage systems [4]. Alumina is used as catalyst support in
heterogeneous catalysis [5] and ionic exchange processes
[6]. Activated alumina prepared methods are mainly include
rapid dehydration roasting aluminum hydroxide or roasting
pseudo-boehmite. Unfortunately, these methods exist many
drawbacks, such as using raw ore for production indirectly,
high energy consumption, and complex operation, etc.
According to the above problem, this paper uses the spray
pyrolysis technique to prepare activated alumina products.
Various techniques have been used to activated alumina,
such as limestone sintering process, sodium carbonate sin-
tering process, acid process [7–9], spray pyrolysis, etc. Spray
pyrolysis has become one of the most widely used low cost,
simple technique, requires short processing time and can be
performed in atmospheric conditions for the preparation of
oxide. The main advantages of spray pyrolysis over

© The Minerals, Metals & Materials Society 2017 93

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_14
94 W. Long et al.

conventional methods include low cost, simple technique. 1.8

Because of its low cost and simple technique, the spray 1.6
pyrolysis, widely used in the industry, thin film materials
1.4
[10–14], ultrafine metal and oxide powder preparation
1.2

Chlorinity/wt%
[14–20]. With the advantages of open to atmospheric envi-
1.0
ronment operation, wide substrate scope, simple equipment
and easy to realize large-scale preparation, etc., this method 0.8

shows the broad application prospect. 0.6

In this work high surface area activated alumina was 0.4

synthesized using AlCl3 solution as the raw material via
spray pyrolysis which was reported in our previous work
[21, 22]: Direct spray pyrolysis of aluminum chloride solu-
tion for alumina preparation and Research on activated
alumina obtained by spray pyrolysis method. Although, the
technique of processing alumina from AlCl3 solution
reported in this work and our previous work [21, 22] is
novel, the innovation of the current study comes specifically
from tube furnace employed in using AlCl3 solution as the
raw material via spray pyrolysis which resulted into acti-
vated alumina. Another attraction of the current study is
attributed to characterization of activated alumina production
study presented. XRD, SEM and the specific surface area
analysis are used to characterize the spray pyrolysis prod-
ucts. This paper studies on tube furnace in different tem-
peratures on the effect of pyrolysis efficiency, surface
structure, the phase composition, systematically studies the
mechanism of pyrolysis reaction.
Experimental
Materials
Reagents for the experiments are AlCl3
6H2O (Analytically
pure), distilled water (Homemade).
0.2
0.0
600 700 800 900 1000
T/K
Fig. 1 Chlorine content of pyrolysis products at different temperatures
Researches showed that decomposition efficiency of the
AlCl3 solution in the pyrolysis reaction and product categories
were affected by temperature. When the pressure was 0.2 MPa
and aluminium chloride solution concentration was 15%,
spray pyrolysis experiments were conducted as the tempera-
ture was between 600–1000 °C. From Fig. 1, the chlorine
contents were gradually reduced with temperature rised which
was illustrated that temperature had important influence to
the process of spray pyrolysis. When the temperature was
1000 °C, the chlorine content was as low as 0.18%.
Crystalline structure and morphology
Regardless the precursors’ composition, the diffraction anal-
ysis (Fig. 2) shows that the products under 600 °C by spray
pyrolysis have a crystalline structure which corresponds to
simple cubic crystal alumina (Al2O3, a = b = c = 7.95, a = b =
c = 90°). When the temperature is 1000 °C, the products have
a change that crystalline structure corresponds to rhombo-
hedral alumina (Al2O3, = b = 4.7540, c = 12.9900, a = b =
90°, c = 120°). The crystallite sizes where calculated using
Scherrer formula:

Experimental Process
2 2
Activated alumina were prepared in tube furnace (Home- 2 2
2
2
2 22
made) at different pyrolysis temperatures. The physical 2 2

characterization of activated alumina was studied by using

1 1 1
XRD (Model PW3040/60) and surface structure of the
Intensity

products was measured by using SEM (Model Hitachi

1 1 1
SU8010). The open-framework structure of the products
with different conditions were carried out by using ASAP
(Model ASAP2020). 1 1 1

1 1 1

Results and Discussion 0 10 20 30 40 50 60 70 80 90 100

Performance of AlCl3 solution by spray pyrolysis in Fig. 2 XRD analysis of spray pyrolysis process Fig. 3 height and
tubefurnace FWHM curve of the 311 diffraction peak with temperature
Characterization of Activated Alumina Production via Spray … 95

700 as the (311) diffraction direction and the (400) diffrac-

650 Height 1.2
FWHM
tion direction. When the temperature is 1000 °C, the alu-
600
550 1.0
minum oxide crystal shape changed, new alumina crystal
500 were observed. The higher peak intensity corresponds to
450 0.8 sample 900 °C, and can be the consequence of the crystal

FWHM/
Height/cts

400 growth with the rise of temperature. But the much higher
350 0.6
peak intensity corresponds to sample 1000 °C than sample
300
900 °C. This is because a-Al2O3 generated in large quanti-
250 0.4
200
ties and crystal more completely. Using only the diffraction
150 0.2 analysis it is difficult to establish the influence of the tem-
100 perature on the nucleation and crystal growth. However,
50
600 700 800 900 1000
0.0 during the pyrolysis process, more analysis can be visualised
T/℃ in the scanning electron microscopy studies.
From Fig. 2, 311 diffraction peak intensity gradually
Fig. 3 Height and FWHM curve of the 311 diffraction peak vary with strengthened, half tall wide with temperature rise and fall,
temperature
alumina from the amorphous form to crystal. The intensity
of diffraction peak was enhanced at 800 °C, diffraction peak
Kk 0:9k
D¼ ¼ ð1Þ half high width slightly higher, which prove that 800 °C
FWHM
COSh FWHM
COSh
formed more crystalline incomplete crystal alumina. The
The largest crystallite sizes of the (440) diffraction diffraction peak half width decreased rapidly at 900 °C,
direction (Table 1) correspond to the samples obtained from same as the diffraction peak intensity. More fully explain
the precursor at 900 °C which can be explained considering product crystallization under 900 °C. The diffraction peak
that the crystal nucleus growth gradually along the intensity was enhanced at 1000 °C, and the diffraction peak
(440) diffraction direction. But when the temperature was half high width decreased rapidly, under 1000 °C, that is
1000 °C, the new diffraction peaks were observed with the because that a lot of amorphous crystallization intermediate
(440) diffraction direction disappeared, which was as same into completely alumina.

Table 1 XRD analysis of spray T/°C 2h/° hlk H F d/10–10 m

pyrolysis product
600 37.8437 311 118.01 0.9446 2.37,738
43.0017 400 40.75 0.9446 2.10341
67.5108 440 241.96 0.672 1.38631
700 37.9096 311 189.94 0.9446 2.37339
42.7693 400 81.64 0.9446 2.1143
67.6124 440 349.89 0.8659 1.38561
800 37.9163 311 361.59 1.0234 2.37301
42.8003 400 130.36 0.4723 2.11285
67.5733 440 490.25 0.2362 1.38632
900 37.5814 311 363.81 0.7085 2.39337
42.6872 400 104.56 0.4723 2.11818
67.5108 440 471.32 0.1968 1.38744
1000 25.7337 012 833.14 0.1574 3.46197
35.295 104 1318.91 0.1968 2.54299
37.9262 110 686.06 0.1574 2.3724
43.4821 113 1283.25 0.2558 2.08128
52.6877 024 506.84 0.1771 1.73728
57.6053 116 1001.67 0.1771 1.60013
66.5976 214 532.44 0.2362 1.40423
68.3222 300 601.92 0.096 1.37181
76.9592 119 165.30 0.2362 1.23795
96
Temperature is the main factors in the reaction, through
the analysis of microcosmic morphology under different
temperatures and energy spectrum analysis, study the influ-
ence of temperatures on reaction. Of which oven powder in
800 °C drift out along with the furnace thermal, which is not
completely in the middle of the product (Fig. 4).
a 600
c 900
e oven powder in 800
Fig. 4 SEM of spray pyrolysis products
W. Long et al.
From Table 2, Al, O atom ratio is about 2:3 at Point B,
which illustrated that aluminum oxide generated at 600 °C,
but the content is less, the chlorine content is higher in
crystal. When temperature is 900 °C, no chlorine residue
was observed in energy spectrum analysis. Chlorine residues
in products reduced with rise of temperature. Point G
b 700
d 1000
Characterization of Activated Alumina Production via Spray … 97

Table 2 Energy spectrum Element A B C D E F G

analysis atomic percentage (%)
O 35.573 59.898 50.741 55.450 48.442 62.470 44.482
Al 62.910 39.244 47.270 44.550 51.558 33.063 45.567
Cl 1.517 0.858 1.989 – – 4.467 9.951

a 600 ×3000 b 700 ×3000

c 800 ×3000 d 900 ×3000

e 1000 ×1000 f Oven powder in 800 ×3000

Fig. 5 Microstructure analysis of product

98
Table 3 The BET and Pore Temperature/°C
volume and pore width of spray
product under different BET specific surface area/m2/g
temperature BJH average pore size/nm
BJH total pore volume/cm3/g
chlorine content is higher than point F chlorine content,
which stated that in spray pyrolysis process, the external
temperature was higher than internal temperature in droplets,
first crusting, reaction more fully, the chlorine content was
low. Raising temperature and reducing the droplet volume
could make the droplets heated rapidly which will be more
conducive to response.
From Fig. 5, the 800 °C powder is a hollow spherical
micro powder furnace, and the size of most around 5 µm,
which has reached the expected effect of spray device. Small
droplets in the falling process by surface tension and
spherical in shape. In the process of heating, droplet surface
first crusts, internal solute subsequently poly shrinkage in the
ball shell. Products not found more complete spherical par-
ticles, that sphere in aluminum chloride in the process of
falling and water continue to react and decomposition,
caused by broken sphere, and under the effect of high tem-
perature and at the bottom of each other of adhesion and
sintering together, thus forming the porous product.
Specific surface area of the pyrolysis products
The specific surface areas of spray products under different
temperatures were calculated by the BET method; the results
are shown in Table 3. Compared with spray products under
different temperatures exhibits a sharp decrease of the
specific surface area; this decrease is attributed to the
increase of temperature, consistent with the SEM results
(Fig. 5). The specific surface area of pyrolysis products
conformed to the requirements of the index of activated
alumina. The method provided a new way of preparing
activated alumina.
Conclusions
By means of tube furnace and different reaction conditions
the pyrolysis experiments obtained the optimum conditions
for the reaction: 1000 °C, 15%, 0.2 MPa with 0.18% of
chlorine content in tube furnace. The chlorine contents were
gradually reduced with temperature rised which was illus-
trated that temperature had important influence to the pro-
cess of spray pyrolysis. Pyrolysis products in tube furnace
the products have multiple diffraction peaks, generate
c-Al2O3 and a-Al2O3. The crystallization of pyrolysis
products in tube furnace more completed, effect of pyrolysis
was better. Products coexist as granulate in tube furnace. As
W. Long et al.
600 800 800(2 mol)
105.0158 56.4125 56.08
10.5952 15.1607 13.95
0.2592 0.2465 0.2672
temperature increased, pores in product collapsed, forming
irregular concave surface morphology. The products in
tube furnace conformed to the requirements of the index of
activated alumina and provided a new way of preparing
activated alumina.
Acknowledgements This work was financially supported by the Joint
Funds of the National Natural Science Foundation of China(No.
U1202274, No.U51374064), the National Natural Science Foundation
of China (No.51004033), the National Science and Technology Sup-
port Program (No.N100302005), doctor startup foundation in Taiyuan
University of Science and Technology(20142001), science and tech-
nology research projects of Liaoning education department(L2014096),
specialized Research Fund for the Doctoral Program of Higher Edu-
cation(20120042110011).
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pyrolysis method. Light Metals (2016)
 Part III
Alumina and Bauxite: Non-traditional Resources
 New Process Research on Aluminium
Production from Non-Traditional Aluminum
Resource by Microwave Chlorination

Ting-an Zhang, Guozhi Lv, Long Wang, Zhihe Dou, Weiguang Zhang,
Yukun Huang, and Yanxiu Wang

Abstract
A novel method was developed to prepare aluminium via fluidizing chlorination with
untraditional aluminum resources as raw materials. The main steps in this method were:
alumina transformed into aluminium chloride through fluidizing chlorination; aluminium
chloride reacted with NaOH solution for aluminium hydroxide and NaCl; NaOH and Cl2
were recycled from NaCl solution by electrolytic process. The new process for preparing
aluminium resources by fluidizing chlorination method was proposed to realize efficient
separation of the valuable components in non-traditional aluminum resources such as fly
ash or low grade bauxite, silicon in untraditional aluminum changed into SiCl4 in fluidizing
chlorination which could be used as raw materials for high purity Si products. Furthermore,
the tailings emission of this process was quite lower than that of Bayer process. This paper
mainly introduce the principle of this new process, the thermodynamics of fluidizing
chlorination is analysis as well.

Keywords

Non-traditional aluminum Anhydrous aluminium chloride Microwave chlorination
Fluidized bed Chlor-alkali industry

Introduction taken advantage [7–10]. More and more researcher both at

The fly ash [1] is solid waste after coal burning, which has
many kinds of oxides, such as Al2O3, SiO2, Fe2O3, K2O,
Na2O, TiO2, CaO, MgO, etc. [2]. There into, SiO2 and
Al2O3 account for 60–90% of mineral composition. Fly ash
is the main source of suspended particulate matter [3] and a
regional air pollution which is harmful to human body health
[4]. Long-term storage of fly ash [5, 6] can also contaminate
soil and water, and threaten to human health at the same
time. From environmental benefits, social benefits, or from
the consideration on the economic benefits, fly ash should be
T. Zhang (&)
G. Lv
L. Wang
Z. Dou
W. Zhang
Y. Huang
Y. Wang
School of Metallurgy of Northeastern University, Key Laboratory
of Ecological Metallurgy of Multi-metal Intergrown Ores of
Education Ministry, Special Metallurgy and Process Engineering
Institute, Shenyang, 110819, Liaoning, China
e-mail: zta2000@163.net
home and abroad focused on the comprehensive utilization
of fly ash problem [11, 12], the fly ash applied research on
the technology can be divided into low, medium and high
three levels: Low level refers to the applicable for Road-dam
construction, etc.; The medium is used as building materials;
And high level refers to waste utilization of mineral sepa-
ration, etc. The alumina content of fly ash is equivalent to the
low grade bauxite in China, high-alumina fly ash [13] is
potential of alternative bauxite resources of alumina industry
in China. In recent years, researchers at home and abroad put
forward many new technology in view of the high-alumina
fly ash extract alumina problems, but the each process has its
limitations. So far, extract alumina from high-alumina fly
ash is still not economically into commercial application.
Chloride metallurgy [14] has more advantages than tra-
ditional pyrometallurgy, such as strong adaptability, low
operating temperature, high separating efficiency and well

© The Minerals, Metals & Materials Society 2017 103

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_15
104 T. Zhang et al.

comprehensive utilization. After years of research and
development, chloride metallurgical has become a complex
ore to one of the effective methods of comprehensive
recovery of valuable elements. In the case of high grade ore
resources drying up, for a lot of low grade, complicated
composition lean ore reserves which is difficult to choose,
the advantage of chloride metallurgy will become more
obvious.
A novel method was developed to prepare aluminium via
microwave fluidized bed [15] chlorination with
non-traditional aluminum resources as raw materials. This
paper explores a new approach to prepare aluminium which
contains three steps: Anhydrous aluminium chloride pro-
duced from non-traditional aluminum resource by micro-
wave fluidized bed chlorination process; Aluminium
hydroxide prepared by chlor-alkali industry [16] with
anhydrous aluminium chloride as raw materials; Aluminum
produced via electrolysis process of alumina which was
obtained by calcination of aluminum hydroxide. The key
technology of the proposed process including microwave
fluidized bed chlorination of fly ash and separating of
chloride is analyzed in detail. Research on chlorinated
reaction thermodynamics of fly ash had also investigated.
Experimental
Thermodynamic Analysis
Microwave fluidized bed chlorination was put into use in fly
ash chloride process. The main composition of fly ash
Al2O3, SiO2, Fe2O3, K2O, Na2O, TiO2, CaO, MgO may
occur as the following reactions (1–8):
Al2 O3 þ 1:5C þ 3Cl2 ¼ 2AlCl3 þ 1:5CO2 ð1Þ
Fe2 O3 þ 1:5C þ 3Cl2 ¼ 2FeCl3 þ 1:5CO2 ð2Þ
lowest energy principle and the principle of entropy
increase.
X X
DH0 ¼ DH0ðPÞ  DH0ðRÞ ð9Þ
X X
DS0 ¼ DS0ðPÞ  DS0ðRÞ ð10Þ
DG0 ¼ DH0  TDS0 ð11Þ
The results of the accordingly reaction thermodynamics
analysis are shown in Fig. 1, From Fig. 1, in the range of
273.15–1273.15 K, the standard gibbs free energy of the
chloride reaction in fly ash is negative which indicated the
reactions above in the temperature range can be positive;
The standard gibbs free energy of silica which is the main
composition of fly ash in chloride reaction is highest, the
reaction compared with the other main phase alumina
chlorination reaction is more difficult, the standard gibbs free
energy of iron oxide chloride reaction is more negative
reaction then alumina, then reaction more easily. Refer to
various chloride molten boiling point can be seen, in
273.15–1273.15 K, the phase of partial chloride products
happened to change, prompted a turning point of the stan-
dard gibbs free energy. According to the chlorination reac-
tion standard gibbs free energy, when temperature is higher
than 900 K, chlorination reaction sequence shows as follow:
K2O > Na2O > Fe2O3 > CaO > Al2O3 > TiO2 > MgO >
SiO2. When temperature is less than 973 K, the products
which are more easily happen than alumina oxide is more
solid, for the convenience of separation of products, the
perspective of thermodynamics suggested reaction before
973 K.
The gas in the back of the chlorination reaction mainly:
AlCl3, FeC13, NaCl, KCl, MgC12, FeC12, CaC12, SiCl4,
CO, CO2, Cl2, COCl2, N2, etc. The slag in the back of the
chlorination reaction mainly: SiO2, MgO, TiO2, CaO. The
slag discharge regularly, furnace gas will put into the

K2 O þ 0:5C þ Cl2 ¼ 2KCl þ 0:5CO2 ð3Þ

Na2 O þ 0:5C þ Cl2 ¼ 2NaCl þ 0:5CO2 ð4Þ -200 1.1

1.2
1.3
-300 1.4
1.5
TiO2 þ C þ 2Cl2 ¼ TiCl4 þ CO2 ð5Þ 1.6
1.7
-400 1.8

CaO þ 0:5C þ Cl2 ¼ CaCl2 þ CO2 ð6Þ -500

SiO2 þ C þ 2Cl2 ¼ SiCl4 þ CO2 ð7Þ -600

-700
MgO þ 0:5C þ Cl2 ¼ MgCl2 þ 0:5CO2 ð8Þ
-800
In order to examine various oxide chloride reaction of fly
-900
ash, the calculation of thermodynamic [17] for possible 200 400 600 800 1000 1200 1400

reactions was calculated by software (HSC Chemistry [18]).

According to the (9)–(11) to calculate the process mainly on Fig. 1 Curve of standard gibbs free energy and temperature from
the basis of thermodynamic principle and criterion, the 273.15 to 1273.15 K
New Process Research on Aluminium Production from Non-Traditional …
subsequent processing. Furnace gas turns into solid by ter-
tiary condensate recovery unit. Among them, the cooling
temperature of the first level is 200 °C which made the
impurities such as FeC13, NaCl, KCl, MgC12, FeC12 and
CaC12 in the solid way to remove; The cooling temperature
in second level at 160 °C which made the AlCl3 out in solid
way form bottom and SiCl4, TiCl4 discharge by the upper;
The cooling temperature in third level at 100 °C which made
the TilCl4 out form bottom in solid way and the impurities
such as SiCl4, CO, CO2, Cl2, COCl2 and N2 in the solid way
to remove. After refined the exhaust gas containing SiCl4,
CO, CO2, Cl2, COCl2 and N2, SiCl4 product was obtained
after bag dust collecting device. After removing impurity
and purification, AlCl3 which the purity was more than 99%
was obtained.
A novel method was developed to put microwave [19]
chlorination process of fly ash and chlor-alkali industry
together. By the reaction of AlCl3 solution with NaOH
solution, AlCl3 after alkalization, precipitation, filtration and
Fig. 2 The flow diagram for the preparation of aluminum by microwave fluidized bed chlorination
105
solid-liquid separation, Al(OH)3 and NaCl solution were
obtained; Among them, the productions of NaOH, Cl2 and
H2 were acquired form NaCl solution via the electrolysis.
Cl2 as raw material was returned to microwave fluidized bed
chlorination process of fly ash, NaOH as raw materials was
returned to separation purification process for settlement of
AlCl3 which make NaOH and Cl2 recycling. The goal of
zero discharge in the whole process and meanwhile provide
clean energy—hydrogen was achieved.
Brief Description of the Process
Through the literature and the thermodynamic analysis
shows that the fly ash via microwave fluidized bed chlori-
nation process is feasible for the preparation of AlCl3, the
flow diagram for the preparation of aluminum by microwave
fluidized bed chlorination process with fly ash as raw
materials is shown in Fig. 2.
106
Aluminum was prepared by high-alumina fly ash as raw
material via process, greatly reduced the production cost and
achieved the optimal utilization of fly ash, worked out the
problems of contaminate soil and water, and threaten to
human health by long-term storage of fly ash, with higher
environmental benefits, social benefits, or from the consid-
eration on the economic benefits. By microwave heating
mode [20], many advantages such as heating speed, sensitive
response, uniform heating, high thermal efficiency, equip-
ment cover small, high degree of automation and the
advantages of environmental protection and energy saving
was utilized. The efficient separation of chloride was realized
by the three-level condensate recovery unit, Chloride was
realized using the three-level condensate recovery unit of
efficient separation. By the reaction of AlCl3 solution with
NaOH solution which puts microwave chlorination process
of fly ash and chlor-alkali industry together, after alkaliza-
tion, precipitation, filtration and solid-liquid separation, Al
(OH)3 and NaCl solution were obtained. Among them, the
productions of NaOH, Cl2 and H2 were acquired from NaCl
solution via the electrolysis which recycles NaOH and Cl2.
The goal of zero discharges in the whole process and
meanwhile provide clean energy—hydrogen is achieved.
Conclusions
1. The results of the accordingly reaction thermodynamics
analysis are shown in Fig. 1, From Fig. 1, In the range
of 273.15–1273.15 K, the standard gibbs free energy of
the chloride reaction in fly ash is negative which indi-
cated the reactions above in the temperature range can
be positive; According to the chlorination reaction
standard gibbs free energy, when temperature higher
than 900 K, chlorination reaction sequence shows as
follow: K2O > Na2O > Fe2O3 > CaO > Al2O3 > TiO2 >
MgO > SiO2.
2. Aluminum was prepared by high-alumina fly ash as raw
material via process, greatly reduced the production cost
and achieved the optimal utilization of fly ash. By
microwave heating mode, many advantages such as
heating speed, sensitive response, high thermal effi-
ciency, etc. was utilized. The efficient separation of
chloride was realized by the three-level condensate
recovery unit, chloride was realized using the three-level
condensate recovery unit of efficient separation. By the
reaction of AlCl3 solution with NaOH solution which
puts microwave chlorination process of fly ash and
chlor-alkali industry together, after alkalization, precipi-
tation, filtration and solid-liquid separation, Al(OH)3 and
NaCl solution were obtained. Among them, the
T. Zhang et al.
productions of NaOH, Cl2 and H2 were acquired from
NaCl solution via the electrolysis which recycles NaOH
and Cl2. The goal of zero discharges in the whole process
and meanwhile provide clean energy—hydrogen is
achieved.
Acknowledgements This work was financially supported by the Joint
Funds of the National Natural Science Foundation of China
(No. U1202274, No. U51374064), the National Natural Science
Foundation of China (No. 51004033), the National Science and
Technology Support Program (No. N100302005), doctor start up
foundation in Taiyuan University of Science and Technology
(20142001), science and technology research projects of Liaoning
education department (L2010096), specialized Research Fund for the
Doctoral Program of Higher Education (20120042110011).
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reinforcing filler in ethylene propylene diene monomer rubber.
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 Opportunities of Pseudoboehmite Processing
from Aluminum Content Raw Material
at Sintering Method

Rustam A. Seytenov, Vadim A. Lipin, Evgeny A. Vlasov,

and Natalia V. Maltseva

Abstract
Technology for processing aluminum raw materials derived from the sintering method
enables produce the aluminum hydroxide in the form of pseudoboehmite directly in the
production cycle from processing aluminate liquors. Pseudoboehmite was prepared by
carbonation. Pseudoboehmite dewatering capacity was of 20–200 kg/h m2. Studies on the
properties of carbonation pseudoboehmite showed that its properties are similar to the same
product obtained in other ways. At the same time, pseudoboehmite from aluminate liquors
has lower specific surface area, includes other modifications of aluminum hydroxide, and
other features. The dried pseudoboehmite under normal conditions has a high porosity, and
can be used in the matrix for the zeolite Y containing hydrocarbon conversion catalyst to
produce a catalyst of suitable attrition resistance and catalytic activity for use in fluid
cracking systems etc.

Keywords
Alumina Filtration Pseudoboehmite Aluminum hydroxide

Introduction
Aluminum materials processing (ash [1] nepheline [2, 3],
and others.) with sintering method includes the sintering,
leaching of the cake, solution desiliconization and hydroxide
recovering through decomposition and carbonation. As a
result of the carbonization can be obtained pseudoboehmite
(PB) [1, 4–6].
Pseudoboehmite or X-ray amorphous aluminum hydrate
is an aluminum monohydroxyde, and its chemical formula is
similar to boehmite AlOOH. But, in contrast to boehmite,
R.A. Seytenov (&)
Outotec CIS, V.O., 7-th Line 76, Lit. A, 199178 St. Petersburg,
Russia
e-mail: rustam.seytenov@outotec.com
V.A. Lipin
St. Petersburg Polytechnical University, 29, Polytechnicheskaya
St, 195251 St. Petersburg, Russia
E.A. Vlasov
N.V. Maltseva
St. Petersburg State Technological Institute (Technical
University), 26, Moskovsky Pr, 190013 Saint-Petersburg, Russia
PB does not have a clear crystal structure and does not have
a water molecule in its composition, and because of this, the
sediment moisture after filtration of PB cannot be below
75% w/w.
Aluminium hydroxide as a volumetric gel or as PB
conditions can be obtained from aluminium-containing
liquors by certain processing. PB is used for binding the
catalytic mass which is subjected to granulation or extrusion.
PB is a desirable form of hydrated alumina for use in the
matrix for the zeolite Y containing hydrocarbon conversion
catalyst to produce a catalyst of suitable attrition resistance
and catalytic activity for use in fluid cracking systems [7].
Activated alumina (AOA) is based on PB precursors [7].
AOA is applied as desiccants, sorbents, catalysts etc. The
opportunities of use of AOA in these areas are determined
by its properties, namely specific surface, type of porous
structure, contents of impurity, ability of initial raw material
to extrusion granulation, form and size granules, mechanical
durability of the granules, cost of the raw material and the
cost of waste recovery.

© The Minerals, Metals & Materials Society 2017 109

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_16
110 R.A. Seytenov et al.

In catalysts AOA from PB are used as active catalyst and

support (Claus-process, isomerization, cracking, reforming,
dehydration etc.). One of the largest modern-day uses of
AOA is that of a catalyst support for catalytic muffler on
automobiles.
X-ray amorphous aluminum hydroxide is also widely
used in pharmaceutics [8].
The neutralisation of aluminium-containing solutions is
carried out in conditions favourable to precipitation of PB.
The most widespread acid for neutralisation of aluminate
solutions is nitric acid because the anion NO3− is the most
effective stabiliser of the PB structure. With reference to the
solutions of alumina production it could be done by passing
of carbon dioxide gas through an aluminate solution at a low
temperature.
The problems in separating phases arise in filtration of
aluminium hydrate of an X-ray amorphous structure similar
to the pseudoboehmite structure. Various types of filters and
filtration flow diagrams are used to separate the cakes from
Fig. 1 Picture of bench-scale test unit of filter
the liquid during the extraction PB or X-ray amorphous
aluminum hydroxide. All of them are characterized by low
productivity and there is no single point of view for the
choosing of equipment [9].

Experimental

In carbonization method to prepare pseudoboehmite CO2 was

introduced into aluminate liquor at temperature 25–30 °C [4].
The mechanism of carbonization process is not yet enough
despite of numerous researches. The sequence of reaction in
carbonization process at PB preparation can be primitive
submitted by the following reaction:

CO2 þ 2H2 O ¼ H3 O þ þ HCO

3 ð1Þ
 
AlðOHÞ4 þ H3 O þ ¼ AlOOH þ 3H2 O ð2Þ

Aluminate solutions obtained from an alkali aluminosil-

icate raw materials by the process of sintering were car-
bonized in experimental-industrial conditions.
Separation of phases after precipitation and washing of
solid phase test work has been done. For this, the filter of
belt type Pannevis was used. Laboratory Pannevis belt filter
is a special Buchner funnel, simulating the belt filter filtering
process, and Bunsen flask (Fig. 1).
Laboratory belt filter Outotec Pannevis designed for
laboratory tests carrying out for the vacuum filtration of
different products to separate solid and liquid phases with
quality washing. Laboratory test unit simulates the operation
of the industrial Outotec Larox® belt filters. Specific per- Fig. 2 XRD diffraction images of different PB products at technology:
formance of industrial filter, residual cake moisture, filtrate a sulphate; b nitrate; c carbonate
Opportunities of Pseudoboehmite Processing from Aluminum … 111

quality, washing liquid consumption based on results of the
tests.
During test work, samples goes to analysis for solids
content in filtrate and moisture content. Depending on the
washing requirements, there are used one or multi-stage
washing of the cake with water or saline. Also during the
tests, carried out the selection and addition of various
reagents that improve filtration.
Density of filtration feed was 110–1200 g/l, solids con-
tent in slurry was 3.0–3.5%, Liquid contents, g/l: R2Oku—
5.0–7.0; R2Ou—38–40; Al2O3—5.0–5.5 (were R2O
Na2O + R2O as Na2O).

Fig. 3 PB thermal treatment SEM results at, °C: a 100; b 400; c 600; d 800
112 R.A. Seytenov et al.

Table 1 Results of determining pore structure parameters of PB R2O total content in the solid phase after washing was
product after thermal treatment at 500 °C according to the below 0.05 g/l.
adsorption-desorption isotherms of nitrogen under vacuum conditions
Particle size distribution results for PB were obtained by
Surface area data (m2/g) laser analyzer, %: −5 mkm—15–20; −10 mkm—40–60;
Single point BET 198.8 −20 mkm—85–95; −40 mkm—10.
Multi point BET 207.0 XRD diffraction patterns of PB products produced by
BJH cumulative adsorption 125.7 carbonization method in comparison with produced from
BJH cumulative desorption 175.3 aluminum sulphate and aluminum nitrate liquors are shown
DFT cumulative 201.2
in Fig. 2.
3 From these data, it follows that the PB, obtained from
Pore volume data (cm /g)
aluminate solutions in alumina refinery, in conditions close
Total pore volume for pores with diameter less than 0.335
to the industry, similar to the PB produced by alternative
571.31 nm at P/Po = 0.996617
methods. However, it differs in that it has in its composition
BJH cumulative adsorption 0.295
a significant proportion of other modifications of aluminum
BJH cumulative desorption 0.314 hydroxide, gibbsite is mainly.
DFT cumulative 0.296 Pseudoboehmite obtained after carbonization put into
Pore size data (nm) drying-roasting electrical furnace and heat in accordance
Average pore diameter 6.47 schedule: 100–120 °C—12 h; 350 °C—1 h; 500 °C—2 h;
BJH adsorption 4.42 800 °C—2 h. During heating PB undergoes transformation,
BJH desorption 3.8 varied specific surface area, porosity, and others. Product of
PB thermal treatment SEM results were shown as Fig. 3.
DFT 6.08
Volume and area summary for product at 500 °C is
present in Table 1 and Fig. 4. The results in Fig. 4 show that
The filter cake with a 75–85% moisture content washed the main characteristics obtained after heat treatment of
with 1–3 m3/t summary consumption Temperature of active aluminum oxide (AAO) have specific special prop-
washing liquid was 40–80 °C. erties. It defines and partially limits the field of utilization of
SEM images of samples were obtained in a scanning PB, obtained after carbonization. It can be used in the matrix
electron microscope SUPRA 55VP-25-78. for the zeolite Y containing hydrocarbon conversion catalyst
Porous structure AOA was appreciated by study isotherm
adsorption-desorption nitrogen steam at bath temperature
77.35 K and outgas 250 °C on Quantachrome ASWinTM.
Surface area (BET, BJH, DFT), pore volume, pore size were
been calculated on the basis experimental data.
Chemical composition was determined by weight and
flame-photometry methods.
Phase composition was determined by X-Ray method on
Bruker D8 Advance diffractometer using monochromatic
CuKa-radiation (k = 1.54178 Å), with a 0.02 step scan and
exposures 11 s per step. For phase analysis was used ICDD
database (PDF-2).

Results and Discussion

Filtration test work showed (bench scale), that capacity

for filtration and washing may vary in wide range
20–200 kg/h m2.
This value is mainly dependent on the proper selection of
the filter parameters of the regime and the ratio of time of
basic operations. In addition, carbonization conditions in the Fig. 4 Stepped isotherms of nitrogen on the product after thermal
preparation of the pseudoboehmite has some affect. treatment at 500 °C
Opportunities of Pseudoboehmite Processing from Aluminum …
to produce a catalyst of suitable attrition resistance and
catalytic activity for use in fluid cracking systems etc.
Conclusions
PB obtained from aluminate solution by carbonization
technology in their properties close to the PB obtained by
other technologies; however, it may include in its compo-
sition a certain part of other aluminum hydroxide
modifications.
PB filtration with washing is characterized by capacity
20–200 kg/h m2 on the belt filter. Performance of phase
separation and washing determined by regime and the ratio
of basic operations parameters.
Prepared AOA in accordance their characteristics can be
used in the matrix for the zeolite Y containing hydrocarbon
conversion catalyst to produce a catalyst of suitable attrition
resistance and catalytic activity for use in fluid cracking
systems etc.
References
1. X.Q. Zhang et al., Preparation of pseudo-boehmite by using
high-alumina coal fly ash. Light Met. 147–151 (Edited by: Margaret
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substances in alumina refinery. Light Met. 97–101 (Edited by:
Margaret Hyland, The Minerals, Metals & Materials Society) (2015)
 Chemical Alumina Preparation by Using High
Alumina Content Fly Ash

Guozhi Lv, Ting-an Zhang, Weiguang Zhang, Xiaofeng Zhu, Yan Liu,
Long Wang, Zhihe Dou, and Qiuyue Zhao

Abstract
Processes of chemical alumina preparation of high alumina content fly ash raw materials
are put forward in order to solve the problems of bauxite resource shortage in China and
high value application of fly ash. High white aluminum hydroxide and Pseudoboehmite can
be obtained by sintering process with the precipitation and carbonate decomposition. 4A
zeolite is prepared through the pre-roasting and synthesis process, and activated aluminium
oxide is prepared through the acid leaching and pyrolysis method. Typical experiments for
preparing different kind of chemical alumina products are presented as well. Whiteness,
porosity, pore volume, crystalline and other key parameters of chemical alumina products
determined by XRD and ASAP match the industry requirements well.

Keywords
Coal fly ash Zeolite High white aluminum hydroxide Decomposition of carbonate
Spray pyrolysis

Introduction The ash of pulverized coal boiler are obtained basically of

China’s aluminum industry has realized the transformation
process from scratch, weak to strong since the founding of
the country. At present, China’s aluminum production
capacity has reached more than 17 million tons, and alumina
production capacity has reached nearly 40 million tons,
which is the highest in the world. Along with the rapid
development of aluminum industry in China, the shortage of
high quality aluminum resources and contradiction between
the industrial and demand has become a restrict bottleneck
problem for the sustainable development of alumina industry
in China [1–3].
G. Lv (&)
T. Zhang
W. Zhang
X. Zhu
Y. Liu
L. Wang
Z. Dou
Q. Zhao
School of Metallurgy of Northeastern University, Key Laboratory
of Ecological Metallurgy of Multi-metal Intergrown Ores of
Education Ministry, Special Metallurgy and Process Engineering
Institute Shenyang, Shenyang, 110819, Liaoning, China
e-mail: lvgz@smm.neu.edu.cn
T. Zhang
e-mail: zta2000@163.net
two methods: one is in the furnace up bond particulate ash,
falling into the bottom of the boiler. Some form large, after
crushing is discharged from the bottom, which is called gray
slag, ash total weight of approximately 15–30%. The other is
from the exhaust system with dust collection facilities to
collect fine dust down, called fly ash, which is a nature and
do not exist in powdered mineral resources by the human
production and life process produces [4–6].
China’s annual emissions of fly ash have been more than
300 million tons. With the rapid development of China’s
power industry, the emissions of fly ash are increasing. In
recent years, research institutions and enterprises for this
type of fly ash are interested in separation extraction of
alumina and silica, and gradually expanding the industrial
test, obtaining different chemical products. The main meth-
ods used are limestone sintering, acid-out, bases and acid
dissolution method or combined method. In addition, fly ash
to be treated as ordinary use, but this is obviously a waste of
resources [7].
Zeolite is a kind of crystalline aluminosilicates, which has
uniform pore structure, capable of separating molecules of

© The Minerals, Metals & Materials Society 2017 115

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_17
116 G. Lv et al.

different size or selectivity of the reaction as a catalyst or

solid adsorbent. The molar ratio of silica and aluminum
oxide which contains silica to alumina ratio referred to dif-
ferent aluminosilicate zeolites, which have different pore
structure and performance. Zeolite can be divided into nat-
ural and synthetic zeolites two categories. So far, there have
been found 40 kinds of natural zeolite, synthetic zeolite are
150 kinds. Natural zeolite types are low purity and small
applications, but because of artificial zeolite varieties are
high purity, uniform pore size, large surface area, strong ion
exchange and adsorption properties, which is widely used in
industry, environmental protection and other fields [8, 9].
In this paper, preparation of pseudo-boehmite, high white
aluminum hydroxide and 4A Zeolite by using Inner
Mongolia Datang fly ash sintering clinker as raw material
are studied. Experiments were carried out to explore the Fig. 1 SEM photograph of coal fly ash
optimum process conditions of dissolution experiment,
desiliconization experiment, carbonation decomposition
experiment and seed precipitation experiment. Moreover,
XRD spectrum, SEM and the analysis of the specific surface
area and pore structure method was adopted to analyze the
properties of the product. The physical properties of car-
bonation product and seed precipitation product were com-
pared as well.

Experimental

Materials

The main raw material used for preparing the proposed

experiments boehmite is fly ash from Datang Inner Mon-
golia Datang International Tuoketuo Power Generation
Company, the major chemical composition of fly ash sam-
ples are shown in Table 1. The XRD test was carried out by
D8 advance (Bruker, German) using a Cu target with step of
0.0095° for a scanning spectrum of 10°–90°.
Raw fly ash was characterized by SEM (scanning electron
microscope). The photograph is shown in Figs. 1 and 2, the
XRD (X-ray diffraction) as shown in Fig. 3.
Coal fly ash is in irregular shape, with a sponge-like
porous glassy particles and spherical particles with smooth
surface structure of the main evacuation and contains irreg-
ular in shape, fine carbon particles of porous. Ash is the main
component of vitreous bead particles, and the content of more
than 70% of its ingredients is mainly amorphous SiO2 and
A12O3, thus its high chemical activity. Da Tang fly ash shows
that the crystal phase composition of fly ash are mainly
Datang mullite (3A12O3
2SiO2), quartz and corundum, and
Fig. 2 SEM photograph of coal fly ash particle
diffraction peaks appear in both ash XRD part of the region,
indicating that Fly in the presence of the vitreous.
Experimental Procedures
Decomposition of Carbonate, High White
Aluminum Hydroxide and Pseudoboehmite
Because sodium aluminate solution decomposition of car-
bonate is an exothermic process, with the deepening of the
decomposition reaction, the decomposition temperature of
the system will rise sharply. The decomposition temperature
is too high, which will lead to a sharp increase in gibbsite,
boehmite proposed in a large number of impurity phase, and

Table 1 Chemical composition Chemical contents (%) MgO Al2O3 SiO2 CaO Fe Other
of coal fly ash
0.48 42.95 41.90 3.66 2.80 8.21
Chemical Alumina Preparation by Using High Alumina Content Fly Ash 117

High alumina fly ash

M
M-mullite
1400 C-Corundum Acid leaching iron
indnensity(cps)

C
M
M M
Q-quartz
Q NaOH Molten alkali calcined Sodium aluminate
Q M

700 Q M
C C
Aging
C

Different
NaOH hydrothermal crystallization
0 Different Time
30 60 90 concentration at different temperatures
2θ(°)

Fig. 3 X-ray diffraction pattern of CFA Filtered washed and dried

Zeolite Products

Fig. 5 Process of alkali fusion-synthesizing zeolite 4A from high

alumina fly ash

First it will be filled with the pyrolysis saturated AlCl3

solution ceramic crucible placed in a muffle furnace, and
then heated; second, when it reaches the set pyrolysis tem-
perature, the time required to heat; After pyrolysis, a sample
was taken in air cooled to room temperature.

1-CO2 high pressure vessel; 2-rotoe flow meter; 3-stir Results and Discussion
motivation; 4-water bath; 5-stir blade; 6-thermocouple;
7-thermal sensor
Decomposition of Carbonate and High White
Aluminum Hydroxide

Whiteness of aluminum hydroxide, magnesium hydroxide

Fig. 4 Carbonation experiment install
ultimately affect the quality of the proposed boehmite. Thus,
this experiment decomposition system adds a heated water
bath to prevent the rapid increase in the decomposition tem-
perature of the system. Experimental setup is shown in Fig. 4.
4A Zeolite Preparation
High alumina fly ash with alkali melt firing—Hydrothermal
Synthesis of 4A Zeolite route is shown in Fig. 5.
Activated Aluminium Preparation
Activated aluminium oxide is prepared through the acid
leaching and pyrolysis method. The technical parameter of
the equipment is shown in the Table 2.
standard white to monochromatic light of a specific wave-
length absolute reflectance ratio as a benchmark to test the
model corresponding wavelength measured absolute reflec-
tance surface. In many varieties aluminum hydroxide
applications, aluminum hydroxide whiteness, the higher
aluminum hydroxide as filler articles transparency, color
deviation, the higher the product aesthetics.
Figure 6 shows the whiteness of Al(OH)3 products with
different carbonation temperature(60, 65, 70, 75, 80 °C)
under the conditions of Al2O3 to SiO2 mass ratio at 1800 in
liquid, carbonation time at 100 min, CO2 gas concentration
at 40% decomposition and carbonation temperature. As can
be seen from the Fig. 6, the whiteness of carbonation pro-
duct value is more than 97%, in line with high white alu-
minum hydroxide whiteness requirements (>95%).
118 G. Lv et al.

Table 2 Technical parameter of Item Rated Rated Rated Furnace size Quality
SX2-5-12 muffle furnace power current temperature
Technical 5kW 220 V 1200 °C 300  200  120 mm 55 kg
Parameters

99
carbonation semen directly affect the whiteness index silicon
98.5 carbon products division.
98.2
98
98 97.9

97.4 Decomposition of Carbonate Pseudoboehmite

Whiteness

97 Pseudoboehmite has a unique structure, which exhibit unique

physical and chemical properties, which intends to boehmite
specific surface area and pore volume directly affects the size
96 of its properties, the use of ASAP2020 type BET specific
surface area analyzer using nitrogen at −196 °C assay pro-
duct specific surface area and pore volume. Comparative
95 study of the aging time of 4 h, at a temperature of 20, 30, 40
60 65 70 75 80
Temperature and 50 °C, acidity under 30, 40 and 50 g/L, the carbon
products division specific surface area are shown in Fig. 8.
Fig. 6 Carbonation product whiteness under different temperature

Silicon content of aluminum hydroxide and aluminum

hydroxide whiteness has an important impact on the quality 420 30g/L
of products, decomposition late, as the precipitated silica, 40g/L
50g/L
aluminum hydroxide will precipitate together. Carbonation 400
experiments examined the genetic influence of silicon index
BET/m /g
2

of whiteness. Carbon silicon index as abscissa and whiteness 380

as ordinate, subjected to a higher fitting is shown in Fig. 7. It
can be seen that the relationship of the silicon index is y ¼
360
93:09 þ 0:0060x  1:6287  106 x2 and whiteness is R =
0.9702, in which, the y is whiteness, x is carbon silicon
340
index, R is the correlation coefficient. As can be seen,
20 25 30 35 40 45 50
different temperature/

99
0.75
0.70
98 30g/L
0.65 40g/L
50g/L
cm /g

97
0.60
3

0.55
Whiteness

96

Equation
y = Intercept + B1*x^1 + B2*x^2 0.50
95
Weight No Weighting 0.45
Residual Sum of 0.64536

94
Squares
Adj. R-Square 0.94125 0.40
Value Standard Error
Intercept 93.0891 0.42446 0.35
B B1 0.00597 0.00142
93 B2 -1.62871E-6 7.58011E-7
0.30
-200 0 200 400 600 800 1000 1200 1400 1600 1800 2000
20 25 30 35 40 45 50
Silicon Index Temperature

Fig. 7 The relationship of silicon index before carbonation and Fig. 8 Surface area and pore volume of carbonation product under of
carbonation product whiteness aging 4 h
Chemical Alumina Preparation by Using High Alumina Content Fly Ash 119

It could be concluded that pore volume of P-B product
would cut down with increasing temperature, owing to the
decreasing fraction of constitution water in AOOH.
Whereas, pore volume would increase at first, and then
decrease with increasing decomposition concentration.
Conclusively, maximum 0.6920 cm3/g was observed at
40 g/L and 30 °C.
degree of activation, help promote the formation of a growth
phase 4A zeolite supersaturated system. After the molten
NaOH treatment at 850 °C, the highest degree of activation
of fly ash can obtained, and after hydrothermal synthesis, the
sample is mainly 4A zeolite. In Fig. 9 shows that synthetic
4A zeolite at the calcination temperature of purity and
crystallinity are high. Thus, in this experiment the alkali
fusion temperature should be 850 °C.

Preparation of 4A Zeolite
To investigate the impact of temperature on alkali fusion
synthesis of 4A Zeolite, respectively 10 g fly ash and 12 g
NaOH were uniformly mixed in a muffle furnace and cal-
cined to 550, 650, 750 and 850 °C for 2 h, then ground into
powder. After, the fusion product is mixed with water at
liquid to solid ratio 4:1, then stir at room temperature aging
for 6 h, at 90 °C crystallization for 24 h; then dried and
grinding. XRD spectra obtained zeolite sample are shown in
Fig. 9.
As shown in Fig. 9, with the alkali fusion temperature
increasing, the diffraction peak intensity 4A zeolite gradually
increased and reached the maximum at 850 °C. This trend as
well as the sodium silicate and sodium aluminosilicate in
Fig. 9 is very consistent. These results indicate that the
temperature can be increased to improve the alkali fusion of
fly ash inert material (such as mullite, corundum, etc.) the
Pyrolysis and Preparation of Al2O3
Static pyrolytic material is a solution of aluminum chloride
and chlorine from the pyrolysis products and is not com-
pletely aluminum chloride pyrolysis. The content of chlorine
can be seen as the degree of pyrolysis efficiency from the
side. Impact study of pyrolysis temperature and pyrolysis
time on the pyrolysis products in chlorine content and the
results are shown in Table 3, Fig. 10.
Figure 10 shows that with the increase of pyrolysis
temperature and pyrolysis time, the pyrolysis products of
chlorine content are reduced, it is possible by increasing the
pyrolysis temperature and pyrolysis time to minimize the
pyrolysis products of chlorine content, so as to improve the
pyrolysis efficiency.
6.0
ontent of Cl in the product/ %

800
5.5 700
5.0 600
A--- Zeolite4A
A 4.5
A A A
A A A
A T=850 4.0

3.5
A A A A
A 3.0
A A A
T=750
2.5

A A A A 2.0
A A A A
T=650 1.5

1.0
A A A A
A A A 0.5
A T=550
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
t(h)
10 20 30 2θ/ 40 50 60
Fig. 10 Curve of chlorine content of pyrolysis products and temper-
Fig. 9 XRD patterns of samples by different alkali fusion temperature ature (600, 700 and 800 °C) and time (h)

Table 3 Chlorine content of Pyrolysis time (h) Chlorine in the pyrolysis products (%wt)
pyrolysis products in different
pyrolysis temperature and time 600 °C 700 °C 800 °C
1 5.84 3.49 3.52
1.5 5.3 3.05 2.36
2 2.56 1.78 1.13
2.5 2.14 1.13 0.72
120
Conclusions
Silicon content of aluminum hydroxide and aluminum
hydroxide whiteness has an important impact on the quality
of products, decomposition late, as the precipitated silica,
aluminum hydroxide will precipitate together. Carbonation
experiments examined the genetic influence of silicon index
of whiteness. The whiteness of carbonation product value
are more than 97%, in line with high white aluminum
hydroxide whiteness requirements (>95%).
Pseudo-boehmite product could be prepared by carbon-
ation process, maximum 0.6920 cm3/g was observed at
40 g/L and 30 °C.
The temperature can be increased to improve the alkali
fusion of fly ash inert material. After the molten NaOH
treatment at 850 °C, the highest degree of activation of fly
ash can obtained.
With the increase of pyrolysis temperature and pyrolysis
time, the pyrolysis products of chlorine content is reduced, it is
possible by increasing the pyrolysis temperature and pyrolysis
time to minimize the pyrolysis products of chlorine content.
Acknowledgements We acknowledge the National Natural Science
Foundation of China (Nos. U1202274, 51504059, 51374064), Funda-
mental Research Funds for the Central Universities of China
G. Lv et al.
(Nos. N140203005, N140204015), Science and Technology Research
Projects of Liaoning Education Department (No. L2014096), China’s
postdoctoral fund (2015M581352).
References
1. Z. Wang, On the issue of China’s alumina industry is facing and the
direction of development. Nonferrous Met. Indus. 21(2), 23–27
(2000)
2. L. Zhang, J. He, Y. Zhang, Status and counter measure of alumina
industry in China. China Light Met. 2, 3–7 (2006)
3. Ta Zhang, W. Zhu, G. Lv, Aluminum Metallurgy (Science Press,
Beijing, 2014)
4. T.W. Cheng, T.H. Ueng, Y.S. Chen, J.P. Chiu, Production of
glass-ceramic from incinerator fly ash. Ceram 28(7), 779–783
(2002)
5. P. Davini, Flue gas treatment by activated carbon obtained from
coal fly ash. Carbon 40(11), 1973–1979 (2002)
6. H.-L. Chang, W.-S. Shih, Synthesis of zeolites A and X from coal
fly ashes and their ion-exchange behavior with cobaltions. Ing. Eng.
Chem. Res 39(11), 4185–4191 (2000)
7. M. Ahmaruzzaman, A review on the utilization of fly ash. Prog.
Energy Combust. Sci. 36, 327–363 (2010)
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ash. Light Met. (2015)
 A Novel Process of Alumina Production
from Low-Grade Bauxite Containing Sulfur

Bo Wang, Kai Zhao, Huilan Sun, Xuezheng Zhang, Zepeng Li,

and Hongyou Ma

Abstract
Soda-lime sintering process and lime sintering process are the research focus on utilization
of low-grade alumina recently. The latter process can realize dry-sintering process and its
energy consumption is relatively lower. However, its sintering temperature is up to 1350 °
C, which is unfavorable to industrial production. Based on lime sintering method, a novel
process of alumina production from low-grade bauxite containing sulfur or fly ash is carried
out in this paper. The phase of alumina transforms from 12CaO
7Al2O3 (C12A7) to
4CaO
3Al2O3
SO3 (C4A3S), whose alumina leaching property is better, through decreasing
sinter temperature and time and adjusting the content of CaSO4 of the raw materials of lime
sintering process. The main phases of the clinker sintered at 1250 °C are C4A3S and silicon
dioxide. Its leaching ratio reaches 89% after 10 min reaction, and the conditions of leaching
temperature and sodium carbonate’s concentration are lower than that of C12A7.

Keywords
High-sulfur bauxite Calcium sulphoaluminate Alumina leaching Lime-sintering
process

Introduction There are many problems in alumina leaching of

The grade of bauxite decreases obviously with the fast
development of alumina production. The utilization of
low-grade or refractory bauxite becomes the research hot-
spot [1, 2]. China is rich in resources of sulfur-bearing
bauxite, whose content of sulfur is between 0.7 and 4%. Its
proved reserves are 0.15 billion tons, accounting for 11% of
China’s domestic bauxite reserves [3, 4]. Therefore, the
utilization of sulfur-bearing bauxite can release the defi-
ciency of bauxite to a certain extent.
B. Wang (&)
K. Zhao
H. Sun
X. Zhang
Z. Li
H. Ma
School of Materials Science and Engineering, Hebei University of
Science and Technology, Shijiazhuang, 050018, China
e-mail: wangbo1996@gmail.com
B. Wang
Hebei Key Laboratory of Material Near-Net Forming Technology,
Hebei University of Science and Technology, Shijiazhuang,
050018, China
sulfur-bearing bauxite by the Bayer process, such as the
equipment corrosion caused by the leaching of sulfide, the
decrease of alumina leaching ratio and the intensifying of
scab during the evaporation process. In order to solve the
problems mentioned above, the alumina leaching ratio
increased to 81% and the sulfur leaching ratio decreased to
7.05% by adjusting the parameters of Bayer process
according to Zhang’s studies [5]. The optimal process
reduces the leaching ratio of sulfur, but it does not solve the
problem of sulfur’s circulation. Lv [6, 7] roasted the
sulfur-bearing bauxite under 800 °C before Bayer process.
The results indicated that the content of the raw materials
decreased to 0.7%, and it can meet the demand of sulfur
content of the Bayer process. After the pretreatment of lime
roasted, the relative leaching ratio can reach 95.35% by high
pressure digestion [8].
The process mentioned above is suitable for the bauxite
with high grade and low sulfur content, but it is unsuitable
for bauxite or fly ash with middle-low grade or high sulfur

© The Minerals, Metals & Materials Society 2017 121

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_18
122
content. According to our previous study, it is found that the
compound of C4A3S is formed by the elements of Al and S
during lime-sintering process, whose alumina is easily to be
leached out. And also its sintering and leaching temperature
are lower than these of C12A7.
Experiment
Materials
Low-grade bauxite, whose A/S is 3.0, is obtained from
alumina plant. Carbonate calcium, alumina and dihydrate
calcium sulfate, all of the above reagents are analytically
pure.
Alumina leaching solution was prepared by analytically
pure reagents of sodium carbonate and sodium hydroxide
solution.
Equipments
Electronic balance, SFM-II planetary four head mixers,
crusher, SFM-I planetary ball miller, KSL-1700X box-type
high temperature sintering furnace, and thermostatic water
bath are used for experiments. D/MAX-2500 X-ray diffrac-
tometer (Rigaku) and S-4800-I SEM (Hitachi) are used for
analysis.
Sintering of Clinker
The analytical reagents of CaCO3 Al2O3 and CaSO4
2H2O
were weighed according to C/A=1.33 (the molar ratio of
CaO and Al2O3 except for the CaO which combined with
SiO2 to generate 2CaO
SiO2). The content of Al2O3 in raw
material (A/S=2) is 29.2%, and the specific material ratio as
shown in Table 1. They were mixed in the planetary mixer
at the speed of 130 r min−1 for 2 h. The mixed material was
sintered for 2 h at a certain temperature using conventional
sintering system (the mixed material was heat by 10 °C/min
below 1000 °C and 7 °C/min above 1000 °C, cooling with
the same system) and then was taken out when the tem-
perature below 200 °C. After sintering process, a portion of
the sintered clinker was ground to less than 200 meshes
(  74 lm) for the use of XRD analysis and alumina
leaching in the SFM-1 planetary ball mill at the speed of
250 r min−1 for an hour.
Table 1 The proportion of raw Raw materials Bauxite
materials (g)
Proportion 50.00
B. Wang et al.
Alumina Leaching of Clinker
Leaching experiments were carried out in the constant
temperature water bath under the following leaching con-
ditions: leaching temperature was 80 °C, leaching time was
30 min, L/S ratio was 10, stirring rate was 300 r min−1 and
the leaching solution was Na2CO3 (70 g L−1). 100 mL of
leaching solution was accurately measured and was trans-
ferred into the flask-3-neck and preheated to 80 °C. Then
10 g of clinker was poured into the flask-3-neck, stirring and
timing of leaching. Once the certain time was reached, a
certain amount of leaching solution was taken out,
drying-filtered and cooled. Chemical composition analysis
method was used to analyze the concentration of Al2O3 in
filtrate. The alumina leaching ratio was calculated by the
formula (1).
qL  VL  qA  VA
gAO ¼ ð1Þ
mx
Where, qA and qL are the concentration of Al2O3 in
leaching solution before and after leaching, g/L; VA and VL
are the volume of the solution before and after leaching, L;
m is the mass of the added clinker, g; x is the alumina
content of the clinker, %.
Results and Discussions
Effect of Sintering Temperature on Clinkers
The sintering experiments are carried out with the temper-
ature ranges from 1100 to 1375 °C, and Other conditions are
as Section “Sintering of Clinker”. The alumina leaching ratio
of clinkers is shown in Fig. 1.
It can be seen that the alumina leaching ratio improves
obviously with the increase of sintering temperature under
the same holding time and temperature system. And it
reaches 88.85% when the temperature is 1225 °C. After that
the increasing speed becomes slow, and leaching ratio ran-
ges between 89 and 91%. The leaching ratio can reach
91.17% at 1350 °C. Therefore, the absolute leaching ratio of
clinker can reach upto 90% in the CaO–Al2O3–SiO2–SO3
quaternary system. The range of the final sintering temper-
ature is 125 °C, which is wider than that of C12A7, whose
range is 25 °C.
XRD analysis of the clinkers is carried out and the phase
components analysis is shown in Figs. 2, 3, 4, 5.
CaCO3 CaSO4
2H2O
38.64 8.20
A Novel Process of Alumina Production … 123

100 3500

95
1
3000
1-Ca 4(Al 6O12)(SO4)
90
2-Ca 2 SiO4
Alumina leaching ratio/%

85 2500

80
2000

Counts
75
1500
70 1
65 1000 2 1

60 2
500 1 1 2 1
55 2 1

50 0
1100 1150 1200 1250 1300 1350 1400
10 20 30 40 50 60 70 80 90
Sintering temperature /
2-Theta

Fig. 1 Alumina leaching ratio of clinkers under different temperature

Fig. 3 XRD spectrum of clinker at 1250 °C

4000 5000
1
1-CaO 1
3500 1-Ca4Al6O12(SO4)
2-Al 2O3
4000
3-SiO2 2-Ca 2(SiO4)
3000
4-CaSO4
2500 5-Ca4(Al6 O12)(SO4) 3000
Counts

Counts

2000 1
1
2000
1500 4

1
1000 53 1
1000 2
4 11
500 2 4 2 2
2
1 1 11 1 1 2 1 12 2 1
1
1 1
1 2
0 0
10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80
2-Theta 2-Theta

Fig. 2 XRD spectrum of clinker at 1200 °C Fig. 4 XRD spectrum of clinker at 1350 °C

A certain amount of compound C4A3S has been formed porous can increase the contact area of the solid reaction and
at 1200 °C (Fig. 2). There are still a certain quantity of CaO, increase the reaction rate in the process of leaching.
Al2O3, SiO2 and CaSO4, which do not react at this tem- Therefore, calcium aluminate clinker, whose main phases
perature. Therefore, the alumina leaching ratio is lower. are C4A3S and c-2CaO
SiO2 is obtained at 1250–1375 °C
Reactions among the oxides carry out completely when for 1 h. When the sintering temperature is higher than
the temperature is up to 1250 °C (Figs. 3, 4, 5). The main 1300 °C, the phase composition of the clinker does not
phases of the clinker are C4A3S and c-CaO
SiO2. They do change. The alumina leaching rate is high and stable.
not change when the temperature ranges from 1250 to
1375 °C. So, the formation of C4A3S is easy under the
studied temperature range, and the sulfur does not decom- Effect of Leaching Temperature on Leaching
posite at high temperature stage. Ratio of Clinker
The SEM image of clinker at 1350 °C is shown in Fig. 6.
It can be seen that the micro-morphology of the sample The effect of leaching temperature on alumina leaching
which was sintered at 1350 °C for 1 h is porous. These performance of the clinker sintered at 1300 °C for 1 h was
124 B. Wang et al.

100
3500 1

3000 1-Ca4 Al6O12(SO4) 95

2-Ca 2 SiO4

Alumina leaching ratio/%

2500
90

2000
Counts

85
1500
1
1000 1 80
2
2
500 1 1 22 1
2 2 1 1 1 1 2 75
1
0
10 20 30 40 50 60 70 80 90 70
40 50 60 70 80 90
2-Theta
Leaching temperature /
Fig. 5 XRD spectrum of clinker at 1375 °C
Fig. 7 Leaching ratio of clinker under different leaching temperature

98

96

94
Alumina leaching ratio /%

92

90

88

86

84

82
10 20 30 40 50 60
Leaching time /min

Fig. 8 Alumina leaching ratio of clinker with different leaching time

the alumina leaching ratio increased little. The leaching ratio

Fig. 6 SEM image of clinker at 1350 °C
studied under the leaching conditions (NC 70 g/L, NK
10 g/L, leaching time 30 min, stirring speed 400 r min−1,
L/S 10). The results are shown in Fig. 7.
As shown in Fig. 7, the alumina leaching ratio of clinker
increases obviously with the increase of temperature which
ranges from 40 to 50 °C. After that, the effect of temperature
on leaching rate decreases. That is because the reaction
temperature is low, and the molecular irregular motion is not
intense enough. When the temperature is higher than 50 °C,
is above 86% when the temperature ranges from 50 to 90 °C.
As a result, the leaching temperature range of the clinker is
wide.
Effect of Leaching Time on Leaching Ratio
of Clinker
The leaching experiments of clinker sintered at 1300 °C for
1 h with different leaching time are carried out. Other
leaching conditions are: NC 70 g/L, NK 10 g/L, leaching
A Novel Process of Alumina Production …
temperature 80 °C, stirring speed 400 r min−1, L/S 10. The
results are shown in Fig. 8.
As can be seen in Fig. 8, the clinker can be leached in a
short period of time, and the leaching ratio is high. After
10 min leaching, the leaching rate improves little. C4A3S is
easier to leach than C12A7 [9, 10]. As illustrated in Fig. 6,
the micro-morphology of sulfur calcium aluminate clinker is
porous, which increases the contact area of the liquid and
solid, accelerates the reaction rate and makes the reaction
more adequate.
Conclusions
(1) The alumina leaching rate of the CaO–Al2O3–SO3–
SiO2 quaternary system increased with the sintered
temperature. Its main phases are C4A3S and
c-2CaO
SiO2. When the sintering temperature is higher
than 1250 °C, the phase composition of the clinker
does not change. The sintering temperature range is
125 °C.
(2) The porous micro-morphology of the clinker leads to
the high alumina leaching ratio. The effect of leaching
temperature on leaching ratio is little when it is above
50 °C. After 10 min’ digestion, the alumina leaching
ratio can reach 91%.
Acknowledgements The authors greatly acknowledge the financial
support of the Science and Technology Foundation of higher educa-
tioninstitution of Hebei Province (No: BJ2016023, QN2015002), and
the Nature Science Foundation of Hebei Province (No: E2016208107).
125
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high sulfur-containing bauxite. Trans. Nonferrous Met. Soc. China
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(1976)
 Iron Separation from Bauxite Through
Smelting-Reduction Process

Hanne Sellaeg, Leiv Kolbeinsen, and Jafar Safarian

Abstract
In the alumina production process through the dominant commercial Bayer process red
mud, which is not consumable and causes serious environmental challenges is produced.
Alternative sustainable process for bauxite treatment to alumina is the Pedersen process,
which was patented in 1920s and was in operation in Norway for many years before closing
down due to economic reasons. In this process, bauxite is smelted and reduced, which
yields pig iron and a calcium aluminate slag. Alumina is further produced from the slag
through a hydrometallurgical process. In the present study, different bauxites with different
chemical compositions are smelted with lime and reduced by coke. The smelting reduction
is studied through chemical analysis and microstructural study. It is shown that complete
separation of iron from the slag is possible and in addition the process is effective for partial
separation of the other impurities such as Ti, Si, V, from the Al2O3-containing slag.

Keywords

Bauxite Bayer process Pedersen process Alumina Smelting Reduction Pig iron
Slag

Introduction approximately four tons of bauxite [2]. Figure 1 shows that

Aluminum is the third most abundant element in the earth’s
crust, 8.3 wt%, and the most common crustal metal [1]. Due
to its chemical reactivity it only exists in oxidized form. The
principal ore of aluminum extraction today is bauxite,
although aluminum is found in other types of ores [1].
Aluminium is produced in three stages, first it is mined, then
made into alumina (Al2O3) through the Bayer process, and
finally the alumina is reduced to aluminium by the electro-
chemical process Hall-Hèroult [1]. To produce one ton
aluminium it is needed two tons of alumina and
H. Sellaeg
L. Kolbeinsen
J. Safarian (&)
Norwegian University of Science and Technology,
Alfred Getz vei 2, 7491 Trondheim, Norway
e-mail: Jafar.Safarian@ntnu.no
H. Sellaeg
e-mail: hannsel@stud.ntnu.no
L. Kolbeinsen
e-mail: Leiv.Kolbeinsen@ntnu.no
global alumina production has doubled the last 15 years [3].
The increase in alumina production by Bayer process also
increase the amount of the problematic waste product, red
mud. It is a loss of iron from the bauxite ore, and although
utilization of red mud is being investigated, it has not been
solved. So the waste is growing in a rate of one to one and a
half ton of red mud per one ton of alumina being produced
[4]. It is, therefore, of high interest to look at an alternative
method, that was used for over 40 years in Norway; the
Pedersen Process. It eliminates the red mud problem, pro-
duces saleable grey mud, extract pig iron, has lower CO2
emissions than Bayer, can be used for a wider range of
bauxite types with a better overall alumina yield.
The purpose of the present work is to study the
pyro-metallurgical part of the Pedersen process, which is
believed to be a more sustainable process compared to Bayer
process and is described in Section “Pedersen Process”. The
main focus is about the distribution of the elements existing

© The Minerals, Metals & Materials Society 2017 127

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_19
128
Fig. 1 Production development of alumina [5]
in bauxites between the produced iron and slag phases under
different process conditions.
Bauxite
Bauxite is mostly found in countries close to the equator,
like Australia, China and Brazil being the top producers per
2015 [6]. Bauxite comes in a wide range of textures, colors
and content, and is largely composed of a mixture of min-
erals that contains different amounts of hydrated aluminum
oxides and impurities like iron oxide, silica and titanic
dioxide [7]. Three types of minerals are found in bauxite;
gibbsite, boehmite and diaspore. Gibbsite is an aluminium
trihydrate (Al2O3
3H2O), while boehmite (c-AlO(OH)) and
diaspore (a-AlO(OH)) are two forms of alumina monohy-
drate. Bauxite ore contains usually iron minerals such as
goethite (FeOOH) and hematite (Fe2O3), titanium oxide in
the form of ilmenite (FeTiO3), silicon oxide (SiO2), etc. The
processing of the bauxites for alumina extraction is depen-
dent on the ore composition and the presence of impurities
like iron, silicon and titanium [7]. The most dominant being
mined today is gibbsite and boehmite as they are more
economical to process [2].
Bayer Process
The main commercial way to produce alumina is through the
well-known Bayer process, patented by Carl Josef Bayer in
H. Sellaeg et al.
Austria in 1888 [8, 9]. Typically, it produces smelter-grade
alumina of 99.5% Al2O3 [10]. The process simple flowsheet
is shown in Fig. 2. In this hydrometallurgical process, the
bauxite is digested with a hot solution of caustic soda
(NaOH) and lime (CaO). The main reactions in digestion
yielding sodium-aluminate solution is shown in Eq. 1.
Al2 O3 ðsÞ þ 2NaOH(aq) ! 2NaAlO2 ðaqÞ þ H2 O(vÞ ð1Þ
The products of the digestion step are separated in a
clarification process where undissolved impurities such as
silica and iron settles as mud, which is called red mud
residue [8]. Red mud is one of the largest industrial
by-products today (3 billion tons in 2010) [11]. As it does
not have a commercial value, several different methods is
used for its deposition, including deep-sea disposal,
lagooning and dry stacking and disposal. The trend today is
to dry stack or use dry cake disposal [11]. Even so, the red
mud can cause serious environment problems, as it has a
high alkalinity [4]. The sodium-aluminate solution product is
further treated and aluminum hydroxide is precipitated from
the solution according to reaction described in Eq. 2.
Al(OH) þ þ 
4 ðaq) þ Na ðaq) ! Al(OH)3 ðs) þ Na ðaq) þ OH ðaq)
ð2Þ
In the precipitation step a caustic solution is generated,
which is reused in the digestion step after concentration
control through an evaporation step for dewatering. The
main product of the precipitation step is aluminum hydrox-
ide Al(OH)3. A portion of fine Al(OH)3 particles are
Iron Separation from Bauxite Through Smelting-Reduction Process
Fig. 2 Alumina production by Bayer process [12]
separated and used in the precipitation step in order to
improve the process kinetics. The aluminum hydroxide is
further calcined in calcination furnace by using fuel i.e.
methane and alumina is produced. The calcination reaction
can be written as shown in Eq. 3.
2Al(OHÞ3 ðsÞ ! Al2 O3 ðsÞ þ 3H2 O ðvÞ ð3Þ
Pedersen Process
Alternative process for alumina production is the Pedersen
process, which has no red mud production problem. This
process was patented in Norway in the 1920s by Harald
Pedersen, and was used for over 40 years before it was
129
closed down due to economic reasons [13]. It was developed
to process ferruginous bauxites with high TiO2 and SiO2
content, as the Bayer process had limitations in processing
these [8]. The first step in this process is the main difference
compared to Bayer (see Fig. 3). Instead of digestion and
clarification, resulting in red mud, the first step in the Ped-
ersen process is to smelt bauxite, lime as flux and coke as
reduction agent together, and the iron oxide is then reduced
to molten iron and can be taken out and reused in ferrous
industry [8]. The process does not only eliminate the red
mud problem, but also one can extract pig iron. The main
reactions for the smelting-reductionreduction step are the
reduction of iron oxides i.e. Fe2O3 (Eq. 4), and slag for-
mation from bauxite and lime (Eq. 5):
2Fe2 O3 ðsÞ þ 3CðsÞ ! 4FeðsÞ þ 3CO2 ðgÞ ð4Þ
130
Fig. 3 Alumina production by the Pedersen process, after Miller et al. [13]
Al2 O3 ðsÞ þ CaOðsÞ ! ðCaO
Al2 O3 ÞðsÞ ð5Þ
As Fig. 3 shows, the produced calcium-aluminate slag, in
the smelting-reduction furnace, is reduced in size by crush-
ing or milling, before going through a wet stage process,
with digestion and washing. The slag is digested by using a
sodium carbonate solution, and this leaching stage can be
chemically described in Eq. 6:
ðCaO
Al2 O3 ÞðsÞ þ Na2 CO3 ðlÞ ! 2NaAlO2 ðlÞ þ CaCO3 ðsÞ
After the digestion step, the solution goes through a
multiple step washing stages with thickeners, and a grey
mud is extracted. As with pig iron, grey mud is a consum-
able by-product (cement, fertilizer, among others) [13]. The
overall chemistry in this process is simple, but there is a
large number of side-reactions which makes it complicated.
In the precipitation section CO2 is added to the Na2Al2O2
solution in vessels containing slow moving stirrers, and
alumina hydroxide precipitates [13] as described in Eq. 7:
2NaAlO2 ðaqÞ þ H2 O(lÞ þ CO2 ðgÞ
! Al2 ðOHÞ3 ðsÞ þ Na2 CO3 ðaqÞ
The sodium carbonate recycles back into the digestion
step, while the precipitated alumina hydroxide is calcined to
H. Sellaeg et al.
alumina powder [13] through the chemical reaction (Eq. 3)
mentioned above.
Experimental Procedure
The employed experimental work in the present study is
described as follows.
ð6Þ
Materials
Three different types of bauxites were used in this study.
The bauxites mainly contained the phases kaolinite
(Al2Si2O5(OH)4), gibbsite (Al(OH)3) and hematite (Fe2O3).
The samples were delivered in grinded and calcined form,
and their chemical composition is presented in Table 1.
The experiments were done in graphite crucibles with
40 mm outside diameter, 32 mm inside diameter and 50 mm
height. Three different mixture of materials were put in the
crucibles.
ð7Þ
1. Bauxites (A, B, C);
2. Bauxite B with added CaO;
3. Bauxite B with added CaO and coke.
Iron Separation from Bauxite Through Smelting-Reduction Process 131

Table 1 Chemical composition of bauxite samples in weight% on dry basis

Bauxites Al2O3 SiO2 Fe2O3 TiO2 FeO Total wt%
A 55.75 33.50 6.25 1.75 2.74 100
B 59.77 15.93 21.84 2.46 – 100
C 71.53 17.50 8.93 2.03 0 100

Fig. 4 Induction furnace used for smelting-reduction experiments

The CaO, with purity around 98%, was mixed in order to
obtain a 40% CaO and 60% Al2O3 slag, while the coke
addition was 50% more than the stoichiometric required to
complete the reduction of the hematite (2Fe2O3 + 3C = 4
Fe + 3CO2(g)). The content of the coke was 97 wt% fix-C,
2 wt% ash and 0.41 wt% volatile matter. The bauxites were
further grinded in a vibratory disc mill, mixed and put in
graphite crucibles for smelting.
Smelting-Reduction
The smelting-reduction experiments were done in an
induction furnace illustrated in Fig. 4. A thermocouple type
C was used for measuring the temperature. The thermo-
couple was covered in an insulating tube inserted in a gra-
phite tube, and placed in the large graphite crucible in
between the samples. The heating rate was approximately
20 °C/min up to 1600 °C, followed by keeping at this
temperature for one hour. Then, the samples were cooled
down very slowly at 5 °C/min to the room temperature.
SEM Analysis
All the samples (graphite crucibles containing metal and slag
phases) were machine cut, imbedded in epoxy, grinded and
polished. The crucibles were cut from the middle so that the
cross section from bottom of crucible to the top of the solidi-
fied slag can be studied. The microstructure and composition
of the phases were studied by Scanning Electron Microscopy
(SEM) supported by Energy Dispersive Spectroscopy (EDS).
Results and Discussion
The results of the smelting-reductionreduction and SEM
analysis are presented and discussed as follows.
132
Smelting-Reduction of Single Bauxites
All the bauxite materials became molten at the applied
temperature (1600 °C) as observed from the crucibles top. It
was observed that the smelted bauxites without any addi-
tions give porous structure, after cooling down to the room
temperature. The complete melting of the all bauxites is
proved with regard to the formation of a continuous slag
matrix from all the samples as illustrated in Figs. 5, 6 and 7
for three types of bauxites. In these Figures, the grey phase is
slag and the bright particles distributed in it are metal par-
ticles. SEM study of the samples indicated that the sample
containing highest amount of iron (sample B) is more por-
ous. The SEM images (Figs. 5, 6 and 7) show that iron
Fig. 5 SEM images of
smelted-reduced bauxite A which
contained 6% iron oxide
Fig. 6 SEM images of
smelted-reduced bauxite B which
contained 22% iron oxide
Fig. 7 SEM images of
smelted-reduced bauxite C which
contained 9% iron oxide
H. Sellaeg et al.
oxides were reduced to metallic iron in all samples. The
images show that the amount and size of the iron particles is
increased with increasing the iron oxide content of the
bauxite. Moreover, the particles were equally distributed
throughout the samples and not very large iron particles were
found in the samples. This may be due to the high viscosity
of the slag phases in all the samples, which are high in
Al2O3.
EDS and X-ray mapping of the elements in the
smelted-reduced bauxites clearly shows the complete iron
oxide reduction as shown typically for the bauxite B in
Fig. 8. As seen, there is almost no Fe in the slag phase, while
it contains Al, Ti, Si, and O. Hence, we may say that the slag
contains Al2O3, TiO2 and SiO2. In addition, partial
Iron Separation from Bauxite Through Smelting-Reduction Process
Fig. 8 X-ray mapping of the main elements in smelted-reduced bauxite B
separation of silicon and titanium oxides is observed, which
shows that the slag matrix contains the both three oxides or a
ternary Al2O3–TiO2–SiO2 slag, and the slag contains sig-
nificant Al2O3-rich particles, most likely pure alumina
particles.
Smelting-Reduction of Bauxite with Lime
By adding CaO into the bauxite (with CaO:Al2O3 = 2:3)
significant differences were observed. The iron particles
produced through the reduction have largely increased in
size, and are positioned in the bottom of the crucible as
illustrated in Fig. 9. This is due to the formation of a more
fluid calcium-aluminate slag by using the flux compared to
the smelting-reductionreduction of only bauxite. The metal
particles contain a lot of randomly distributed carbon flakes
(Fig. 9), presumed to be from the graphite crucible in contact
with the smelted iron (approximately 7 wt%). When the
bauxite was smelted and reduced without CaO, the produced
metal micro-droplets were surrounded by the slag phase and
with no contact to the graphite crucible and therefore they
did not contain significant amount of dissolved carbon, or
graphite flakes after solidification. In contrast, when lime is
used, the metal drops are settled in the bottom of crucible
and they will get the carbon saturation level in contact with
133
the graphite crucible. This carbon appeared in the form of
graphite flakes in solidification due to the much lower sol-
ubility of carbon in solid iron. EDS analysis of the slag
shows that it mainly contains Ca, Al, Si, O and Ti elements
(Fig. 9). Carbon peak is from the sample coating by carbon,
and the slag does not have significant carbon.
The microstructural analysis of the slag phase and X-ray
mapping showed that the produced calcium-aluminate slag
contains different phases with different amounts of the var-
ious oxides in them as illustrated in Fig. 10. Compared to the
smelted-reduced bauxite without lime, there is no single
Al2O3-rich phases in the slag and the co-existing phases
contain other oxides as well. In Fig. 10 we see Ca and Mg
elements, which were not observed when only bauxites were
treated; Ca and Mg are originated from the consumed lime.
Smelting-Reduction of Bauxite with Lime
and Coke Addition
Addition of coke does not seem to have an effect on the size
of the pig iron particles. This may indicate that the process
time as 60 min have been long enough for the reduction of
iron oxides in the both experiments with or without coke. In
principle, however, we expect to have faster reduction of the
iron oxides with the addition of coke particles due to
134 H. Sellaeg et al.

Fig. 9 SEM image of bauxite B smelted with CaO (on the left), and EDS analysis of the slag phase

Fig. 10 X-ray mapping of the slag phase produced through the smelting-reductionreduction of bauxite B with lime

providing higher reaction interfacial area. Experiments in
short reaction times may give better overview about the rate
of iron oxide reduction.
The EDS and X-ray mapping of the elements of the
bauxite samples smelted with lime show that vanadium, and
titanium precipitate in a layer around the iron metal particle
(Fig. 11), which are most likely carbides. These carbides are
formed during the solidification of the metal phase from the
dissolved Ti and V particles in the liquid iron as its mech-
anism presented elsewhere [5]. Obviously, an advantage of
bauxite treatment through the smelting-reduction process is
the partial removal of impurities such as Si, Ti, V, in addi-
tion to the complete removal of iron, which is very beneficial
for further hydrometallurgical treatment of the produced
calcium-aluminate slag and production of less process by
product.
Iron Separation from Bauxite Through Smelting-Reduction Process
Fig. 11 X-ray mapping of a metal particle formed in the smelting-reductionreduction of bauxite B with lime
Conclusion
The smelting-reduction of three types of bauxite with dif-
ferent amounts of iron oxides were carried out. In addition,
the high iron-containing bauxite was treated through lime
addition and lime + coke addition. The following results
have been obtained:
(i) The smelting-reduction of bauxite is a feasible way to
separate iron from bauxite and produce a high alu-
mina slag as feedstock for further alumina production.
(ii) Complete reduction of iron oxides occurs, which
yields pig iron. The separation of the produced molten
iron phase from the slag is the best when lime is used,
due to providing a low viscose calcium-aluminate
slag.
(iii) Different phases co-exist in the slag depending on the
lime addition. When bauxites without lime were
treated, Al2O3-rich particles in an Al2O3–SiO2–TiO2
slag matrix were formed. But, when lime was used,
different three-four component slag phases were
formed which all had different amounts of Al2O3.
(iv) The smelting reduction of bauxite with lime indicated
partial removal of Si, Ti, V from the slag into the iron.
Not significant difference between the samples with
and without the use of coke was observed, indicating
the fast reduction of iron oxides from the smelted
bauxite, and calcium-aluminate slag.
Acknowledgements The authors would appreciate the financial sup-
port of this study through the Research Domain 5-Materials and Society
of SFI-metal production, a center for Research-based Innovation in
Norway.
135
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pp. 789–99
 Thermodynamic Behavior of Lime
Desulfurization in Sodium Aluminate Solution

Wu Xianxi, Zhu Weidong, Jiang Hongshi, and Wu Song

Abstract
P o P o
The method of GoR;Ca4Al2SO10
12H2O ¼ Goxide þ GR was used to estimate the Gibbs free
energy of calcium hydroaluminosulfate ð3CaO
Al2 O3
3CaSO4
nH2 O, 3CaO
Al2 O3

CaSO4
12H2 O) and Ca3Al2(OH)12, then to calculate the Gibbs free energies of
desulfurization reaction that lime interacts with sodium sulfate in sodium aluminate
solution. To make judgments about reaction direction, the correctness of calculation was
validated by experiments. Thermodynamic calculation and XRD phase identification
indicate that 3CaO
Al2 O3
3CaSO4
nH2 O and 3CaO
Al2 O3
CaSO4
12H2 O can be gener-
ated in the procces of desulfurization. With the reaction time to extend the calcium
hydroaluminosulfate decomposition, the 3CaO
Al2 O3
3CaSO4
nH2 O has been character-
ized. The thermodynamic behavior of adding lime to desulfurization in the sodium
aluminate solution was discussed.

Keywords
Calcium hydroaluminosulfate Gibbs free energy Estimation Experiment
Thermodynamics

Introduction
China’s bauxite is mainly diaspore ore. The aluminum sili-
con ratio is less than 7. And the conventional Bayer alumina
can not be used to produce alumina economically. In some
areas there is a considerable portion with higher sulfur,
China has proven reserves of five hundred and sixty million
tons of high sulfur bauxite, the prospective reserves reach
two billion tons [1–3]. In recent years China has developed
Lime Bayer process for low alumina silicon ratio diaspore
Foundation item: Project 2136609 supported by National Natural
Science Foundation of China.
W. Xianxi (&)
J. Hongshi
W. Song
College of Chemical Engineering, Guizhou University, Guiyang,
550025, China
e-mail: wuxx2012@sina.co
Z. Weidong
College of Materials and Metallurgy, Guizhou University,
Guiyang, 550025, China
ore, and the economic benefit is obvious, but a large number
of high sulfur bauxite can not be developed and utilized due
to the harmfulness of sulfur on the alumina production. In
recent years China has developed the Lime Bayer process for
the diaspore ore of low alumina silicon ratio, and the eco-
nomic benefit is obvious, but a large number of high sulfur
bauxite have not been got exploitation and utilization yet
because of the harmfulness of sulfur on the alumina pro-
duction [4–6]. Researching and solving the exclusion of
sulfur compounds from Bayer process, thus using low alu-
minum silicon ratio with high sulfur diaspore ore to produce
alumina economically have important practical and theoret-
ical significance.
In the process of producing alumina, the sulfide existing
in a form of pyrite in bauxite reacts with sodium aluminate
and caustic into the solution in the forms of sulfide, thio-
sulfate and sulfite, and finally transforms into sodium sulfate
[7, 8].

© The Minerals, Metals & Materials Society 2017 137

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_20
138 W. Xianxi et al.

For sulfur removal in alumina production by the Bayer
process and the Lime Bayer, literatures [9–11] conducted
some studies about it, thinking that can add lime in sodium
aluminate solution to desulfurize. Ca(OH)2 interacts with
sodium aluminate to generate calcium aluminate monosul-
fate, 3Ca
Al2 O3
CaSO4
12H2 O ðCa4 Al2 SO10
12H2 O). At
the same time under certain conditions calcium aluminate
trisulfate 3Ca
Al2 O3
3CaSO4
nH2 O(Ca6 Al2 SO18
nH2 O)
and other sulfur including compounds would be generated to
achieve the purpose of removing sulfur. Because the number
of water molecules of 3Ca
Al2 O3
3CaSO4
nH2 O is different,
n can be 31, 6 and other different figures. It was noted that
the desulfurization efficiency of calcium aluminate trisulfate,
3Ca
Al2 O3
3CaSO4
nH2 O formed was three times efficient
than that of calcium aluminate monosulfate 3Ca
Al2 O3

CaSO4
12H2 O formed, and the Al2O3 loss reduced. At
present, there is no literature reported about the thermody-
namic data of Gibbs free energy of calcium aluminate sul-
fate, nor definite evidence of the existence of the calcium
aluminate trisulfate given, it is difficult to study further. For
this reason, the thermodynamic conditions for the formation
of calcium hydrate calcium aluminate will be studied, and
the Gibbs free energy calculated here in this paper, and the
results will be confirmed by experiments. And the calcium
aluminate trisulfate was characterized, and its existence
was confirmed. At the same time, the thermodynamic
behavior of lime desulfurization in sodium aluminate
solution was studied, which provided the theoretical and
experimental basis for desulfurization of alumina.
Thermodynamic Analysis
Adding lime in sodium aluminate solution to desulfurize, the
possible reactions of Ca(OH)2 acting with sodium sulfate are
listed in Table 1 [9–11].
To determine if the reaction could happen, it has to know
the reactant’s formation free energy. But there is no any
report on the thermodynamic parameters about calcium
aluminate sulfate at present. Some methods are used to es-
timate in order to obtain a more reliable calcium aluminate
sulfate formation free energy.
Karpov and Kashik [12], Nriagu [13], Chen [14], Tardy
and Garrels [15], have put forward a number of empirical
formula to estimate the thermodynamic data of some min-
erals. The common feature of these formulas is that using the
empirical formula with parameters when calculating, the
parameters are more, cumbersome calculation; some parti-
cles or materials parameters were not given, and the Gibbs
free energy and enthalpy can only be calculated under the
standard condition, thus making the computation has some
limitations.
Wen Yuankai [16, 17] proposed that any complex
oxygen-containing acid salt mineral was taken as complexes
of various acidic oxides and alkaline oxides, the strongest
alkaline oxide first reacts with the strongest acidic oxide when
compounding, then compounds with the second strongest
acidic oxide. Water is present in the form of hydrated salt in
most cases, and sometimes participates in the reactions as a
constitutional water. In this way, the Gibbs free energies of
complex silicate minerals can be regarded as two parts, the
P
sum G0oxide of each oxide’s Gibbs free energy, and the sum
P 0
GR of reaction free energies among the oxides. Using the
above method, Wen Yuankai calculated the standard free
energies of 23 kinds of complex silicate minerals, and most of
the calculated results were in agreement with the experi-
mental results, and the deviation was less than 2%.
But from the above discussion, oxides and composite
oxides that Wen Yuankai said did not apply only in SiO2 and
silicates. In fact, any complex containing oxygen acid salts
and minerals can be calculated according to the method.
Namely the free energy of formation of complex containing
oxygen acid salts and minerals was taken as a sum of free
energies of formation of oxides and reaction free energies
among the oxides, thus the the free energy of formation of
any complex containing oxygen acid salt mineral can be
calculated.
Ducument [18] extended this algorithm, which not only
can be used to calculate the Gibbs free energy of a complex
silicate mineral under the standard state, but also to do that at
any temperature, just needing to change the data under
standard state into the ones at a temperature. But both Wen
Yuankai and ducument [18] used the method to calculate the
Gibbs free energies of complex silicates (such as

Table 1 Correlation reactions
between Ca(OH)2 and sodium
sulfate in sodium aluminate
solution
4CaðOHÞ2 þ Na2 O
Al2 O3 þ Na2 SO4 þ 10H2 O ¼ 3CaO
Al2 O3
CaSO4
12H2 O þ 4NaOH (1)
6CaðOHÞ2 þ Na2 O
Al2 O3 þ 3Na2 SO4 þ 29H2 O ¼ 3CaO
Al2 O3
3CaSO4
31H2 O þ 8NaOH (2)
6CaðOHÞ2 þ Na2 O
Al2 O3 þ 3Na2 SO4 þ 4H2 O ¼ 3CaO
Al2 O3
3CaSO4
6H2 O þ 8NaOH (3)
3CaO
Al2 O3
3CaSO4
6H2 O þ 6H2 O ¼ 3CaO
Al2 O3
CaSO4
12H2 O þ 2CaSO4 (4)
3CaO
Al2 O3
3CaSO4
nH2 O ¼ 3CaO
Al2 O3
CaSO4
12H2 O þ 2CaSO4 þ ðn  12ÞH2 O (5)
Ca4 Al2 SO10
12H2 O ¼ Ca3 Al2 ðOHÞ12 # þ CaSO4 # þ 6H2 O (6)
CaSO4 þ 2NaOH ¼ CaðOHÞ2 þ Na2 SO4 (7)
Thermodynamic Behavior of Lime Desulfurization in Sodium …
CaAl2 Si2 O8
H2 O; Ca3 Al2 Si3 O12 , etc.), and no other salts
were calculated.
Through the complex silicate and their calculation of
comparison, it can be seen that the calcium hydroalumi-
nosulfate is a complex oxysalt, which contains two or more
metallic ions, alkaline oxide (CaO) and acidic oxide (SO3),
and also a hydrated salt or constitutional water exists. Sim-
ilar to complex silicate composition and structure, according
to the principle of this method, the Gibbs free energy cal-
culation of calcium aluminate can be carried out after
modifying.
Because the experiments of adding lime in the sulfur
sodium aluminate to synthetize 3CaO
Al2 O3
CaSO4
12H2 O
were carried out at about 343 K (70 °C) in the literatures [9–
11], and considered to be the best synthesis condition, they
all failed to get a conclusive evidence that the existence of a
calcium aluminate trisulfate generated, the thermodynamic
basis for the existence of the two was not given yet. This
paper will use the method to calculate the Gibbs free ener-
gies of two kinds of calcium aluminate sulfate at the tem-
perature and to determine whether they can generate and
react in the sodium aluminate solution. Because of no cor-
responding data as compared reference, the calculation
correctness and reliability will be tested experimentally.
The Gibbs free energy calculation of 3CaO
Al2 O3

CaSO4
12H2 OðCa4 Al2 SO10
12H2 OÞ, the calcium aluminate
sulfate was decomposed by the composition of oxides and
water, then calculating by the above method.
X X
GoR;Ca4Al2SO10
12H2O ¼ Gooxide þ GoR ð1Þ
X
Gooxide ¼ 4GoCaO þ GoAl2O3 þ GoSO3 þ 12GoH2O
X (2)
GoR ¼ GoR;CaSO4 þ GoR;Ca3Al2O6 þ GoR;Ca3Al2SO10 þ GoR;Ca4Al2SO10
12H2O
Where: GoR;CaSO4 stands for the reaction free energy of
CaSO4 synthesized by a CaO and a SO3; GoR;Ca3Al2O6 stands
for the reaction free energy of combining to form
3CaO
Al2 O3 by 3 CaO and an Al2O3, more than analogy.
From the above analysis, the reaction free energy of
calcium hydroaluminosulfate is composed of energy com-
bining by acidic and alkaline oxides and other energies such
as the energy of oxysalt compositing and that of the attached
water when attaching. In this method, calculation shows that
the energy value of combining acidic and alkaline oxides is
large, accounted for the main part, the energies of other
oxides are negligible, so the Formula (3) can be simplified
as:
X ¼ 17646:23ðKJ=molÞ
GoR ¼ GoR;CaSO4 þ GoR;Ca3Al2O6 ð4Þ
139
The Go value of each oxide under standard condition
(298 K, 25 °C) can be identified from the Handbook of
thermodynamic data, and then the Go of calcium aluminate
sulfate under standard condition can be calculated. In order
to calculate the G value of calcium aluminate sulfate at other
temperature, the Go value of each oxide under standard
condition can be changed into the value at the temperature.
The thermodynamic data at a certain temperature can be
identified from the Handbook of thermodynamic data, or are
calculated with the classical thermodynamic formulas from
the standard condition, such as using the following formula
to calculate DGT.
Z T Z T 
0 0 DCp
DGT ¼ DH298  TDS298 þ DCp dT  T d
298 298 T
ð5Þ
Founding for the thermodynamic data Ho, So and CP from
the Handbook, after calculating the corresponding ΔHo, Δ So
and ΔCP, plug type calculation. Table 2 lists the thermody-
namic data [19] of the oxides under the standard condition
and calculated CP, the thermodynamic data [20] of corre-
sponding materials at 343 K (70 °C).
The calculation for GR of calcium aluminate monosulfate
3CaO
Al2O3
CaSO4
12H2O(Ca4Al2SO1012 H2O) at 343 K
is as follows:
X
Goxide ¼ 4GCaO þ GAl2O3 þ GSO3 þ 12GH2O
(1) ¼ 4  ð648:71Þ þ ð1693:98Þ þ ð486:83Þ þ 12
 ð308:73Þ ¼ 8480:53 ðKJ=molÞ
GR;CaSO4 ¼ GR;CaSO4  GR;CaO  GR;SO3
¼ 1472:13  ð648:71Þ  ð486:83Þ ¼ 336:59 ðKJ=molÞ
ð2Þ
GR;Ca3Al2O6 ¼ GR;Ca3Al2O6  3GR;CaO  GR;Al2O3
¼ 3659:21  3  ð648:71Þ  ð1693:98Þ ¼ 19:1ðKJ=mol)
X
GR ¼ GR;CaSO4 þ GR;Ca3Al2O6
ð3Þ ¼ 336:59 þ ð19:1Þ ¼ 355:69ðKJ=molÞ
P P
(3) GR;Ca4Al2SO10
12H2O ¼ Goxide þ GR ¼ 8480:53 þ ð355:69Þ ¼ 8836:22ðKJ=molÞ
Similarly, GR for calcium aluminate trisulfate at 343 K
(70 °C) can be calculated.
Due to the difference in the number of combined water
molecules, the calcium aluminate trisulfate has different
representations, but the calcium aluminate trisulfate is in
agreement with the molecular formula. Such as
3CaO
Al2O3
3CaSO4
31H2O(Ca6Al2S3O18
31H2O) and 3CaO

 
Al2 O3
3CaSO4
6H2 O Ca6 Al2 ðSO4 Þ3 ðOHÞ12 Calculation
GR 3CaO
Al2 O3
3CaSO4
31H2 OðCa6 Al2 S3 O18
31H2 OÞ
X X
GR;6CaAl2 S3 O18
31H2 O ¼ Goxide þ GR
¼ 16617:36 þ ð1028:87Þ
140 W. Xianxi et al.

Table 2 Thermodynamic data of Materials CaO SO3 Al2O3 H2O CaSO4 3CaO
Al2O3
various materials at 25 and 70 °C
Go (KJ/mol, −646.15 −472.28 −1690.46 −298.08 −1465.48 −3646.10
298 K)
Go (KJ/mol, −648.71 −486.83 −1693.98 −308.73 −1472.11313 −3659.21
343 K)

X X
GR Ca6 Al2 ðSO4 Þ3 ðOHÞ12 ¼ Goxide þ GR DG2 ¼ 17954:96 þ 8  ð451:28Þ  6  ð937:30Þ  2
¼ 8899:11 þ ð1028:87Þ  ð1158:50Þ  3  ð1441:16Þ  30  ð308:73Þ
¼ 9927:98ðKJ=molÞ ¼ 39:02 KJ=mol
Similarly, GR Ca3Al2(OH)12 = −5511.71 (KJ/mol) can
also be calculated. Similarly, after calculation the reaction (3) has DG3 =
The free energy of calcium aluminate sulfate was calcu- −39.02 kJ/mol. Through the calculation for Gibbs free
lated, and the reaction free energies of the reactions (1)–(5) energy of desulfurization reaction equation in sodium alu-
can be calculated, which was used to determine the reaction minate solution: DG1 = −46.67 kJ/mol, DG2, = −39.02
direction at 343 K (70 °C). kJ/mol, DG  0 in the three equations. This shows that
The thermodynamic data of the calculation reaction the reaction trend to form calcium aluminate monosulfate
Eqs. (1)–(5) at 343 K (70 °C) are as shown in Table 3: and calcium aluminate trisulfate is larger. There should be
The above data into the calculation: two kinds of calcium aluminate hydrate formed in sodium
aluminate solution.
DG1 ¼ 8836:22 þ 4  ð451:28Þ  4  ð937:30Þ  2 According to Hess’s law, from the reactions (1)–(3), the
 ð1158:50Þ  ð1441:16Þ  10  ð308:73Þ reaction Eqs. (4) and (5) can be got by addition and sub-
traction operation and finishing,
¼ 46:67 KJ=mol
DG4;5 ¼ 7:65 KJ=mol:

DG6 ¼ 8836:22  5516:39  1472:13  6  ð308:73Þ ¼ 0

Table 3 The thermodynamic data at 70 °C in reaction Eqs. (1)–(5)

Materials Ca(OH)2 NaAlO2 Na2SO4 NaOH H2O
G (KJ/mol, 343 K) −937.30 −1158.50 −1441.16 −451.28 −308.73

Table 4 The Gibbs free energies of reactions (1)–(6)

Reaction equations Calculated △G KJ/mol
4CaðOHÞ2 þ Na2 O
Al2 O3 þ Na2 SO4 þ 10H2 O −46.67
(1)
¼ 3CaO
Al2 O3
CaSO4
12H2 O þ 4NaOH
6CaðOHÞ2 þ Na2 O
Al2 O3 þ 3Na2 SO4 þ 29H2 O −39.02
(2)
¼ 3CaO
Al2 O3
3CaSO4
31H2 O þ 8NaOH
6CaðOHÞ2 þ Na2 O
Al2 O3 þ 3Na2 SO4 þ 4H2 O −39.02
(3)
¼ 3CaO
Al2 O3
3CaSO4
6H2 O þ 8NaOH
3CaO
Al2 O3
3CaSO4
6H2 O þ 6H2 O −7.56
(4)
¼ 3CaO
Al2 O3
CaSO4
12H2 O þ 2CaSO4
3CaO
Al2 O3
3CaSO4
nH2 O −7.56
(5)
¼ 2CaSO4 3CaO
Al2 O3
CaSO4
12H2 O þ þ ðn  12ÞH2 O
Ca4 Al2 SO10
12H2 O 0
(6)
¼ Ca3 Al2 ðOHÞ12 þ CaSO4 þ 6H2 O
CaSO4 þ 2NaOH −3.86
(7)
¼ CaðOHÞ2 þ Na2 SO4
Thermodynamic Behavior of Lime Desulfurization in Sodium …
DG7 ¼ 1472:11 þ 2  451:28937:26  1441:16
¼ 3:86 KJ=mol
The above calculation results are listed in Table 4:
It can be seen from the calculated results of Table 4 that
except the reaction (6) is a balance reaction, the rest of the
reactions are to the right. But so far, the exact evidence for
forming 3CaO
Al2 O3
3CaSO4
nH2 OðCa6 Al2 S3 O18
nH2 O)
of lime desulfurization in sodium aluminate solution and the
process of the above reaction have not been reported.
The thermodynamic calculation is reliable, because there
is no corresponding report, unable to compare and judge, the
experiments will be used to verify here.
Experiments
The sodium aluminate solution was prepared by analytical
reagents of sodium hydroxide and aluminium hydroxide
with the Gundam autoclave. Calcium oxide was got by
putting analytical reagent of calcium hydroxide into the
crucible, calcining at 900 °C in a muffle furnace for 2 h, then
cooling in a dryer, and finally preserved under the sealing
and drying conditions.
Prepared in a molar ratio of 3:1 sodium aluminate
solution was diluted 4 times with distilled water. The
diluted sodium aluminate solution (500 ml) was placed in a
1L of stainless steel cup, and then Na2SO4 reagent was
added to it. The experiment was performed in a constant
temperature bath (the temperature precision was automati-
cally controlled in ±1 °C under stirring by an agitator at a
constant speed). A certain amount of calcium oxide was
dissolved in water to make lime milk, which was slowly
added to the sodium aluminate solution (24 g/L of SO24)
under stirring condition, stirring for 50–150 min at 70 °C.
The solution was decompressed and filtered after the
reaction and the filter cake quality was determined. The
cakes were washed repeatedly with water and dried with
Fig. 1 XRD pattern of molar
ratio of 3:1 in desulfurization
product (reaction temperature was
at 70 °C, for 50 min)
141
cold wind. The reaction products were analyzed by chem-
ical methods, X-ray diffraction and infrared spectroscopy.
The reaction times were for 50, 70, 120 and 150 min
respectively.
Results and Discussion
When the adding amount of lime to 8.5 g, reaction tem-
perature was 70 °C, the reaction time reached 50 min, the
reaction products were calcium aluminate monosulfate
(Ca4Al2SO10
12H2O) and calcium aluminate trisulfate
[Ca6Al2(SO4)3(OH)12], and the sum of both contents
reached 96.4%, the effect was very significant. X-ray
diffraction pattern (Fig. 1) shows the diffraction peaks of
the calcium aluminate monosulfate 3CaO
Al2 O3

CaSO4
12H2 O in the desulfurization products, its d values
were 8.9, 4.45, 3.99, 2.87, 2.42, and 2.233  10-1nm etc.
eigenvalues. At the same time, the diffraction peaks of the
calcium aluminate trisulfate [Ca6Al2(SO4)3(OH)12] were
also shown, its d values were 9.8, 5.61, 5.54, 4.91, 3.88,
2.79, and 2.56  10-1 nm etc. eigenvalues. A diffraction
pattern is an important basis for determining the reaction
product. It is confirmed that there was calcium aluminate
trisulfate formed, which has not been reported previously.
Experiment shown in Fig. 1 is consistent with the
aforementioned DGo  0, the judgment for that should have
two kinds of calcium aluminate sulfate generated. It illus-
trates that the above method of calculating the Gibbs free
energy of calcium aluminate hydrate is correct, and the result
is more reliable.
Figure 2 shows the experiment under the same conditions
as shown in Fig. 1. Only the reaction time was different, the
reaction time was 70 min, and the reaction product was only
calcium aluminate monosulfate (Ca4Al2SO10
12H2O) and
Ca3Al2 (OH)12, CaSO4 by XRD diffraction analysis, and
calcium aluminate trisulfate (Ca6Al2(SO4)3(OH)12) disap-
peared. And the main component of the product is
142
Fig. 2 XRD pattern of molar
ratio of 3:1 in desulfurization
product (reaction temperature was
at 70 °C, for 70 min)
Ca4 Al2 SO10
12H2 O ðCa4 Al2 SO10
12H2 OÞ, the content of
about 78%, the desulfurization efficiency of up to 80%.
According to Hess’s law, the reaction can be obtained by
coupling reactions (1) and (3):
3CaO
Al2O3
3CaSO4
6H2O þ 6H2O
¼ 3CaO
Al2O3
CaSO4
12H2O þ 2CaSO4
(4):
G4 ¼ DG1  DG3 ¼ 46:67  ð39:02Þ
¼ 7:65 KJ=mol\0:
Due to DG4<0, prolonging the reaction time, the calcium
aluminate trisulfate 3CaO
Al2 O3
3CaSO4
6H2 O will
decompose a calcium aluminate monosulfate 3CaO
Al2 O3

CaSO4
12H2 O and CaSO4 according to reaction (4).
The reaction Eq. (1) subtracts the reaction Eq. (2),
DG = −7.65 is still available, from this (5) can be deduced.
Fig. 3 XRD pattern of molar
ratio of 3:1 in desulfurization
product (reaction temperature was
at 70 °C, for 120 min)
W. Xianxi et al.
3CaO
Al2 O3
3CaSO4
nH2 O
¼ 3CaO
Al2 O3
CaSO4
12H2 O þ 2CaSO4
þ ðn  12ÞH2 O
G5 ¼ 46:67  ð39:02Þ ¼ 7:65 KJ=mol\0:
Figure 2 and the above calculations show that
3CaO
Al2 O3
3CaSO4
nH2 O is a metastable substance,
which decomposes into 3CaO
Al2 O3
CaSO4
12H2 O and
2CaSO4 with the reaction time extending.
Figure 3 also shows the experiment under the same experi-
mental condition shown as in Fig. 1, the reaction time was
120 min. Through XRD analysis, there were only calcium
aluminate monosulfate (Ca4Al2SO10
12H2O) and Ca3Al2
(OH)12, CaSO4 in reaction products, the contents of other two
substances Ca4Al2SO10
12H2O (Ca4Al2SO10.12H2O) in prod-
ucts did not differ much, about 40%, indicating that Ca4Al2-
SO10
12H2O and 3CaO
Al2O3
3CaSO4
nH2O were all the same
metastable substances, with the reaction time prolonging,
decomposition quantity of Ca4Al2SO10
12H2O increased.
Thermodynamic Behavior of Lime Desulfurization in Sodium …
Fig. 4 XRD pattern of molar
ratio of 3:1 in desulfurization
product (reaction temperature was
at 70 °C, for 150 min)
When the experiment was carried out to 150 min, the
XRD diffraction analysis of the reaction product was shown
in Fig. 4.
There was no Ca4Al2SO10
12H2O in the reaction product,
only the major component Ca3Al2(OH)12, followed by Ca
(OH)2 and a small amount of CaSO4. But previously calcu-
lated DG6 = 0, the reaction Ca4Al2SO10
12H2O =
Ca3Al2(OH)12 + CaSO4 + 6H2O (6) should be reversible.
Why is the reaction carrying out to the right with time? This
may be the reaction CaSO4 + 2NaOH = Ca(OH)2 + Na2SO4
(7) existing in an environment of sodium aluminate solution,
after calculation, △G7 = −3.86 kJ/mol. The reaction makes
CaSO4 consumption, so that the destructed balance makes the
reaction move to the right, finally Ca4Al2SO10
12H2O dis-
appeared, leaving only Ca3Al2(OH)12 Ca(OH)2 and CaSO4.
To sum up in sodium aluminate solution, the reaction
process of adding lime at 70 °C is that:
When reaction lasted for 50 min, 3CaO
Al2 O3

CaSO4
12H2 O and 3CaO
Al2 O3
3CaSO4
nH2 O were gen-
erated, reacting continuously to 70 min, 3CaO
Al2 O3

3CaSO4
nH2 O disappeared and decomposed into 3CaO

Al2 O3
CaSO4
12H2 O and CaSO4. Thereafter continuing to
react, 3CaO
Al2 O3
CaSO4
12H2 O began to decompose,
from 70 to 120 min, the amount of 3CaO
Al2 O3
CaSO4

12H2 O reduced continuously (78–40%), to 150 min, the
reaction completely disappeared, only Ca3Al2(OH)12, Ca
(OH)2 and CaSO4 were left in the solution.
From the point of view of the desulfurization, the reaction
products were mainly the solid ones of 3CaO
Al2O3
143
3CaSO4
nH2O, 3CaO
Al2O3
CaSO4
12H2O and CaSO4.
Reacting at 70 °C for 70 min ago, the desulfurization effi-
ciency could reach 80%. Namely under the experimental
conditions, desulfurization efficiency of the reaction to add
lime in the sulfur sodium aluminate solution is high, then
with the reaction time extending desulfurization efficiency
decreased gradually.
Conclusions
1: The Gibbs free energy of complex calcium aluminate
sulfate can be calculated with the sum of the Gibbs free
energies of the compositive stable oxides and the sum of
those of chemical reaction of the acid and alkali oxides
P o P o
(i.e. GoR;Ca4Al2SO10
12H2O ¼ Goxide þ GR ), this paper
calculated GR,Ca4Al2SO10
12H2O, GR,6CaAl2S3O18
31H2O, GR,
Ca6Al2(SO4)3(OH)12, GR, Ca3Al2(OH)12 at 343 K
(70 °C). The experimental verification is basically
credible.
2: The calculated DG and test under the conditions in this
paper all showed that adding lime in sodium aluminate
solution containing sulfur can generate 3CaO

Al2O3
3CaSO4
6H2O, the diffraction peaks detected by
XRD were 9.8, 5.61, 5.54, 4.91, 3.88, 2.79 and
2.56  10-1nm etc.
3: In sodium aluminate solution, the reaction process of
adding lime is:
144
4: Desulfurization reaction products of adding lime in the
calcium aluminate sulfate solution are mainly
3CaO
Al2O3
3CaSO4
nH2O, 3CaO
Al2O3
CaSO4

12H2O and CaSO4, reacting at 70 °C for 70 min ago,
desulfurization efficiency up to 80%. Then with the
reaction time extended desulfurization efficiency
decreased gradually.
Foundation item Project 2136609 supported by National Natural
Science Foundation of China
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 Part IV
Alumina and Bauxite: Poster Session
 A Study on Optimization of Processing
Parameters for Synthesis of Calcium
Hydroaluminosulfate Using Response Surface
Methodology

W. Xianxi, Z. Weidong, L. Jun, and W. Song

Abstract
The synthesis rate of calcium hydroaluminosulfate, which has an important effect on
desulfurization and desilicon in alumina production, was studied in this research; Based on
the analysis of the two-level multifactor test, the reaction temperature (°C), reaction time
(min), Na2SO4 concentration in solution (g/L) and total alkali concentration (g/L). It is
important to emphasize the significant factors that affect the synthesis of calcium
hydroaluminosulfate have been screened out. Taking the significant factors as the study
object, and by the central composite experimental design and response surface analysis to
simulate the synthesis process of calcium hydroaluminosulfate, a prediction model of the
synthesis rate of calcium hydroaluminosulfate has been got. The technological conditions
are obtained by optimization as that: reaction temperature 75 °C, reaction time 65 min,
Na2SO4 concentration in solution 40 g/L and total alkali concentration 45 g/L. Under this
condition experiment, synthesis rate of calcium hydroaluminosulfate obtained was 69.72%,
with the small difference from model prediction value 70.24%. This illustrates that the
prediction model and the optimized process conditions can be used to guide the experiment
and production.

Keywords
Response surface methodology Calcium hydroaluminosulfate Synthesis rate Alumina

Introduction production by Bayer or Lime Bayer process, the addition of

Calcium hydroaluminosulfate (3CaO
Al2O3
CaSO4
12H2O)
added in the process of producing alumina by sintering process
is a profitable silicon removal agent. The conditions and
properties synthesis have an effect on study of the mechanism
to remove of silicon and improving the removal efficiency of
silicon, so as to affect the quality of alumina produced by
sintering process is affected [1]. In the process of alumina
Foundation item: Project 2136609 supported by National Natural
Science Foundation of China.
W. Xianxi (&)
L. Jun
W. Song
College of Chemical Engineering, Guizhou University,
Guiyang, 550025, China
e-mail: wuxx2012@sina.com
Z. Weidong
College of Materials and Metallurgy, Guizhou University,
Guiyang, 550025, China
lime in order to react with the harmful substance sodium sul-
fate (Na2SO4) in the solution to produce calcium hydroalu-
minosulfate, which will be discharged with red mud, this
reaction promotes the removal of sulfur and reduces the alkali
consumption [2, 3]. Therefore, this reaction has an important
theoretical and practical significance, so, the study and the
optimization of this synthesis conditions in the product of the
calcium hydroaluminosulfate was development.
In this research, according to total alkali concentration
(NT, it is Na2O) (including NaOH, and Na2CO3, and con-
verting them to Na2O to calculate), Al2O3, Na2SO4, CaO,
reaction time and reaction temperature as the important fac-
tors, by the two-level multi factor test, the significant factors
affecting the synthesis of calcium sulphoaluminate would be
screened out. Then establishing the corresponding regression
model for the target (yield of calcium sulphoaluminate) with
response surface methodology (RSM) was established [4, 5].

© The Minerals, Metals & Materials Society 2017 147

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_21
148 W. Xianxi et al.

Conducting the experiments and the statistical analysis, in Experimental Method

order to optimize the process conditions for the synthesis of
calcium hydroaluminosulfate, and finally privide the desul-
furization and the desilicon in the alumina production.
Experiments and Reagents
Experimental Apparatuses and Drugs
In order to performance the synthesis of calcium hydroalu-
minosulfate, the calcium oxide was dissolved in the water to
prepare the lime milk of CaO 4–10 g/L. Then CaO and
Al2O3 at a certain molar ratio was added to the sodium
aluminate solution with SO42−, stirring at 60–80 °C for 60–
80 min. The product was filtrated and dried and analyzed by
X-ray diffraction (XRD).

The autoclave model XYF-u446 by stainless bombs was

used. The reagents, with analytical grade, used during the
test were sodium hydroxide, aluminum hydroxide and
sodium sulfate.
Preparation of Sodium Aluminate Solution
Sodium aluminate solution was prepared in the XYF-u446
type autoclave heated with inorganic salt NaNO2. According
to the design requirements of the test, a certain amount of the
agents NaOH (24.4 g) and Al (OH)3 (15.5 g) reagents were
added in the stainless bombs. Adding 100 ml distilled water,
when the molten salt temperature reached 15 °C higher than
the required dissolution temperature (170 °C), the stainless
bombs were put in, starting the agitator, the rotational speed
was at 45 r/min, and then beginning the time recording. After
the steel bombs were put into the autoclave, the reaction
happened at a constant temperature for 1.5*2 h, closing the
mixing device, taking the stainless bombs in the reaction
kettle out, and cooling them in water to room temperature and
then unscrewing the stainless bombs. The sodium aluminate
solution was taken out and put in a beaker. In order to prevent
precipitation of sodium aluminate solution formed, the
sodium aluminate solution should be kept under heating.
Experimet Design
According to the results and data [6, 7] from previous ther-
modynamic research [8], this study took NT (taking Na2O as
total alkali concentration), Al2O3, Na2SO4, CaO, reaction
time, reaction temperature as the important factors. The factor
level and the experiment plan are shown in Table 1. The test
design scheme was completed by expert design 7.0, and the
data analysis was carried out by SPSS statistical software.
Response Surface Experimental Design
After the factors that affect the synthesis of calcium
sulphoaluminate were screened out, the significant factors
were further researched with central composite design, in
order to obtain the better synthesis conditions of calcium
sulphoaluminate. From the experimental results of two-level
factorial design it could be confirmed that the reaction
temperature, reaction time, Na2SO4 and NT were the sig-
nificant factors to affect the synthesis of calcium sulphoa-
luminate. Therefore, these four factors were taken as the
variables that the central composite design needed. The
factor level and code could be observed in Table 2.

Table 1 Level and code Variable Symbol Unit Coded levels

variables for two-level factorial
design −1 1
NT X1 g/L 60 120
Al2O3 X2 g/L 50 100
Na2SO4 X3 g/L 20 40
CaO X4 g/L 6 12
Reaction time X5 Min 60 80
Reaction temperature X6 °C 50 80
A Study on Optimization of Processing Parameters for Synthesis … 149

Table 2 Level and code variable Variable Symbol Unit Coded levels
for CCD
−a −1 0 a +1
Reaction temperature X1 °C 65 70 75 85 80
Reaction time X2 min 55 60 65 75 70
Na2SO4 X4 g/L 30 35 40 50 45
NT X3 g/L 45 50 55 65 60

Table 3 Level and code variables for two-level and experimental results
Test serial Test influence factors Test result
number NT Al2O3 Na2SO4 CaO Reaction time Reaction (%)
(g/L) (g/L) (g/L) (g/L) (min) temperature (°C)
1 60.0 100.0 40.0 10.0 60 80 63.2
2 120.0 50.0 20.0 10.0 80 80 61.5
3 120.0 50.0 40.0 4.0 60 80 45.3
4 120.0 100.0 40.0 4.0 80 60 29.3
5 120.0 50.0 20.0 4.0 80 60 52.7
6 60.0 100.0 20.0 4.0 80 80 67.6
7 120.0 100.0 20.0 10.0 60 60 19.5
8 120.0 50.0 40.0 10.0 60 60 35.4
9 60.0 50.0 40.0 10.0 80 60 61.5
10 60.0 100.0 40.0 4.0 60 60 40.7
11 120.0 100.0 40.0 10.0 80 80 35.4
12 120.0 100.0 20.0 4.0 60 80 30.3
13 60.0 50.0 40.0 4.0 60 80 70.5
14 60.0 100.0 20.0 10.0 80 60 55.4
15 60.0 50.0 20.0 4.0 60 60 58.5
16 60.0 50.0 20.0 10.0 60 80 80.1

Experimental Results and Discussion
Screening of Factors Affecting the Synthesis
of Calcium Sulphoaluminate
NT, Al2O3, Na2SO4, CaO, reaction time and reaction tem-
perature were defined as the investigation factors, and 16
sets of tests were designed with two-level factorial design
software of design expert 7.0. The test results are shown in
Table 3. And ANOVA was used to analyze the test results.
Analysis results are shown in Table 4. It can be observed in
Table 4 that Al2O3 (P = 0.8826 > 0.05), CaO (P =
0.8260 > 0.05) are not significant factors that affect the syn-
thesis of calcium sulphoaluminate. P = NT (P <
0.0001 < 0.05), Na2SO4 (P = 0.0327 < 0.05), reaction time
(P = 0.0229 < 0.05), reaction temperature (P =
0.0022 < 0.05) are the significant factors that affect the syn-
thesis of calcium sulphoaluminate. So, these four factors
selected are the key factors to influence the synthesis of
calcium sulphoaluminate. The effect of these four factors on
the synthesis of calcium aluminate was studied further.
Establishing of Data Model for the Synthesis
of Calcium Sulphoaluminate
By central composite design, the four significant factors
screened from two-level test were optimized with response
surface methodology witch could establish continuously
variable surface model and simultaneously optimize and
evaluate multiple influence factors level [9, 10], it is an
experimental design method the most widely used currently.
Considering the synthesis rate of calcium hydroalumi-
nosulfate as a response value, corresponding to the depen-
dent variable Y, central composite design and test results are
shown in Table 5. Using Design-Expert 7.0 software to
two-polynomial-fit the data in the table, the yield of calcium
hydroaluminosulfate could be obtained.
150 W. Xianxi et al.

Table 4 Analysis of the main effects for the two-level design

Sum of squares df Mean square F-Value p-value Prob > F Remarks
Model 4657.43 6 776.24 17.06 0.0002 sig
NT 2527.58 1 2527.58 55.54 <0.0001 sig
Al2O3 771.45 1 771.45 16.95 0.826 nonsig
Na2SO4 205.21 1 205.21 4.51 0.0327 sig
CaO 1.05 1 1.05 0.023 0.8826 nonsig
Reaction time 341.33 1 341.33 7.50 0.0229 sig
Reaction temperature 810.83 1 810.83 17.82 0.0022 sig
Residual 409.61 9 45.51
Cor Total 5067.04 15

Table 5 CCD matrix of the variables and the actual values

Test serial number Influence factors Test result (%)
Reaction temperature (°C) Reaction time (min) Na2SO4 (g/L) NT (g/L)
1 70.00 60.00 35.00 50.00 63.5
2 80.00 60.00 35.00 50.00 50.4
3 70.00 70.00 35.00 50.00 54.4
4 80.00 70.00 35.00 50.00 54.2
5 70.00 60.00 45.00 50.00 47.2
6 80.00 60.00 45.00 50.00 47.1
7 70.00 70.00 45.00 50.00 45.4
8 80.00 70.00 45.00 50.00 50.1
9 70.00 60.00 35.00 60.00 43.8
10 80.00 60.00 35.00 60.00 68.5
11 70.00 70.00 35.00 60.00 44.9
12 80.00 70.00 35.00 60.00 68.0
13 70.00 60.00 45.00 60.00 39.2
14 80.00 60.00 45.00 60.00 45.1
15 70.00 70.00 45.00 60.00 43.6
16 80.00 70.00 45.00 60.00 47.5
17 65.00 65.00 40.00 55.00 40.5
18 85.00 65.00 40.00 55.00 65.3
19 75.00 55.00 40.00 55.00 34.2
20 75.00 75.00 40.00 55.00 40.3
21 75.00 65.00 30.00 55.00 66.3
22 75.00 65.00 50.00 55.00 61.7
23 75.00 65.00 40.00 45.00 69.7
24 75.00 65.00 40.00 65.00 58.6
25 75.00 65.00 40.00 55.00 54.7
26 75.00 65.00 40.00 55.00 66.1
27 75.00 65.00 40.00 55.00 64.1
28 75.00 65.00 40.00 55.00 65.4
29 75.00 65.00 40.00 55.00 65.7
30 75.00 65.00 40.00 55.00 64.9
A Study on Optimization of Processing Parameters for Synthesis … 151

Multiple regression equations of (Y) for the independent
variables of the reaction temperature (X1), reaction time
(X2), Na2SO4 (X3) and NT (X4):
Y ¼ 6214 þ 4:13X1 þ 0:75X2  3:85X3  1:3X4
þ 0:97X1 X2  1:29X1 X3 þ 4:18X1 X4
þ 0:71X2 X3 þ 0:81X2 X4  1:11X3 X4  2:25X12
 0:715X22  0:47X32  0:51X42
From the regression equation, interaction among the
influencing factors was analyzed, to determine the influence
of each factor on the experimental results [11]. The results
of the variance analysis of the model are shown in Table 6.
It can be observed in Table 6 that the extremely significant
(P = 0.0014 < 0.05) and absence of fit was not significant
(Pm = 0.1663 > 0.05) of the quadratic regression model,
illustrating that the model fits well with the experiments,
and can be used for yield analysis and prediction of calciu
hydroaluminosulfate. The test results of coefficient signifi-
cance of the regression equation are shown in Table 6. The
data in the table have shown that the parameters X21 (P =
0.0141), X22 (P < 0.0001), X23 (P = 0.0359), X24 (P =
0.0439) have an significant impact on calcium hydroalu-
minosulfate yield. The impacts in rank are: reaction
time > reaction temperature > sodium sulfate concentra-
tion > total alkalinity. The interaction among X1, X3; X1,
X4,and X3, X4, has a significant effect on the yield of cal-
cium sulphoaluminate, but that between X1 and X2 and that
between X2and X3, as well as that between X2 and X4 have
not a significant effect.
RSM Analysis of the Effect of the Factors
on the Yield of Calcium Hydroaluminosulfate
Based on ANOVA results, design expert was used to draw
CAS contour maps and 3D graphics of each factor. The
shape of the contour could reflect the intensity of the inter-
action effect [12, 13]. Round affirms that interaction between
the two is not significant. The oval indicates that the inter-
action of the two is significant, the greater the eccentricity of
the ellipse, the more significant the interaction between the
two factors. Figure 1 is the one for 3D graphics and contour
map of CAS interaction. The contour map (Fig. 1b) is close
to a circle, so it can be described that the interaction is not
strong. This is the same result as in front of ANOVA
(P = 0.5362 > 0.05), that is, the combined effects of tem-
perature and time have not a great influence on the synthesis
of calcium hydroaluminosulfate. It can be known from the
3D graphic (Fig. 1a) that the effect of temperature and time
on the yield of calcium hydroaluminosulfate increased with
the increase of temperature and time, and then decreased.
From Fig. 1, it can be seen that the temperatures were
from 75 to 80 °C, CAS reached the maximum of this test.
Because calcium hydroaluminosulfate is a kind of metastable
compound, temperature is the main influencing factor of its
synthesis. Increasing temperature is beneficial to improve the
reaction rate of synthesis of calcium hydroaluminlfosuate,
but at the same time, it will decrease the stability of calcium
hydroaluminosulfate, making it rapid decomposition into a
stable hydrated calcium aluminate. This is consistent with our
previous thermodynamic analysis and literature [1].

Table 6 ANOVA for response Source Sum of squares df Mean Square F-Value P-Value Prob > F
surface quadratic model of
3CaO
Al2O3
CaSO4
12H2O Model 2752.46 14 196.60 5.25 0.0014
X1-temperature 409.20 1 409.20 10.92 0.0048
X2-time 11.90 1 11.90 0.32 0.5814
X3-Na2SO4 354.97 1 354.97 9.47 0.0077
X4-NT 40.82 1 40.82 1.09 0.3131
X1X2 15.02 1 15.02 0.40 0.5362
X1X3 26.78 1 26.78 0.71 0.4112
X1X4 279.73 1 279.73 7.47 0.0154
X2X3 7.98 1 7.98 0.21 0.6511
X2X4 10.40 1 10.40 0.28 0.6060
X3X4 19.58 1 19.58 0.52 0.4809
X21 289.16 1 289.16 7.72 0.0141
X22 1405.90 1 1405.90 37.52 <0.0001
X23 6.11 1 6.11 0.16 0.0359
X24 8.58 1 8.58 0.23 0.0439
Residual 562.02 15 37.47
Lack of Fit 467.05 10 46.71 2.46 0.1663
Pure Error 94.97 5 18.99
Cor Total 3314.49 29
152
Fig. 1 Response surface plot (left) and respective counter of 3CaO
Al2O3
CaSO4
12H2O versus temperature and time
Decomposition reaction calcium hydroaluminlfosuate is
in equation is in Eq. 1.
D
3CaO
Al2 O3
CaSO4
12H2 O ! CaðAlO2 Þ2

6H2 O þ CaSO4 þ 6H2 O
The reaction time of this experiment is 65 min for the
better synthesis time of calcium hydroaluminosulfate. This
result is because that the formed metastable substance is
calcium hydroaluminosulfate, if the heating time is too long,
it will be easy to change into a more compact cubic system
of hydrated calcium aluminate.
W. Xianxi et al.
Figure 2 shows the interaction between temperature and
Na2SO4 on the yield of calcium sulphoaluminate. The con-
tour map on the Fig. 2b is the half of the oval, thus showing
the effect of Na2SO4 and temperature on the yield of CAS
ð1Þ has very strong interactivity. It can be observed from Fig. 2
that the effect of temperature on the yield of calcium
sulphoaluminate increased with the increase of temperature,
and then decreased. The optimum temperature conditions
should be between 75 and 80 °C. Within the concentration
range of the study, the effect of Na2SO4 on the production of
calium sulphoaluminate increased with the decrease of
Na2SO4 concentration.
A Study on Optimization of Processing Parameters for Synthesis …
Fig. 2 Response surface plot (left) and respective counter of 3CaO
Al2O3
CaSO4
12H2O versus temperature and concentration of sodium sulfate
Figure 3 shows the interaction of time and Na2SO4 on the
yield of CAS. The contour map on the Fig. 3b is half oval,
which shows the effects of time and Na2SO4 have a very
strong interactivity on the production of CAS. It can be
observed from Fig. 3 that the effect of time on the yield of
calcium sulphoaluminate first increased with time, and then
decreased. The best time of the test should be around
65 min. However, the effect of Na2SO4 on the yield of CAS
increased with the decrease of Na2SO4 concentration.
Figure 4 is the 3D map and contour map about t the
interactive effect of NT and time on CAS. The contour map
153
on the Fig. 4b is close to a circular one, so it can be deter-
mined that the interaction is not strong, and this is the same
as in front of the ANOVA results (P = 0.6060 > 0.05). It
can be observed from the 3D map on the Fig. 4a that the
effect of time on the yield of calcium sulphoaluminate first
increased with time, and then decreased. The best time for
testing should be 65 min. The effect of NT on the production
of calcium sulphoaluminate first slowly increased with the
increase of total alkalinity NT, and then decreased sharply.
Therefore, the optimum range of total alkalinity NT was
40–50 g/L.
154
Fig. 3 Response surface plot (left) and respective counter of 3CaO
Al2O3
CaSO4
12H2O versus time and concentration of sodium sulfate
Optimization Result Verification Analysis
To solve the regression equation of response surface opti-
mization, within the range of experimental factors, and the
better experimental conditions solved for the production of
calcium hydroaluminosulfate and the predictive value of the
response are shown in Table 7.
The average value of the results of multiple experiments
under the optimum conditions was 69.72%, compared with
the forecast value, the error was 0.74%, illustrating that the
optimization of the process is feasible.
W. Xianxi et al.
The products obtained under the optimum experimental
conditions were analyzed by XRD, and Fig. 5 is for the
XRD pattern.
The diffraction pattern shows the diffraction peaks of cal-
cium hydroaluminosulfate 3CaO
Al2O3
CaSO4
12H2O, their
d values are the characteristic ones of 8.9  10−1nm, 4.45 
10−1nm, 3.99  10−1nm, 2.87  10−1nm, 2.42  10−1nm,
2.233  10−1nm, etc. respectively. The diffraction pattern is an
important basis for determining that the reaction product is the
calcium hydroaluminosulfate [14].
A Study on Optimization of Processing Parameters for Synthesis … 155

Fig. 4 Response surface plot (left) and respective counter of 3CaO
Al2O3
CaSO4
12H2O versus time and total concentration of alkali

Table 7 The best condition of Reaction temperature (° Reaction time min Na2SO4 Total alkalinity NT g/L Yield
experiment and forecast response C) g/L (%)
value
75 65 40 45 70.24
156
Fig. 5 XRD patterns of
3CaO
Al2O3
CaSO4
12H2O
Conclusions
Using response surface methodology to optimize the syn-
thesis of calcium hydroaluminosulfate in adding lime into
sodium aluminate solution containing Na2SO4 is simple and
feasible. The experimental conditions obtained by optimiz-
ing were 75 °C, the reaction time 65 min, the concentration
of Na2SO4 40 g/L and the total alkali concentration 45 g/L.
The production rate of synthesis of calcium hydroalumi-
nosulfate was 69.72%. Using response surface analysis
method could obtain the optimal experiment and production
process parameters for the further experimental study and
production services.
References
1. L. Lianli, Z. Yuchun, T. Yanwen et al., Synthesis of calcium
hydroaluminosulfate. Chin. J. Nonferrous Met. 13(2), 506–510
(2003). (in Chinese)
2. L. Yuchang, L. Chunyu, Z. Yuxiu, Study on desulfurization of lime
Bayer process. Proceedings of The fifth national metallurgical
process of physical chemistry Annual Meeting Proceedings, vol. 1,
Publishing on line: 2003, P149 (in Chinese)
3. L. Yuchang, Y. Changlong, A study of desulphurization of sodium
aluminate solution. Light Met. 4, 9–11 (2003). (in Chinese)
W. Xianxi et al.
4. R. Guihai, Practical Encyclopedia of Statistical Analysis System
(Tsinghua Unversity Press, Beijing, 2002). (in Chinese)
5. M. Gionni, Response surface methodology and product optimiza-
tion. J. Food Technol. 37(11), 41–45 (1983). (in Chinese)
6. W. Youwei, Experimental Design and Data Processing (Suzhou
University Press, Suzhou, 2002). (in Chinese)
7. D.C. Montgomery, Design and Analysis of Experiments, 5th edn.
(Wiley, New York, 2001)
8. W. Xianxi, J. Hongshi, Z. Weidong, Gibbs free e nergies
calculation of calcium aluminate sulfate hydrates. J. Chin. Ceram.
Soc. 44(8), 1243–1248 (2016)
9. V.I. Vitanov, N. Javaid, D.J. Stephenson, Application of response
surface methodology for the optimisation of micro friction
surfacing process. Surf. Coat. Technol. 204(21/22), 3501–3508
(2010)
10. P.K. Dasa, Y. Zheng, Cumulative formation of response surface
and issues in reliability analysis. Probab. Eng. Mech. 15(4), 309–
315 (2000)
11. D.C. Montgomery, Design and Analysis of Experiments, 6th edn.
(Wiley, New York, 2006)
12. Y. Zhanliang, S. Huixian, H. Xiaocai et al., Study on optimization
of processing parameters for recycling iron from red mud by
reduction roasting—magnetic separation method using response
surface methodology. Light Met. 12, 10–17 (2014). (in Chinese)
13. L. Caolong, C. Xiujuan, Y. Jing et al., Optimization for
fermentation conditions of protease—producing strain by response
surface analysis. Chin. Brew. 32(6), 89–93 (2013). (in Chinese)
14. W. Yinghua, Basis of X-Ray Diffraction Technique (Atomic
energy press, Beijing, 1993). (in Chinese)
 Part V
Aluminum Alloys, Processing and Characterization:
Alloy Development and Applications
 Design of New 6xxx Series Al Alloy Using
the Calphad Thermodynamic Database

Senlin Cui, Raj Mishra, and In-Ho Jung

Abstract
A comprehensive and accurate thermodynamic database for Al 6xxx series alloy
encompassing Al-Mg-Si-Cu-Fe-Mn-Cr has been developed based on the critical evaluation
and optimization of all the available literature data and new phase diagram experiment.
Based on this database, the thermodynamic calculations are performed to understand the
phase evolution during casting, homogenization, and final tempering process. In particular,
the equilibrium phase fraction diagrams of all the possible precipitate phases are mapped in
the composition range of 0–1.1 wt% Mg and 0–0.7 wt% Si at different processing
temperatures. The influence of the variation of minor alloying/impurity elements such as
Cu, Fe, Mn, and Cr to the amount of each type of precipitates is also taken into account.
Considering conventional Al processing technologies from casting, homogenization,
extrusion, and final age-hardening stages, the calculation results will be interpreted for
logical Al alloy design.

Keywords
Aluminum alloy Thermodynamic calculation Solidification Alloy design

Introduction boundary particles determined the surface finish [1]. Fe pre-

Al alloys are widely used as the structural part in transporta-
tion sector. As the requirement for the lightening of the weight
and the increasing of fuel efficiency of automobiles, high
strength Al extruded profiles of complex shape are needed in
transportation industry. The as-cast billet of 6xxx series alloy
cannot always be successfully extruded after homogenization
process, because of different types of precipitates formed
during casting. For instance, the size and distribution of
Mg2Si critically determined the extrusion speed, and the grain
S. Cui (&)
I.-H. Jung (&)
Department of Mining and Materials Engineering, McGill
University, 3610 University Street, Montreal, QC H3A 0C5,
Canada
e-mail: cuisenlin@gmail.com
I.-H. Jung
e-mail: in-ho.jung@mcgill.ca
R. Mishra
General Motors R&D Center, Warren, MI 48090, USA
sents in Al alloys in the form of Fe-bearing intermetallic
phases since the solubility of Fe in Al solid solution is very
low. b_AlFeSi is claimed to cause poor ductility and severely
reduces the hot workability of Al alloys during extrusion
process. On the other hand, a_AlFeSi is less harmful. It does
not contribute to the pickup defect during extrusion process
and even can improves the properties and surface finish of the
final products [2]. Suitable amount of Cr and Mn has been
used to modify the microstructure. However, the introduction
of Mn and Cr in Al alloys will dramatically increase the
amount of coarse a_Al(Fe, Mn, Cr)Si which drastically
deteriorates the mechanical properties of Al alloy [3]. The
unfavourable b_AlFeSi phase in commercial 6063 alloys can
transform into the less detrimental a_AlFeSi by prolonged
heat treatment process [4]. However, the production cost will
be increased.
Al casting process and heat treatment process like
homogenization and final annealing cannot be dictated by
the Scheil calculation and the equilibrium thermodynamic

© The Minerals, Metals & Materials Society 2017 159

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_22
160
calculation, respectively. However, such calculations using
the CALPHAD thermodynamic database can give reason-
able understanding of the microstructure at each process
stage, and can be used for new Al alloy design or process
optimization. In this study, we systematically studied the
effect of alloying elements, such as Cu, Fe, Mn, and Cr, on
both the solidification precipitates and equilibrium precipi-
tates in AA 6063 alloy using the accurate and comprehen-
sive CALPHAD thermodynamic database.
CALPHAD Thermodynamic Database
and Calculations
All the CALPHAD type thermodynamic calculations in this
study are carried out using the FactSage software [5] with
the newly developed Al alloy database suitable for 6xxx
series alloys by the present authors. The new thermodynamic
database is critically focused on the Al-Mg-Si-Cu-Fe-Mn-Cr
system. This new alloy database contains the Gibbs energy
descriptions of all the solid and liquid phases relevant to Al
6xxx alloys. All the 21 binary systems and 18 key ternary
systems including the Al-Cu-Cr, Al-Cu-Mg, Al-Cu-Mn,
Al-Cu-Si, Al-Cr-Mg, Al-Cr-Mn, Al-Cr-Si, Al-Fe-Si,
Al-Fe-Mn, Al-Mg-Si, Al-Mg-Mn, Al-Mn-Si, Cu-Fe-Cr,
Cu-Mg-Si, Cu-Fe-Mn, Fe-Mg-Si, Fe-Cr-Si, and Fe-Mn-Si
systems were thermodynamically optimized based on the
available phase diagram and thermodynamic property
experimental data. Several important quaternary systems
such as the Al-Cu-Mg-Si system were also assessed. The
Gibbs energies and phase equilibria of other ternary and
quaternary systems which are less important for Al alloys
were predicted from binary and ternary systems. The major
phases in 6xxx series Al alloys include liquid, fcc_A1,
Al14Fe3, a_AlFeSi, b_AlFeSi, a_AlMnSi, b_AlMnSi,
Mg2Si, Al2Cu, Si, Q, and Al7Cr, which are all well described
in this new database.
In the present study, the variation of microstructure dur-
ing casting and homogenization process was investigated
with the change of alloy composition. The base alloy com-
position in this study is AA 6063. The Scheil solidification
calculations were carried out to estimate the as-cast
microstructure. The Scheil calculation assumes the
Table 1 Al 6063 alloy and Alloy Al Si
modified alloys studied in this
study 6063 Bal. 0.4
Com1 Bal. 0.4807
Com2 Bal. 0.5639
Com3 Bal. 0.5921
S. Cui et al.
complete diffusion of the liquid phase and zero diffusion of
the solid phases. The equilibrium calculations were per-
formed to predict the microstructure (type and amount of
precipitates) after homogenization process at 500 °C and
final annealing process at 177 °C.
Results and Discussions
The alloy compositions of AA 6063 and three modified
alloys (alloy #1 to #3) are given in Table 1. The calculated
solidification path of the standard 6063 alloy is presented in
Fig. 1. The solidification starts at 654 °C and ends at 512 °C.
According to the calculated diagrams, the solidification
sequence is fcc_A1 ! Al14Fe3 ! a_AlFeSi ! b_AlFeSi
Mg2Si ! Al8FeMg3Si6(p) ! Si ! Q. The starting tem-
perature of each secondary phase formation and their amount
can be read from the diagram. The solidification sequences of
the three modified alloys are quite similar to the standard AA
6063 except that alloys #1 and #3 containing Cr show Al7Cr
formation before fcc_A1 phase.
Figure 2 shows the SEM back-scattered image of the
as-cast microstructure of alloy #1. The Chinese script shaped
a_AlFeSi is obviously found, and very narrow needle like
b_AlFeSi and spherical shaped Q phase are also observed. It
is worth to note that Al8FeMg3Si6 particle with the same
shape as Q is also observed in alloy #3. A lot of fine particles
rich in Cr are observed in the Al matrix under high magni-
tude SEM analysis. Other phases are not marked since the
particles are very small. In general, the calculated secondary
phases from the Scheil cooling are reasonably matching with
the as-cast microstructure analysis of alloy samples.
In order to investigate the effect of major alloying elements
on the as-cast microstructure, Scheil calculation was utilized
to compute the amount of each precipitate by changing the
composition of individual element from the baseline alloy
composition 6063. The maps for the secondary phases after
Scheil solidification were generated. For example, Fig. 3
shows the effect of Cr on the amounts of secondary phases
(precipitates) formed during solidification process. According
to the calculations, Cr starts to form Al7Cr when it reaches
near 0.1 wt%. Then, the amount of Al7Cr is linearly
increasing with increasing Cr. Although it is not very
Mg Cu Fe Cr Mn
0.49 0.01 0.16 0 0.029
0.4965 0.148 0.1951 0.182 0.0965
0.9118 0.1351 0.2011 0 0.095
0.9171 0.1437 0.1987 0.1974 0.0957
Design of New 6xxx Series Al Alloy …
Fig. 1 Scheil cooling calculation
for Al 6063 alloy. a Solidification
sequence, and b phase
distribution with temperature
noticeable in Fig. 3, the amounts of a_AlFeSi, b_AlFeSi,
Mg2Si, Si, and Al8FeMg3Si6 slightly increase, and those for
Al14Fe3, Al2Cu, Al4(Cr, Mn), Al28Cu4Mn7, and Q decrease
slightly with increasing Cr content. The calculated effects of
different alloying elements on as cast microstructure are
summarized in Table 2. Increase is indicated by “"” and
decrease is indicated by “#”. This summary can give a general
161
guidance for alloy design. In particular, for the harmful pre-
cipitate b_AlFeSi can be slightly increased by increasing Cr
and Cu as well as by increasing Fe and Si which are the
constitutional elements of b_AlFeSi.
The equilibrium phase distribution of Al 6063 is calcu-
lated in Fig. 4. According to the calculated result, there is no
temperature where all the precipitates are completely
162
Fig. 2 SEM Back scatter micrograph of the as cast microstructure of
alloy #1
dissolved and only the fcc_Al phase can be formed. The
most optimum homogenization temperature would be 500–
620 °C. When homogenization is performed at 580 °C or
above, a_AlFeSi can be stable and b_AlFeSi is metastable.
But the homogenization below 580 °C can produce harmful
b_AlFeSi. The extrusion temperature of Al 6063 can be
typically between 460 and 550 °C. It should be noted that
according to the calculated equilibrium phase fraction in
Fig. 4, the secondary phase amount can rapidly increase
below 460 °C.
Fig. 3 Effect of Cr on the
amounts of precipitates formed
during solidification process
(Scheil cooling calculation)
S. Cui et al.
In the present study, the amounts of all the equilibrium
phases were mapped at 500 °C (extrusion temperature) with
variation of alloying elements. This calculation can tell the
possible amount of precipitates during the extrusion process
at 500 °C. The precipitates can significantly influence the
extrusion ability. For example, Fig. 5 shows the calculated
diagram for the phase amount of Mg2Si with the variation of
Mg, Si, and Cr. The Cr concentrations of 0.02 wt% or 0.20
wt% were fixed for the calculation and Mg and Si were
varied from 0 to 1.1 and from 0 to 0.7 wt%, respectively. Of
course, the amount of Mg2Si increases as the Mg and Si
content increase as shown in Fig. 5. The influence of Cr to
Mg2Si formation is negligible.
The strength of Al 6xxx series alloys is mainly controlled
by the fine precipitate of b′ and b″ formed in the last
annealing state. The over-aging at this stage can reduce the
strength by forming Mg2Si. Therefore, the annealing time is
also very important process parameter. The prediction of
such evolution of Mg2Si is very complex. Nevertheless, the
largest potential to form b′ and b″ can be calculated when
the largest equilibrium amount of Mg2Si reached. The pos-
sible amount of b′ and b″ formed during annealing can be
the difference between the equilibrium amount of Mg2Si at
aging temperature (for example, 177 °C for 6063 alloy) and
the equilibrium amount of Mg2Si at homogenization
temperature.
In Fig. 6, the equilibrium amount of Mg2Si is calculated
at 177 °C for Al alloys with composition of
Design of New 6xxx Series Al Alloy … 163

Table 2 Influence of alloying Phase Mn Cr Fe Cu Mg Si

elements to the amount of
secondary phase in as cast a_AlFeSi # " " " # "#
microstructure calculated from b_AlFeSi # " " " # "
this study
Al13Fe4 " # " # " #
Al2Cu " # " " " #
Al4(Cr,Mn) " # " "# # "#
Mg2Si " " " # " "
Si " " # # # "
Al8FeMg3Si6 # " #" " "# "
Q " " "# " " "#
Cu4Mn7Al28 " # # " " #
Al7Cr – " – – – –
One arrow and two arrows indicate slight and rapid increase or decrease with increasing of each alloying
element

Fig. 4 Calculated equilibrium

phase distribution of 6063 alloy
as a function of temperature

Al-Mg-Si-0.02Cr-0.05Cu-0.15Fe-0.03Mn. According to the
results, Mg2Si has its maximum amounts along the Mg/Si
ratio 1.73:1. Addition of Mg more than this maximum Mg/Si
ratio does not change the amount of Mg2Si, while the further
addition of Si decreases the amount of Mg2Si formation. The
red line in Fig. 6 indicates the composition limit for the
stable Mg2Si formation at 500 °C (see Fig. 5). Therefore, it
is less ideal to have Mg and Si concentration above this
boundary because the additional Mg and Si do not increase
b′ and b″ formation for the strengthening of Al alloy.
The green colored rectangular in Fig. 6 indicates the
range of alloy composition of commercial 6063 alloy. The
calculation results certainly tell the precipitation hardening
by b′ and b″ formation in commercial 6063 alloy can be
largely changed depending on the Mg and Si concentration
in the alloy. Therefore, more precise control of Mg and Si is
necessary to maximize the strength of 6063 alloy. That is,
most optimum concentration of Mg and Si from the view
point of Mg2Si formation would be about 0.7 and 0.4 wt%,
respectively. However, the real strengthening mechanism is
164 S. Cui et al.

more complex than simply dictating by the amount of

potential Mg2Si formation at annealing temperature. Gupta
et al. [6] reported that the excess Si increases the strength of
Al alloy by modifyig the precipitation morphology of b″ and
promote the stability of b″ against stable Mg2Si. So, the real
optimum composition of Mg/Si can be reduced from 1.73:1
toward 1:1.

Summary

A comprehensive and accurate thermodynamic database for

Fig. 5 Phase fraction map of Mg2Si at 500 °C for Al alloy with
composition of Al-Mg-Si-0.05Cu-0.15Fe-0.03Mn with 0.02Cr or 0.20Cr
in wt%. Lines in the diagram indicate the iso-amount of Mg2Si in wt%
the 6xxx series Al alloys has been developed. Based on the
Scheil cooling calculations and equilibrium calculations at
500 and 177 °C, the phase fraction map of each phase
depending on alloy composition was constructed to study the
influence of each alloying elements on the microstructure
evolution. The controlling of the b_AlFeSi phase was in
particularly discussed in solidification and homogenization
stages. The phase fraction maps of Mg2Si at 500 and 177 °C

Fig. 6 Phase fraction map of

Mg2Si at 177 °C in Al alloy with
composition of the
Al-Mg-Si-0.02Cr-0.
05Cu-0.15Fe-0.03Mn in wt%.
Lines in the diagram indicate the
iso-amount of Mg2Si in wt%
Design of New 6xxx Series Al Alloy …
were constructed to explain the strategy for maximizing
precipitation strengthening of Al 6xxx alloys.
3.
References 4.
1. A.E.-H.K. Abdel-Aziz, A.A. Vertman, A.M. Samarin, Thermochem- 5.
istry of Fe and Ni melts. Izv. Akad. Nauk SSSR, Met. 19–30 (1966) 6.
2. K.B.S. Couto, S.R. Claves, W.H. Van Geertruyden, W.Z. Misiolek,
M. Goncalves, Effects of homogenisation treatment on
165
microstructure and hot ductility of aluminium alloy 6063. Mater.
Sci. Technol. 21, 263–268 (2005)
Y. Han, K. Ma, L. Li, W. Chen, H. Nagaumi, Study on
microstructure and mechanical properties of Al-Mg-Si-Cu alloy
with high manganese content. Mater. Des. 39, 418–424 (2012)
S. Onurlu, A. Tekin, Effect of heat treatment on the insoluble
intermetallic phases present in an AA 6063 alloy. J. Mater. Sci. 29,
1652–1655 (1994)
http://www.factsage.com/
A.K. Gupta, D.J. Lloyd, S.A. Court, Precipitation hardening in
Al-Mg-Si alloys with and without excess Si. Mater. Sci. Eng.
A A316, 11–17 (2001)
 Study of an Al-Ca Alloy with Low Young’s
Modulus

Jun Yu, Yasuo Ishiwata, Yoshihiro Taguchi, Daisuke Shimosaka,

Ryosuke Taniguchi, Takutoshi Kondo, and Nobuki Tezuka

Abstract
Aluminum alloys with low Young’s Modulus have not been well studied. This study offers
properties and production methods of an Al-Ca alloy. Here, an Al-Ca alloy with a small
amount of Fe addition was prepared by Direct-Chill (DC) casting, extrusion and rolling,
microstructure and mechanical properties were investigated after every process. Low
Young’s Modulus of less than 55 GPa and increased yield strength was achieved when
adding heat treatment after extrusion and rolling.

Keywords
Young’s modulus Al4Ca Extrusion Rolling Microstructure

Introduction
Al-Ca alloys are known for their low Young’s Modulus as
they contain Al4Ca [1]. In a research work about phase
transformation of Al4Ca, it was reported that a martensitic
transformation occurs in Al4Ca with Ms  130 °C and the
structure changes from a tetragonal to a monoclinic structure
which causes a decrease of Young’s Modulus with
decreasing temperature above Ms [2].
In other research works, for example, Al-Ca and Al-Ca-M
(M = Mg or Zn) systems were studied as amorphous alloys,
in which the composition range of Ca was 9–11 at.% [3]. It
was also reported that Al-Ca alloys containing a high per-
centage of the Al4Ca second phase exhibit superplastic
behavior [4]. And the Al-Al4Ca eutectic was then investi-
gated as a new superplastic aluminum alloy [5].
While as the demand for low rigidity materials is limited,
properties of Al4Ca and production methods of Al-Ca alloys
have not been well studied. In addition, although Al-Ca
alloys have low Young’s Modulus, their low strength needs
to be increased.
So in this work, in order to achieve both low Young’s
Modulus and increased strength, an Al-Ca alloy with Fe
addition was investigated. As a small amount of Fe addition
into an Al-Ca alloy does not inhibit the formation of Al4Ca
[6], Young’s Modulus can remain low. And Fe addition is
advantageous to improve the homogeneity of casting struc-
ture according to our research.

J. Yu (&)
Y. Ishiwata
Y. Taguchi
D. Shimosaka
Experimental

R. Taniguchi
Nippon Light Metal, 161 Kambara, Al ingot (99.99% grade), Al-10 wt%Ca (99.99% Al ingot and
Shimizu-ku, 4213203, Shizuoka-shi, Japan
Ca) and Al-5%Fe were selected as raw materials. In order to
e-mail: jun-yu@nikkeikin.co.jp
fabricate billets for extrusion by DC casting, Ca concentration
T. Kondo
was determined to be less than the Al-Ca eutectic point, 7.7 wt
Nikkei Niigata Co. Ltd., 1572-19 Tarodai,
Kita-ku, 9503101, Niigata-shi, Japan %Ca (Fig. 1). Billet with a diameter of 203 mm was fabricated
by DC casting, the chemical composition is shown in Table 1,
N. Tezuka
Tohoku University, 6-6-02 Aoba, concentrations of Ca, Fe and Si were analyzed by ICP-AES.
Aramaki, Aoba-ku, 9808579, Sendai-shi, Japan Al-3 wt%Ti-1 wt%B rod was added as grain refiner during

© The Minerals, Metals & Materials Society 2017 167

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_23
168
Fig. 1 Al-Ca phase diagram
[7, 8]
Table 1 Composition of billet Ca (wt%) Fe (wt%)
7.44 0.048
casting. Before extrusion, homogenization (HO) was carried
out for the billet at 550 °C for 4 h. Then after heated to 450 °C,
the billet was extruded into a flat bar with a cross section of
150 mm  5 mmt, and rolled at room temperature (cold
rolling) into a thickness of 4mmt, with a reduction of 20%.
Finally heat treatment (annealing and air cooling) was carried
out for the rolled specimen at 200 °C for 1 h.
Specimens after casting, HO, extrusion and cold rolling
were polished and microstructure was observed using optical
microscope. Image analysis was used for measuring particle
size and area ratio. Tensile test was carried out for all the
specimens. XRD was used for specimens before and after
heat treatment. Electric conductivity, Vickers hardness was
also measured for the specimens.
Results and Discussions
Microstructure
For Al-7.4 wt%Ca-0.05 wt%Fe, microstructure was
observed and Fig. 2 shows the results. Figure 2a shows
J. Yu et al.
Si (wt%) Al (wt%)
0.005 Bal.
the microstructure of as-cast billet, containing a-Al and
eutectic structure, which can be considered as Al and
Al4Ca according to the Al-Ca phase diagram (Fig. 1).
After HO, the eutectic structure became course, and most
of the Al4Ca phase turned into granular structure, as
shown in Fig. 2b. Though the diffusion coefficient of Ca
in Al is not clear, it is considered that diffusion of Ca
occurs at high temperature, and for Al4Ca, to reduce the
interfacial energy, it is more stable in particles than in
layers.
Figure 2c shows the microstructure after extrusion, in
which only particles and metal matrix can be observed,
during hot working, Al4Ca particles were formed and
dispersed in the Al matrix. Average particle size was
1.5 µm, and the area ratio of Al4Ca particles was 35.4%
according to image analysis. While after cold rolling,
almost no change in microstructure can be found as
shown in Fig. 2d.
Above all, it can be concluded that during HO and hot
working, microstructure of the Al-Ca alloy extremely
changed as a result of diffusion and deformation, while cold
working does not change microstructure.
Study of an Al-Ca Alloy with Low Young’s Modulus 169

Fig. 2 Microstructure of Al-7.4Ca-0.05Fe. a as-cast billet, b HO billet, c after extrusion, d after cold rolling

Table 2 Results of tensile test of Tensile strength Yield strength Elongation Young’s Modulus
Al-7.4Ca-0.05Fe (MPa) (MPa) (%) (GPa)
After DC casting 228 89 6 51
After extrusion 245 125 22 59
After rolling 282 204 11 59
After heat 268 195 13 51
treatment

Mechanical Properties hardening, and with no change in Young’s Modulus. As

Results of tensile test after every process are listed in
Table 2. After extrusion, Young’s Modulus became 59 GPa,
which was higher than that of billet, but it was nearly
10 GPa lower than that of most aluminum alloys, which is
about 70 GPa. Compared with billet, the yield strength was
although increased but still low.
In order to increase the strength, cold rolling process
was carried out, and the result was in good agreement
with prediction, nearly 80 MPa was increased by work
microstructure had no change before and after cold
rolling, it can be considered that the increase of
strength is due to an increase of dislocation during cold
rolling.
Annealing was carried out after cold rolling in order to
decrease the residual stress. To remain the increased strength
by cold rolling, relatively low temperature was chosen. After
annealing at 200 °C for 1 h, strength was decreased a little
as predicted, but Young’s Modulus was dramatically
decreased into the low level before extrusion. Compared
170
Fig. 3 Change in properties of
Al-7.4Ca-0.05Fe after annealing
at different temperature
Fig. 4 Microstructure of Al-7.4Ca-0.05Fe before (a) and after (b) annealing at 200 °C for 1 h
with the decrease in strength, which was about 4%, the
decrease in Young’s Modulus was nearly 14%.
As known for all, for usual aluminum alloy, Young’s
Modulus does not change before and after hot working or
heat treatment. So it is necessary to investigate reasons for the
dramatic change in Young’s Modulus of Al-7.4Ca-0.05Fe.
To see the differences before and after annealing at sev-
eral temperature, electric conductivity and Vickers hardness
were also measured, along with the results of tensile test,
Fig. 3 shows the results. After annealing at 150–220 °C for
J. Yu et al.
1 h, there was only a small change in electric conductivity,
Vickers hardness, yield strength and tensile strength, but
only for Young’s Modulus, a change of about 14% occurred.
It is difficult to explain the reasons for the decrease in
Young’s Modulus. For volume fraction of Al4Ca phase
which has low Young’s Modulus, it was not changed
according to the microstructure shown in Fig. 4. And as
Vickers hardness and electric conductivity had only a small
change, the influence of solid solution also could not be
considered.
Study of an Al-Ca Alloy with Low Young’s Modulus
Fig. 5 XRD results of Al-7.4Ca-0.05Fe before and after annealing at 200 °C for 1 h
As written in the introduction, Al4Ca could have a
martensitic transformation, and the structure changes from a
tetragonal to a monoclinic structure which causes a decrease
of Young’s Modulus. So it is possible that a martensitic
transformation occurs during hot working and annealing,
leading to a dramatic change in Young’s Modulus. In order
to see the crystal structure of Al-7.4Ca-0.05Fe, XRD was
carried out for the specimens before and after annealing.
According to the results shown in Fig. 5, there were
several differences in the peaks before and after annealing.
Because data of only Al4Ca with a tetragonal structure can
be found, it is difficult to determine which peaks show Al4Ca
with a monoclinic structure, but it is clear that besides the
peaks of tetragonal structure, some other peaks also appear.
Based on these results, we conjecture that the reason for a
change of Young’s Modulus before and after annealing could
be a martensitic transformation of Al4Ca phase. As no differ-
ence in Young’s Modulus was observed under cooling condi-
tion (air cooling/water quenching) after annealing, it is possible
that during annealing, under the influence of heat, or along with
the decrease in residual stress, crystal structure of Al4Ca par-
tially changes, leading to a decrease in Young’s Modulus.
As for the change in Young’s Modulus before and after
extrusion, the reason could be a decrease in the defects of
casting structure, or it could be a deformation induced
martensitic transformation of the Al4Ca during hot working.
And to prove these predictions, further investigation is car-
ried out by our group.
171
Conclusions
To achieve low Young’s Modulus and increased strength at
the same time, an Al-Ca alloy with a small amount of Fe
addition was investigated.
Al-7.4Ca-0.05Fe alloy was fabricated by DC casting,
extrusion, cold rolling and annealing. After extrusion and cold
rolling, strength of the alloy can be increased, but Young’s
Modulus is also increased. By adding annealing at 200 °C
after cold rolling, strength can remain high, while Young’s
Modulus can decrease furthermore. The reason for a change in
Young’s Modulus could be a martensitic transformation of
Al4Ca phase during the manufacturing process.
As a result, an Al-7.4Ca-0.05Fe alloy with increased
yield strength of close to 200 MPa and low Young’s
Modulus of less than 55GPa was successfully developed.
References
1. N. Dudzinski: J, Inst, Metals 81, 50–51 (1952–1953)
2. H. Zogg, P. Schwellinger, J. Mater. Sci. 14, 1923–1932 (1979)
3. A. Inoue, N. Nishiyama, T. Masumoto, K. Hatakeyama, Materials
transactions. JIM 35(4), 282–285 (1994)
4. G. Pellegrini, G. PIATTI, Eurospectra 13, 112 (1974)
5. G. Piatti, G. Pellegrini, R. Trippodo, J. Mater. Sci. 11, 186 (1976)
6. A. Prince, Ternary alloys. VCH 3, 600–603 (1990)
7. T.B. Massalski, Binary Alloy Phase Diagrams, 2nd edn. pp. 130–133
8. Calphad: Comput. Coupling Phase Diagrams Thermochem. 13,
133–137 (1989)
 Production of 3004 Aluminum Alloy Sheet
for Structural Applications from Twin Roll
Casting

Ali Ulaş Malcıoğlu and Seda Ertan

Abstract
3004 aluminum alloys have received wide range in automotive, packaging and building
industries due to it is high strength, high corrosion resistance and good machinability.
Besides, 3004 alloys commonly produced by Direct Chill Casting method. Furthermore,
Twin Roll Casting method which is an alternative of traditional method, came forward in
recent years. In the present work; 3004 aluminum alloys were prepared by twin roll casting.
Aiming for high strength and good bendability, alternative thermo-mechanical processes
were done in laboratories using laboratory mill and furnace. Mechanical tests were
performed for indicating the required temper designation. Characterization of the samples
was accomplished through metallographic investigation in order to examine the effect of
process parameters and examining the morphology. In addition to this, Vickers
micro-hardness, electrical conductivity tests and bending tests were performed on the
samples for the characterization.

Keywords
3004 aluminum alloy Twin roll casting Bending Microstructure

Introduction quality and producibility. Although high casting speed

Aluminum alloy sheets can both produced by twin roll
casting process and traditional direct chill (DC) casting
process. Twin roll casting process has gained wide attention
in recent years and have some advantages such as environ-
mental and energy savings compared to DC casting [1–3].
Besides, cold rolled aluminum strips are attractive engi-
neering material for building, beverage can, packaging and
automotive industries [4].
Casting parameters have detrimental effects on the mi-
crostructure of materials which produced from twin roll
casting. Alterations of casting rate, strip gauge, nozzle set-
back and metal temperature have an influence on material’s
A.U. Malcıoğlu (&)
S. Ertan
ASAŞ Alüminyum San, ve Tic. A.Ş., Kışla Alanı Mevkii,
Küçücek Beldesi, 54400, Sakarya, Turkey
e-mail: ulas.malcioglu@asastr.com
S. Ertan
e-mail: seda.ertan@asastr.com
increases the overall process efficiency but also produces
centerline segregation in the cast microstructure [5].
In terms of grain structure, there are significant differ-
ences between DC cast and twin roll cast sheets. For material
which produced from DC cast, it is easy to be recrystallized.
However, the material which produced from twin roll cast, it
is hard to obtain fully recrystallization in the same heat
treatment conditions. On the other hand, twin roll casting
have advantages in industry such as energy and economic
savings while reducing environmental emissions compared
to DC casting process [6, 7].
The intermetallics for 3xxx alloys have essential effect on
improving microstructure. Variations in size, density and
distribution, have an impact on recrystallized grain size,
anisotropy, formability and surface finish. Furthermore,
during homogenization heat treatment, two phase transfor-
mations observed during the process. First one is the trans-
formation of Al6(Mn, Fe) into a-Al(Mn, Fe)Si phase which
is the consequence of eutectoid transformation. Besides that

© The Minerals, Metals & Materials Society 2017 173

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_24
174 A.U. Malcıoğlu and S. Ertan

the latter one is the intracellular precipitation of a-Al(Mn,
Fe)Si dispersoids on dislocation cells. In low temperature of
homogenization (300–400 °C), Al6(Mn, Fe) intermetallics
have tendency to precipitate and in high homogenization
temperature (450–600 °C) Al6(Mn, Fe) intermetallics dis-
solve and a-Al12(Mn, Fe)3Si intermetallics have tendency to
precipitate [8–11].
The present work investigates the effect of thermo-
mechanical processes on the mechanical and the
microstructural properties of material obtained by twin roll
casting method.
Experimental Procedure
In this study, 3004 aluminum alloy was produced in
industrial scale twin roll caster by ASAŞ Alüminyum and
material’s chemical composition is shown in Table 1.
Samples for examining the mechanical properties, tension
tests were carried out using Zwick/Roell Z050 model testing
machine. Tensile samples prepared from the sheets at 90° to
the rolling direction and tensile strength, yield strength and
elongation were determined from 2 specimens for each
experiment.
Rolling processes were carried out using laboratory type
roll testing machine.
For specimen’s metallographic preparation, specimen grin-
ded with SiC papers and polished with diamond suspension and
colloidal silica. ZEISS Scope. A1 model optical microscope
was used to examine the grain structure. The average grains size
was determined using linear intercept method.
Heat treatment processes were conducted using labora-
tory type Nabertherm model over-temperature limiter fur-
nace chamber. Laboratory annealing tests at different
annealing temperatures were carried out at different gauges
for both processes.
Table 2 summarizes different downstream processes
carried out in this study.
Specimens electrical conductivity values were identified
using Fischer Sigmascope SMP10-HF electrical conductiv-
ity measurement device using a frequency of 60 kHz.
Besides that, 5 measurements were carried out per sample
and averaged.
Vickers micro-hardness (Zwick/Roell ZHV 10) mea-
surements were performed by using applied load 0.2 g for
10 s. 5 readings were measured for every sample in trans-
verse cross-section and averaged.
T-Bending photographs were obtained from ZEISS Stemi
2000-C model Stereo Optic Microscope.
The thickness of as-cast sample of Process A-B and
as-cast sample of Process C-D are 7.37 and 6.24 mm
respectively.
The specimen’s phase identification were examined in
SEM-EDS equipped JEOL JSM-6060LV and ZEISS MA15.
Results and Discussion
Mechanical test results are shown in Tables 3 and 4
respectively. For Process B specimen, partial annealed for
long time as to alternative processes for ensuring temper
condition in H24. For Process A temper condition of H24
could not achieved in similar temperatures for partial
annealing.
The effect on process parameters on the electrical con-
ductivity values are shown in Fig. 1. Conductivity decreased
as the homogenization temperature was increased up to
550 °C due to decreasing in the particle density of disper-
soids at 550 °C. Huang et al. [8] observed that, there is a
relationship between precipitation of dispersoids and
homogenization temperatures. In addition to this, electrical
conductivity decreases with increasing homogenization

Table 1 Chemical composition Alloy Fe Si Mn Mg Cu Cr

of 3004 alloy used in this study
wt% 0.3–0.6 0.1–0.3 1.0–1.3 0.9–1.2 0.1–0.3 0.03–0.08

Table 2 Process parameters Name As-cast Hom. Inter. ann. Partial ann Recrys.
thick (mm) Thick.-Temp. Thick-Temp. Ann.
A 7.37 4.8 mm – – 0.87 mm
480 °C 300 °C/4sa
B 7.37 4.8 mm – 0.87 mm 0.87 mm
550 °C 260 °C/20 h 300 °C/3sa
C 6.24 6.24 mm 1.4 mm 0.87 mm 0.87 mm
550 °C 340 °C 260 °C/3sa 300 °C/3sa
D 6.24 6.24 mm 1.4 mm 0.87 mm 0.87 mm
550 °C 450 °C 260° C/3sa 300 °C/3sa
Production of 3004 Aluminum Alloy Sheet … 175

Table 3 Mechanical test results Process name Yield strength (MPa) Tensile strength (MPa) Elong. (%) Temper
after recrystallization annealing
A 78 188 20.4 0
B 79 180 23.4 0
C 103 185 13.6 0
D 88 182 19.5 0

Table 4 Mechanical test results Process name Yield strength (MPa) Tensile strength (MPa) Elong. (%) Temper
after partial annealing
B 189 230 12.5 H24
C 185 223 6.8 H24
D 181 220 7.2 H24

Fig. 1 Electrical conductivity

values for process A, B, C and D

temperature from 460 to 600 °C. Besides that, increasing
homogenization temperature causes decrement in the particle
density and indicating that precipitation was less and the
quantity of solution was greater compared as to homoge-
nized at 460 °C.
Furthermore, the conductivity of the specimens which
were homogenized at same temperature varied depending on
the int. annealing temperature. Li et al. [12] observed that
electrical conductivity of 3xxx aluminum alloy primarily
controlled solid solution grade of Fe + Mn and in low
homogenization temperatures, alloy’s mechanical properties
increase due to high density of fine dispersoids.
Etched transverse cross section of 7.37 mm and 6.21 mm
thickness as-cast strips on optic microscope images are
shown in Fig. 2. As shown in Fig. 2, grains sizes of as-cast
specimens increase from outermost layers to middle plane as
it is typical behavior of twin roll casting. Furthermore,
as-cast sheet in 6.24 mm gauge exposes slightly thinner
grain structure as to 7.37 mm thick as-cast sheet due to
solidification kinetic. (Grain sizes for Process A and B in
subsurface regions 74 and 65.1 µm respectively.)
As shown in Fig. 3. grain structures of the specimens
homogenized in 480 and 550 °C were similar (Grain sizes
for Process A and B after homogenization in subsurface
regions 42.7 and 48.7 µm respectively.). There is obvious
difference in grain structures for Process C and D between of
the homogenized specimens which annealed in different
thicknesses (Grain size after homogenization for Process C
and D in subsurface region 110 µm.) Particularly, for Pro-
cess C and D in which the specimens were homogenized
without undergoing reduction, the microstructure features
elongated grains in outermost layers and subsurface regions.
Whereas in Process A subsurface region composes of
equiaxed grains.
176 A.U. Malcıoğlu and S. Ertan

Fig. 2 Microstructure of as-cast samples a 7.37 mm gauge b 6.24 mm

gauge

High solidification rate gives rise to finer intermetallics.

During the polygonization process, subgrains forms grains.
If the intermetallics are lower than 1 micron, pinning
mechanism occurs and this mechanism inherits the polygo-
nization and results in coarse grains. In this case, the grains
which are able to occur will be coarser because of no grains
around it to prevent growing. On the contrary the size of the
intermetallics are so high such as 8 µm, this situation brings
difficulties in T bending performance [10, 13].
At the final thickness, all specimens from different pro-
cesses were recrystallized (Fig. 4). In Process C and D
outermost regions are composed of coarsed layers whereas
final microstructure after Process B features homogenous
grain size distribution and fine grains. (Grain sizes for Pro-
cess B after annealing in subsurface regions 28.6 µm.)
Because of the initial grain size after homogenization and
high deformation ratio before final thickness Process B
showed finer grain size. Grain sizes for Process C and D
after annealing in subsurface regions 43 and 46.6 µm
respectively. The heterogeneous grain size distributions were
observed for all of them like as-cast and homogenized
specimens. Fig. 3 Microstructure of samples after homogenization a Process
As it shown in Fig. 5, there are obvious differences in A-4.8 mm gauge b Process B-4.8 mm gauge c Process C/D-6.24 mm
grain structure between Process B and Process C-D which gauge
Production of 3004 Aluminum Alloy Sheet … 177

Fig. 4 Microstructure of samples after recrys. annealing for a Process Fig. 5 Microstructure of samples after partial annealing for a Process
B b Process C c Process D (cross section-transverse to casting B for b Process C c Process D (cross section-longitudinal to casting
direction) direction)
178
Table 5 HV0.2 measurements Process
for Process B, C and D
As-cast
Cold rolled
Homogenization
Cold rolled
Int. annealing
Cold rolled
Partial annealed
Recrys. annealed
partial annealed. As explained before, the specimens have
narrow temperature range to get H24 temper. It is clear that
the recrystallization had already started for Process C-D.
Besides that, relation has found between of grain struc-
tures and T bending performance after partial annealing.
Furthermore there are obvious differences for Process B
compared to Process C-D. It is clear that, outermost regions
consist of elongated layers and recrystallization was not
started after annealing for Process B. In addition to this, for
Process C and D subsurface regions were partially recrsy-
tallized whereas microstructure of Process D subsurface
regions recrystallization ratio is higher than Process C as in
the same region.
Table 5 shows HV0.2 results for Process B, C and D in
different process steps. According to results, coherence had
been seen between of mechanical test results and Vickers
microhardness measurements after partial and recrystalliza-
tion annealing.
T-Bending stereo microscope images are shown in Fig. 6
for determining 0T-bending performance in same temper
conditions (H24) for Process B, C and D after partial
annealing. In study, 0T-Bending behaviour cannot be iden-
tified for Process A in H24 condition because process
parameter insufficient to achieve H24.
Besides that, obvious crack propagations have observed
for Process B after partial annealing. Furthermore the pro-
cesses which have int. annealed, have better 0T-Bending
performance although they are in same temper condition
after partial annealing. In this context, Process D has slightly
better T-Bending behaviour than Process C and observed
that recrystallization ratio enhanced material’s 0-T Bending
results. The reason for better surface after bending is
recrystallized grains.
SEM-BSE images of the samples are shown in Fig. 7.
According to SEM-EDS results, microstructure consist of
A.U. Malcıoğlu and S. Ertan
Name
B C D
72.8 71.8 71.8
92.8 – –
57.2 55.6 55.6
– 96 96
– 65.75 49.6
104.6 92.6 83
74 74.4 71.8
53.6 64 55
intermetallic phases in centerline segregation which includes
major phase of gray Al6(Mn,Fe) intermetallic, minor phase
of black Mg2Si, and low ratio of a-Al(Mn,Fe)Si inter-
metallic phase [12].
Chen et al. [11] investigated the precipitation behavior of
dispersoids pursuant to the heat treatments. In addition to
this, a-Al(MnFe)Si intermetallics dissolve slowly and
Al6(MnFe) intermetallics precipitate with increasing
homogenization temperature.
For 3004 as-cast sample, microstructure consisted of
intermetallic phases such as Al6(MnFe) and a-Al(MnFe)Si
intermetallics. Using BSE images; a-Al(MnFe)Si inter-
metallic can identified from Al6(MnFe) intermetallics.
Figure 8. shows that increasing homogenization temper-
ature from 480 to 550 °C influences intermetallic phases and
morphology changes. Specifically, after homogenization in
480 °C secondary phase morphology distributes in matrix in
lamellar shape whereas after homogenization in 550 °C
secondary phase morphology changes from lamellar to
granular.
Alexander et al. [14] studied the morphology of the
transformation of Al6(Mn, Fe) to a-Al(Mn, Fe)Si and
observed that as a-Al(MnFe)Si phase producing duplex
dispersoids, with nucleates at the particle-matrix interfaces
through the dispersoids. Besides that, the rate of transfor-
mation from Al6(Mn, Fe) to a-Al(Mn, Fe)Si has limitation
by the ratio of silicon in the alloy. Silicon has a major effect
on the transformation. In this context, increasing silicon in
the matrix increases the ratio of transformation to
alpha-phase in both as-cast and homogenized 3004 alloys.
Furthermore there is relation between of fraction of alpha
phase and homogenization time. So a-Al(MNFe)Si inter-
metallic increases with annealing time but during the
increment, percentage of alpha phase has tendency to limi-
tation due to thermodynamic equilibrium.
Production of 3004 Aluminum Alloy Sheet … 179

Fig. 7 SEM-BSE image of as-cast sample

Fig. 6 Stereo microscope images of 0 T-Bending tests for partial Fig. 8 SEM-BSE images of centerline segragation after homogeniza-
annealed a Process B b Process C c Process D tion a Process A b Process B
180
Conclusions
Decreasing strip thickness for as-cast samples effect grains
size and leads to finer grains as compared to sample which
thickness is 7.37 mm.
According to SEM-BSE images 3004 as-cast mi-
crostructure in centerline segregation consists of Al6(MnFe),
Mg2Si, and a-Al(MnFe)Si intermetallic phases indepen-
dently from the casting thickness. Segregation morphology
is in lameller shape.
Homogenization temperature has effect on segregation’s
morphology. Although after homogenization at 480 °C
centerline segregation exist in lamellar shape, increasing
homogenization up to 550 °C morphology changes to
granular shape.
Deformation ratio before homogenization has influence
on grain structures and giving rise to finer grains after
homogenization. After deformation, the dislocation were
propagated to the material and played an essential role for
nucleation.
Initial grain heterogeneity after homogenization was not
changed after thermomechanical processes. Coarsened sur-
face grains are claimed by the pinning of grains by the fine
dispersoids due to rapid solidifications during casting.
Depending on the thermo-mechanical conditions, H24
temper was obtained from Process B, C and D. However, the
temperature interval was so narrow to get target mechanical
properties.
Electrical conductivity increased with homogenization
compared as to as-cast sample. Besides that, conductivity
slightly decreased with increasing homogenization temper-
ature from 480 to 550 °C due to decrement in the particle
density of dispersoids.
Recrystallized surface grains improved the 0T- Bending
performances. But this type of grains on the surfaces can get
in a narrow temperature range. This is not applicable in
industrial furnace conditions.
It is obvious that alloy modification or different thermo-
mechanical processes should be studied to get intermediate
tempers.
Acknowledgements The authors would like to thank to Mr. Samet
Sevinç, technician of ASAŞ R&D Center Laboratory for his precious
works during metallographic works and mechanical studies. Also
A.U. Malcıoğlu and S. Ertan
special thanks to Sakarya University and ZEISS Center for supporting
SEM images.
References
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continuous cast and direct chill cast AA 5052 aluminum alloy
during cold rolling. Metall. Mater. Trans. A 34(4), 951–956 (2003)
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heating rate on the microstructure, texture and tensile properties of
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4. M. Aghaie Khafri, The effect of homogenization on the recrys-
tallization of an Al-Mn-Mg alloy sheet”. J. Mater. Sci. 40,
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5. N. Sun et al., Microstructural evolution in twin roll cast AA3105
during homogenization. Mater. Sci. Eng. A 416, 232–239 (2006)
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aluminum alloys 3105 and 3015 during cold rolling and annealing.
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7. J.T. Liu, S.W. Banovic, R.J. Fields, J.G. Morris, Effect of
Intermediate heat treatment on microstructure and texture evolu-
tion of continuous cast Al-Mn-Mg Alloy Sheet. Metall. Mater.
Trans. A 37(6), 1887–1898 (2006)
8. H.-W. Huang, O. Bin-Lung, C.-T. Tsai, Effect of homogenization
on recrystallization and precipitation behavior of 3003 aluminum
alloy. Mater. Trans. 49(2), 250–259 (2008)
9. M. Dehmas, P. Weisbecker, G. Geandier, P. Archambault, E.
Aeby-Gautier, Experimental study of phase transformations in
3003 aluminium alloys during heating by in situ high energy X-ray
synchrotron radiation. J. Alloy. Compd. 400, 116–124 (2005)
10. H.D. Merchant, J.G. Morris, D.S. Hodgson, Characerization of
intermetallics in aluminum alloy 3004. Mater. Charact. 25(4),
339–373 (1990)
11. K. Liu, X.-G. Chen, Development of Al–Mn–Mg 3004 alloy for
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 Aluminum Alloys with Tailored TiB2 Particles
for Composite Applications

Xingtao Liu, Yanfei Liu, David Yan, Qingyou Han, and Xiaoming Wang

Abstract
TiB2 particles are dispersed into aluminum alloys to improve their mechanical properties.
The TiB2 particles are produced in situ by chemical reactions of a mixture of K2TiF6 and
KBF4 salts with aluminum and are subsequently dispersed in the aluminum alloys as
reinforcement. Through adjusting the processing chemistry by adding different alloying
elements, TiB2 particles can be tailored to desired morphologies and sizes. The results are
discussed in view of interfacial energy and heterogeneous nucleation of aluminum grains in
solidification.

Keywords
MMC Al-MMC TiB2 Al-Ti-B

Introduction in forms of fibers or particulates, aiming at homogeneous

Aluminum metal-matrix composites (Al-MMCs) have
attracted a great deal of attention for applications in the
automobile and aerospace industries attributed to their
superior properties over the matrix alloys [1–3]. A combi-
nation of the properties of an aluminum alloy matrix and the
reinforcing particles makes Al-MMCs promising for light-
weight and energy saving while offering improved
mechanical properties. The reinforcements are generally
ceramics with higher strength and moduli than the aluminum
alloy matrix to bear loading while retaining the good duc-
tility of the matrix alloys. It is, therefore, essential to disperse
reinforcing particles uniformly throughout of the matrix to
avoid property heterogeneity for the industrial applications
of Al-MMCs. Numerous processing methods have been
investigated to improve the dispersion of the reinforcement,
X. Liu
Y. Liu
Q. Han
X. Wang (&)
School of Engineering Technology, Purdue University,
401 N. Grant Street, West Lafayette, IN 47907, USA
e-mail: wang1747@purdue.edu
D. Yan
Department of Natural and Applied Sciences, University of
Wisconsin-Green Bay, 2420 Nicolet Drive, Green Bay,
WI 54311, USA
properties [1, 2]. It is also very important to form strong
bonding between the matrix and the reinforcement to
transfer loading from the matrix to the reinforcement.
However, most ceramic materials are not wetted by the
aluminum matrix, leading to difficulties in dispersing the
reinforcement into the matrix, which is still a major hurdle
on the way to the industrialization of MMCs despite certain
kinds of Al-MMCs are commercially available [1, 2, 4].
Al2O3, SiC and TiB2 particulates have long been studied
as primary choices for reinforcement in Al-MMCs due to
their good properties and availabilities [1, 2, 4–7]. Among
them, SiC reacts with aluminum and Al2O3 reacts with
alloying element, particularly Mg, to form brittle Al4C3 and
MgAl2O4 respectively, deteriorating the interfacial bonding
between reinforcement and an aluminum matrix [2, 8]. In
comparison, TiB2 is proven stable in an aluminum melt and
is well-wetted by aluminum. Moreover, it is used routinely
in the grain refinement of aluminum as nucleation sites for a-
Al grains in solidification by the aluminum casting industries
[9–13]. TiB2 is therefore investigated extensively as rein-
forcement for Al-MMCs [1, 5–7, 14–24].
It improves the properties of a wide range of aluminum
alloys, including Al–Si and Al–Cu alloys. However, it is
difficult to disperse the TiB2 particles homogeneously in an

© The Minerals, Metals & Materials Society 2017 181

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_25
182
aluminum matrix and to control the size of the TiB2 particles
attributed to the intrinsic of the process, which involves
chemical reactions of a mixture fluoride salts and molten
aluminum [5, 24, 25]. The process generally produces tita-
nium and boron into an aluminum melt, where they react with
each other and also aluminum to form boride particulates and
Al3Ti when titanium is in excess of the stoichiometry of TiB2.
The boride particles are a solid solution of (Ti,Al)B2 with a
variable Ti/Al ratio intrinsic of the process, likely related to the
concentration of titanium in the aluminum melt [9, 10, 26–29].
The particulates have a hexagonal disk morphology with sizes
of a few micrometers in general, similar to the TiB2 particles in
Al–Ti-B type grain refiners [6, 24, 25, 27]. Efforts were also
made to control the particulate size, for example reducing the
size to a sub-micrometer level at lower temperatures than what
is used industrially for the molten salt reaction, i.e. for the
production of Al–Ti-B master alloys. Lowering process tem-
perature may result in slow processing and reduced recovery
of titanium and boron, which can be overcome by the appli-
cation of an external agitation, such as through ultrasonic
sonication [7]. The molten salt reaction method is rooted from
the grain refinement practice in the aluminum industries.
Al–Ti-B master alloys containing TiB2 and Al3Ti particles are
produced by the reaction of molten aluminum and a mixture of
hexafluorotitanate (K2TiF6), tetrafluoroborate (KBF4) salts.
Therefore, the in situ fabrication technique for TiB2 reinforced
Al-MMCs can easily be adapted with the existing equipment
for casting. By controlling the K2TiF6/KBF4 ratio, TiB2 and
Al3Ti reinforcing particles in controllable amounts can be
produced simultaneously. A small amount of Al3Ti is essential
for a homogeneous dispersion of the reinforcing particles
[26, 27]. Reactions that may dictate the formation of these
reinforcing phases are given in reactions 1 to 3.
K2 TiF6 þ 2KBF4 þ 10=3Al ¼ TiB2 þ 4=3ð3KF

AlF3 Þ þ 2AlF3 ð1Þ
2K2 TiF6 þ 2KBF4 þ 23=3Al ¼ TiB2 þ Al3 Ti þ 2ð3KF

AlF3Þ þ 8=3AlF3
ð2Þ
K2 TiF6 þ 13=3Al ¼ Al3 Ti þ 2=3ð3KF
AlF3 Þ þ 2=3AlF3
ð3Þ
This paper presents findings on the formation and dis-
persion of TiB2 particles in Al-MMCs through molten salt
reactions. The effects of variables on the formation and
dispersion of the reinforcing particles are discussed in view
of interfacial energy and heterogeneous nucleation of a-Al
grains in solidification. It provides an insight into the
phase relationships in Al–Ti-B alloys to promote the
heterogeneous
X. Liu et al.
nucleation of a-Al grains on TiB2 particles for a homoge-
neous dispersion of TiB2 particles in an aluminum matrix for
property improvement while grain refining the alloy matrix.
Experimental Procedure
Experiments were designed according to reaction 1 to pro-
duce TiB2 (5 wt. pct.) without considering the possibility of
forming (Ti,Al)B2 solid solution despite the formation of a
solid solution of (Ti,Al)B2 was confirmed in the Al–Ti-B
alloy system [9, 10, 13, 27, 28, 30]. This simplified approach
avoided the complexity of forming a (Ti,Al)B2 solid solution
with a variable Ti/Al ratio. The effects of Ti, Mg and Zr on
the dispersion and morphology were studied by adding a
small amount of each alloying element (2 wt. pct.). Ti and Zr
were added in forms of K2TiF6 and K2ZrF6 salts respec-
tively, while Mg was added as a pure metal.
In each test, 250 g of commercial purity aluminum or
aluminum alloys was melted inside a graphite crucible by an
electrical resistant furnace at 820 °C, followed by the addition
of a salt mixture, holding for 15 min, stirring by using a gra-
phite rod and pouring. The pouring was made into a steel mold
at 720 °C and allowed to solidify. The temperature drop from
820 to 720 °C was due to cooling during stirring and handling.
The casting ingots were sectioned for microstructural
analysis. The samples for scanning electron microscopy
(SEM) were polished to a 1 µm finish and examined using
an FEI 3D Quanta Dual Beam SEM operated at 20 kV.
Samples were also deep-etched by using a solution of
250 ml methanol containing 10 g iodine and 25 g tartaric
acid to expose the reinforcing particles.
Results and Discussions
The dispersion of TiB2 particles in an aluminum matrix is
shown in Fig. 1a, where TiB2 particles agglomerate into
clusters along the aluminum grain boundaries. This phe-
nomenon has been well-documented in the literature as TiB2
being pushed into the grain boundaries of a-aluminum,
which nucleated on certain particles including TiB2 [5, 10,
11, 24, 25, 30–32]. An image of a deep-etched sample, as
shown in Fig. 1b, revealed agglomeration of particles in two
different sizes. The particles are loosely bounded, an evi-
dence of particle pushing in solidification, i.e. individual
particles formed and dispersed inside the aluminum melt
after chemical reactions of the salt mixture with aluminum.
However, the particles are weak in nucleating a-Al grains,
resulting in being pushed into the aluminum grain bound-
aries. As TiB2 is stable in aluminum, the particles are not
bounded together or grew. Large particles are in sizes of a
Aluminum Alloys with Tailored TiB2 Particles …
Fig. 1 a SEM back-scattered electron image (BEI) showing TiB2 particles along the aluminum grain boundaries. b SEM secondary electron
image (SEI) of deep-etched sample showing the morphology of in-situ TiB2 particles
few micrometers while the smaller ones are sub-micrometers
in size, which is probably due to the comparatively low
processing temperature in this investigation and the
exothermic nature of the chemical reactions. The later
caused local temperature fluctuation, resulting in the growth
of some of the particles. Uniform particle size can be pro-
duced through the application of external forces that
increases the mass transfer from the salt/melt interface into
the aluminum melt [7]. The effects of alloying elements on
the dispersion and morphology of TiB2 particles are pre-
sented in Fig. 2 to Fig. 4. As shown in Fig. 2a, TiB2 parti-
cles are situated along the a-Al grain boundaries in the
presence of magnesium. However, the particles formed a
dense narrower layers in comparison with the TiB2 in
Fig. 1a, where a salt mixture was added to pure aluminum.
This dispersion is a direct result of the presence of magne-
sium as an alloying element, which made the TiB2 particles
much vulnerable to be pushed into the a-Al grain boundaries
by the solidifying front. Furthermore, the particles are in
smaller sizes than the TiB2 particles in Fig. 1b, which can be
explained by the adsorption of magnesium to the salt/melt
interface and therefore an increased nucleation rate of TiB2.
Magnesium is a surface active alloying element that has a
high tendency to be absorbed onto an interface, including a
surface [33]. Therefore, magnesium participates actively in
the reactions of the salt mixture and aluminum. The reaction
produces KMgF3, which forms a solution with KAlF4 with
an increased melting temperature, and therefore an increase
viscosity [34]. All of these lead to a reduced supply of
titanium and boron from the salt mixture. As a result, the
growth of TiB2 is restricted and smaller particles are
183
produced. It was also reported that the formation of KMgF3
favors the formation of AlB12, a metastable phase of a lay-
ered structure existing at temperatures higher than 975 °C or
at a high concentration of boron [25, 29]. When a mixture of
KBF4 and K2TiF6 is added into an aluminum melt, KBF4
reacts with aluminum to form aluminum boride, AlB12 and
AlB2, due to the lower melting point (460 °C) of KBF4
compared to K2TiF6 (899 °C), which leads to the buildup of
boron at the Al/salt interface and the formation of AlB12.
The AlB12 layers decompose to AlB2 when cooling down.
However, the layered structure is inherited and are pushed
into the aluminum grain boundaries in this case.
The effects of excess titanium than the stoichiometry of
TiB2 has no obvious effects on the dispersion of TiB2, as
shown in Fig. 3a, in comparison with Fig. 1a. TiB2 particles
agglomerate into the aluminum grain boundaries, while large
blocky Al3Ti particles are in the centers of aluminum grains,
which is a typical microstructure of Al–Ti-B master alloys
[9–12, 27, 28, 30, 32]. However, the influence of titanium on
the morphology is obvious, as shown in Fig. 3b. In com-
parison with Figs. 1a and 2a, TiB2 particles in a variable size
formed in Fig. 3b, where large TiB2 particles are in the
centers of the clusters and smaller particles are on the sur-
face. It is evident that titanium causes coarsening of the TiB2
particles inside the clusters. One thing is clear that TiB2 is
fully wetted by aluminum, however, is weaker in nucleating
aluminum grains itself. The nucleation of aluminum grains
by TiB2 is through a layer of Al3Ti on its surface [27, 35].
The effects of zirconium on the dispersion and mor-
phology of TiB2 particles can be seen from Fig. 4a, b. There
is not an obvious difference between Figs. 1a and 4a, where
184 X. Liu et al.

Fig. 2 a SEM BEI showing TiB2 particles along the aluminum grain boundaries. b SEM SEI of deep-etched sample showing the morphology of
in-situ TiB2 particles

Fig. 3 a SEM BEI showing TiB2 particles along the aluminum grain boundaries and Al3Ti in the aluminum grain centers. b SEM SEI of
deep-etched sample showing the morphology of in-situ TiB2 particles

the TiB2 particles are all located along the aluminum grain
boundaries. However, it can be found that the TiB2 particles
in Fig. 4a are larger in size than those in Fig. 1a, which
means zirconium leads to the growth of the TiB2 particles.
It can be attributed to the formation of a solid solution of
(Zr,Ti)B2 with a variable composition [30]. However,
deep-etched sample in Fig. 4b revealed a different growth of
the (Zr,Ti)B2 solid solution from the published findings.
Instead of growing into rod-like (Zr,Ti)B2 along the <0001>
crystal direction, Fig. 4b shows a tetragonal plate-like mor-
phology. Smaller TiB2 particles are found on the surface of
the tetragonal plates, which is similar to the composite
Al3Ti/TiB2 particles in Al–Ti-B master alloys [10, 13].
According to the tetragonal shape, the plates are aluminides
rather than borides. However, aluminides are in larger sizes
than the plates in Fig. 4b and in the aluminum grain centers
Aluminum Alloys with Tailored TiB2 Particles …
Fig. 4 a SEM BEI showing TiB2 particles along the aluminum grain boundaries and large (Ti,Zr)B2 particles (high brightness). b SEM SEI of
deep-etched sample showing large plates of (Ti,Zr)B2 with fine TiB2 disks
in general. Further analysis is therefore under the way to
identify the phase of the plates, including micro X-ray
diffraction and transmission electron microscopy.
From previous discussions, alloying elements play import
roles in the formation of the reinforcing particles in the
production of TiB2 reinforced Al-MMCs. Their effects on
the dispersion of the reinforcing particles are minor under
the present processing conditions. However, the alloying
elements participate in the formation of the boride particles
by forming solid solutions of the borides, either restrict or
promote the growth of the reinforcing boride particles.
Strong boride formers, such as zirconium, promote the
growth of the boride particles, while surface-active alloying
elements, such as magnesium, leads to the formation of fine
particles due to an increased nucleation rate.
Conclusions
The morphology of the in situ TiB2 particles can be tailored
by the addition of alloying elements. Overall, boride parti-
cles, in two different sizes, agglomerate into clusters along
the aluminum grain boundaries. This is an effect of particle
pushing by the solidifying front, which is also evident that
the boride particles themselves are weak nucleation sites for
aluminum grains in solidification. However, alloying ele-
ments have significant effects on the growth of the boride
particles, which also change the morphologies of the parti-
cles. Magnesium increases the nucleation rate of the TiB2
particles, leading to fine particles. In comparison, zirconium
leads to the growth of the boride particles into tetragonal
185
shapes with larger particles sizes. Excess titanium than the
stoichiometry of TiB2 forms Al3Ti, which nucleates alu-
minum grains and are situated in the aluminum grain centers.
Acknowledgements The authors would like to acknowledge AMG
Aluminum North America for supplying raw materials for the research.
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 Development of Low Expansion and High
Strength Aluminum Matrix Hybrid Composite

Jamuna Sethi, Siddhartha Das, and Karabi Das

Abstract
An aluminum (Al) matrix hybrid composite reinforced with yttrium tungstate (Y2W3O12) and
aluminum nitride (AlN) is synthesized by high energy ball milling followed by compaction
and sintering. Y2W3O12, a negative thermal expansion material (−7.1
10−6/K), is chosen
as one of the reinforcements to lower the coefficient of thermal expansion (CTE) of the
composite. AlN is added to the composite in order to improve the strength and thermal
conductivity of the composite. X-ray diffraction patterns of the milled powders as well as
sintered composites reveal the presence of only Al, AlN and Y2W3O12 peaks indicating no
chemical reaction between the matrix and reinforcement during milling and sintering. The
scanning electron micrograph shows fairly uniform dispersion of reinforcement in the matrix.
Hardness, elastic modulus and CTE are measured by Vickers hardness test, nanoindentation
test, and dilatometry, respectively. It is observed that a composite with high hardness, high
Young’s modulus and low CTE can be obtained by adding 15 wt% AlN and 30 wt%
Y2W3O12 into the Al matrix.

   
Keywords


Aluminum matrix Hybrid composites X-ray diffraction Nanoindentation Vickers
hardness Elastic modulus

Introduction some structural parts in aerospace, measuring instruments,

Aluminum matrix hybrid composites (AMHCs) are the new
generation of metal matrix composites having potential of
satisfying the recent demands of advanced engineering
material applications [1]. The AMHCs have some unique
combination of properties, making them very popular and
top choice candidate material for a wide range of applica-
tions [2]. The properties of aluminum matrix composites
(AMCs) which make them suitable for various technical uses
are high specific strength and stiffness, low coefficient of
thermal expansion (CTE), high thermal conductivity, and
good wear and abrasion resistance [3]. The AMHCs with
low CTE and high strength are used in many areas such as
J. Sethi  S. Das  K. Das (&)
Department of Metallurgical and Materials Engineering, IIT
Kharagpur, Kharagpur, 721302, West Bengal, India
e-mail: karabi@metal.iitkgp.ernet.in
general optics, sensors, microwave components, electronic
packaging, heat sink, and antenna. For AMCs with single
functional reinforcement, it is difficult to obtain very low
CTE and high strength at the same time [4]. The most
effective way to lower the CTE is to use negative thermal
expansion (NTE) material as reinforcement. However, with
the increase of volume fraction of NTE, material properties,
such as Young’s modulus and thermal conductivity decrease
immensely. As a result, the composite loses its scope for
practical applications [4–8].
In the present study, aluminum metal matrix is reinforced
with two reinforcements to get the required properties, i.e.,
low CTE and high strength. One of the reinforcement is
yttrium tungstate (Y2W3O12) and the second reinforcement
is aluminum nitride (AlN). The Y2W3O12 is a negative
thermal expansion material (NTE), and it has some unique

© The Minerals, Metals & Materials Society 2017 187

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_26
188
advantages over other NTE materials such as high NTE
value (a = −7.0
10−6/K) over a wide temperature range,
can be easily synthesized, stable at room temperature and
shows no phase transition [2, 9–11]. Aluminum nitride is the
second most filler material for an aluminum matrix. AlN is
an ideal candidate due to its very high thermal conductivity,
high Young’s modulus, no toxicity and stable crystal
structure [12–14, and 15].
Experimental Procedure
In the present study, Al (98%, Loba chem. ™), yttrium
tungstate (Y2W3O12) and aluminum nitride (AlN) (99.9%
Alfa Aesar™) powders were used as starting materials. The
yttrium tungstate was synthesized in our laboratory [11].
The single reinforced composites with 30 wt% AlN and
30 wt% Y2W3O12 and the hybrid composite reinforced with
30 wt% Y2W3O12 and 15 wt% AlN were fabricated by solid-
state powder metallurgy route. The powders were milled in a
high energy Fritsch pulverisette- 4 vario-planetary ball mill
for 10 h followed by compaction, sintering and forging. The
milled powder and forged samples were characterized in D8
Advanced X-ray diffractometer which was used to investigate
Fig. 1 SEM micrographs of a Al/Y2W3O12, b Al/AlN and c Al/ Y2W3O12/ AlN composites
J. Sethi et al.
the structural changes and phase identification. FEG Quanta
250 scanning electron microscope (SEM) was used for the
microstructural characterization of forged pellets. The density
was measured by Archimedes principle and hardness mea-
surement was done by Vickers hardness tester with 100 N as
applied load and 10 s of dwell time. Nanoindentation test was
performed by Hysitron TI 950 TriboIndenter at 293 K using
a Berkovich diamond indenter with pyramidal tip of face of
face angle 65.3°. The CTE measurement of all the specimens
was conducted from room temperature to 873 K at a heating
rate 10 K/min using a Bahr Thermo analysis DIL 805 A/D
dilatometer.
Results and Discussion
Microstructure and X-ray Diffraction
The SEM images of the forged Al/Y2W3O12, Al/AlN and
Al/Y2W3O12/AlN composites are shown in Fig. 1. It is
observed that Y2W3O12/AlN particles are fairly uniformly
distributed in the Al matrix.
Figure 2 shows the X-ray diffraction patterns of 10 h
milled powders of pure Al, AlN and synthesized Y2W3O12.
Development of Low Expansion and High Strength Aluminum … 189

Fig. 2 X-ray diffraction patterns of 10 h milled powders of pure Al,

pure AlN and Y2W3O12 Fig. 3 X-ray diffraction patterns of 10 h milled powders of
Al/Y2W3O12, Al/AlN and Al/Y2W3O12/AlN composites

Figure 3 shows the X-ray diffraction patterns of 10 h milled

powders of Al/Y2W3O12, Al/AlN and Al/Y2W3O12/AlN.
The XRD pattern of the milled powder shows only peaks of
Al, AlN, and Y2W3O12 which implies that no chemical
reaction has occurred between the reinforcement and matrix
during milling.
Figure 4 shows the X-ray diffraction patterns of forged
Al/ Y2W3O12, Al/AlN, and Al/Y2W3O12/AlN composites. It
is also seen that there are no chemical reaction has occurred
during sintering as only the precursor peaks are present.

Density and Hardness Measurement

The density measurement is done precisely by modified

Archimedes principle by removing the error introduced due
to interconnected and disconnected pores. This measurement
process involves determination of the weight of the sample
in the air (Wa), weight of the sample when it is in the liquid
(Wl) and finally weight of the sample in the air after soaking Fig. 4 X-ray diffraction patterns of Al/Y2W3O12, Al/AlN and
in liquid for about 30 min (Ws). In the present study, diethyl Al/Y2W3O12/AlN composites
190
Fig. 5 Density of Al/Y2W3O12, Al/AlN and Al/Y2W3O12/AlN
composites
phthalate (C12H14O4) is used as liquid media for density
measurement whose density is qliq = 1.117–1.119 g/cm3 at
room temperature. The density (q) of samples is calculated
by using the following equation.
Wa
qliq
qsample ¼ ð1Þ
Ws  Wl
Figure 5 shows experimental and theoretical density of
forged single and hybrid reinforced composites. It is found
that when AlN, Y2W3O12 or AlN + Y2W3O12 is added to
the Al matrix, density of composite increases because the
density of both Y2W3O12 (4.37 g/cm3) [1] and AlN
(3.26 g/cm3) [7] is higher than the density of Al (2.7 g/cm3).
By comparing the theoretical, as calculated by rule of
mixture (ROM) and experimental density, it is found that the
difference between the two densities is higher in hybrid
composite compared to single reinforced composite. This is
due to the generation of high amount of porosity in the
hybrid composite, caused by the presence of high amount of
reinforcement particles and subsequent formation of
agglomerates.
Hardness measurement of the composite is one of the
most informative and rapid methods to determine the
mechanical properties. The hardness values of single and
hybrid reinforced composites are shown in Fig. 6. The
composite shows higher hardness than the Al matrix due to
(a) both Y2W3O12 and AlN have higher hardness than that of
Al, (b) bothY2W3O12 and AlN are reasonably well dispersed
into the Al matrix and hinder the movement of dislocation
resulting in dispersion hardening, (c) The Al matrix contains
higher dislocation density which is generated due to the
mismatch in CTE between the matrix and reinforcement in
composites resulting in higher hardness [16]. Among all the
J. Sethi et al.
Fig. 6 Vickers hardness of Al/Y2W3O12, Al/AlN and Al/Y2W3O12/
AlN composites
composite, Al/AlN composite has the highest hardness.
A comparison between the theoretical, as calculated using
ROM and experimental values reveals that the difference
between the two values is relatively high for the hybrid
composite compared to the single reinforced composite. This
is again due to the higher amount of porosity in the hybrid
composite.
Elastic Modulus Measurement
Nanoindentation technique helps to measure the mechanical
properties on the submicron level. It is mostly used to
determine the reduced elastic modulus and hardness by
continuously measuring the load–displacement curve during
loading and unloading of indentation. The elastic modulus of
the sample is obtained from the following relation.
 1
1 1  v2i 1  v2s
¼ þ ð2Þ
E Ei Es
where, E = Reduced Young’s modulus, Ei = Young’s
modulus of a diamond indenter tip = 1140 GPa, Es =
Young’s modulus of the specimen, vi = Poisson’s ratio of
diamond indenter tip = 0.07, and vs = Poisson’s ratio of the
specimen, generally varies between 0 and 0.5 [17]. The
typical load-displacement curves of Al/Y2W3O12, Al/AlN
and Al/Y2W3O12/AlN are shown in Fig. 7. There is some
structural changes of the load-displacement curves during
the test. It can be clearly observed that the unloading
behavior of the Al/Y2W3O12 composite is different from
Al/AlN and Al/Y2W3O12/AlN composites. It is also found
that after unloading final displacement of this composite is
higher than the other two composites. It is assumed that,
Development of Low Expansion and High Strength Aluminum …
Fig. 7 Load versus displacement
curve of Al/Y2W3O12, Al/AlN
and Al/Y2W3O12/AlN composites
by nanoindentation
materials are deformed both elastically as well as plastically
during loading. However, during unloading only elastic part
is recovered and the slope of the curve gives the elastic
unloading stiffness [17]. The slopes of unloading curve and
final depth of penetration of Al/AlN, Al/Y2W3O12/AlN
composites are lower as compared to Al/Y2W3O12 com-
posite, which implies that these composites have higher
elastic modulus as compared to Al/Y2W3O12 composite.
This is due to the presence of AlN as it has higher elastic
modulus with respect to Al matrix and Y2W3O12.
The continuous loading and unloading provide a
mechanical fingerprint over the sample. The SEM images of
nanoindenter impression on the surface of Al/ Y2W3O12,
Al/AlN and Al/Y2W3O12/ AlN composites are shown in
Fig. 8. It is clearly observed that, the size of the impression
is smallest in Al/AlN composite among all the composites,
since Al/AlN composite has the highest hardness. Therefore,
it indicates that the presence of AlN particles primarily lead
to higher constraint during indentation resulting in increase
in hardness. Besides contributing towards the improvement
of the hardness, the addition of the AlN particles has also
given a positive effect on the elastic modulus of composites.
The elastic modulus of Al/AlN, Al/Y2W3O12 and
Al/Y2W3O12/AlN composites is shown in Fig. 9. The elastic
modulus of the Al/AlN composite improves drastically with
respect to Al matrix. It is observed that an addition of 30 wt
% AlN to the Al matrix increases the elastic modulus by
about 70%. This is mainly due to the higher elastic modulus
of AlN (345 GPa) than that of Al (70 GPa) [18]. A strong
191
interfacial bonding between Al and AlN also contributes
towards the elastic modulus increment, as has been reported
in the literature [12]. However, an addition of 30 wt%
Y2W3O12 to the Al matrix decreases the elastic modulus by
about 36% due to the lower elastic modulus value of
Y2W3O12 (25 GPa) compared to that of Al [19] and also
most likely due to the week interfacial bonding between the
Y2W3O12 and Al matrix. The elastic modulus of the hybrid
reinforced composite quite naturally falls in-between the
elastic modulus of the two single reinforced composites.
Coefficient of Thermal Expansion (CTE)
The relative linear length change of single as well as hybrid
composites, as measured by dilatometry, is shown in
Fig. 10. Linearity is found in the heating curve which
implies no phase transformation occurs during heating.
The CTE of single and hybrid composites is shown in
Fig. 11. It is observed that the CTE of Al/Y2W3O12 com-
posite decreases drastically from 23.8
10−6/K [6] to
16.19
10−6/K due to the addition of negative thermal
expansion material, i.e., Y2W3O12 [8–11]. In Al/AlN com-
posite, CTE also decreases since AlN is low positive thermal
expansion (4.03
10−6/K) material [5, 6]. A thermal stress
is generated by the mismatch of thermal expansion between
the Al matrix and AlN/Y2W3O12 particle and restricts the
expansion of Al matrix through an interface [14]. In
Al/AlN/Y2W3O12 hybrid composite, CTE value is decreased
192 J. Sethi et al.

Fig. 8 SEM image of nanoindenter impression on the surface of a Al/Y2W3O12, b Al/AlN and c Al/Y2W3O12/AlN composites

Fig. 9 Elastic modulus of f Al/Y2W3O12, Al/AlN and Al/Y2W3O12/ Fig. 10 Relative linear length changes of f Al/Y2W3O12, Al/AlN and
AlN composites Al/Y2W3O12/AlN composites
Development of Low Expansion and High Strength Aluminum …
Fig. 11 CTE of Al/Y2W3O12, Al/AlN and Al/Y2W3O12/AlN
composites
to half of Al matrix, because of addition of AlN and
Y2W3O12. There is no doubt that greater the weight fraction
of reinforcement, the lower the CTE of composites as both
the reinforcing materials have lower CTE than that of the
matrix. It is also found that the experimental CTE values are
higher than the theoretical values. This may be due to the
fact that the composites are not fully dense and also due to
weak interfacial bonding between the matrix and reinforce-
ment [19].
Conclusions
• Al matrix composites reinforced with AlN, Y2W3O12 or
AlN + Y2W3O12 particles have been successfully pro-
duced by solid state powder metallurgy route.
• Addition of AlN and Y2W3O12 increases the hardness of
the composites. Among all the composites, Al/AlN has
the highest hardness.
• Addition of AlN increases the Young’s modulus,
whereas addition of Y2W3O12 decreases the Young’s
modulus of the composite. Among all the composites,
Al/AlN has the highest Young’s modulus.
• The thermal expansion curves for the composites exhibit
linear behavior indicating no phase transition within the
investigated transition temperature range, i.e., room
temperature to 873 K. It is also found that CTE of
composites decreases with the addition of AlN and
Y2W3O12. An addition of 30 wt% Y2W3O12 and 15 wt%
AlN can decrease the CTE value to half of the Al matrix.
• The properties such as hardness, elastic modulus and the
thermal expansion of the composite can be tuned by
adjusting the amount of AlN and Y2W3O12
reinforcement.
193
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 Part VI
Aluminum Alloys, Processing and Characterization:
Solidification and Casting
 A Model for a-Al(Mn,Fe)Si Crystals

Christian J. Simensen and Are Bjørneklett

Abstract
A series of large crystals of a-Al(Mn,Fe)Si with different content of manganese, iron and
silicon have been analyzed using microprobe, X-ray diffraction, pycnometer (density) and
electrical devices (electrical resistivity and Seebeck coefficient). The cubic phase
a-Al(Mn,Fe)Si had a density varying from 3520 to 3620 kg/m3. When iron was increased
from 1.9 to 20.8 wt%, the content of silicon was reduced from 10.7 wt% to 8.6 wt%. The
phase had a low electrical resistivity, 2
10−6 Xm. Large crystals of a-AlMnSi had a large
Seebeck coefficient, viz. 42 µV/K, the crystal containing some iron gave a slightly lower
value, 34 µV/K. All the crystals were n-type semiconductors. A new model for a-AlMnSi
has been proposed, where Si-atoms are connected in hexagonal rings around 0,0,0 and
½,½,½. The rings are linked by Mn and Si atoms, all covalently bonded. According to this
model, the ideal a-AlMnSi crystals have 24 Mn, 18 Si and 96 Al-atoms in the unit cell.
Fe + Al can substitute for Mn + Si atoms in the unit cell. Vacancies can form on Mn-sites.

  
Keywords
Aluminium alloys Crystal structure Seebeck coefficient Covalent bonding

Introduction
The cubic phase a-AlMnSi is commonly present in aluminium
alloys containing more than 0.1 wt% Mn and 0.2 wt% Si. It
often contains other elements such as iron, vanadium, copper,
nickel and chromium which substitute manganese in the unit
cell. The lattice parameter of pure a-AlMnSi is 1.2666–
1.268 nm [1, 2]. The phase consists of 24 Mn-atoms and 114
Al + Si atoms. Chemical analysis indicates that the number of
C.J. Simensen (&)
SINTEF Materials and Chemistry, P.O.Box 124 Blindern,
0314 Oslo, Norway
e-mail: Christian.J.Simensen@sintef.no
A. Bjørneklett
Björneklett-Elektronik, Ragnaröksgatan 14, 72355 Vesterås,
Sweden
silicon atoms in the unit cell is 16–18. Tibballs et al. [1] have
shown that the silicon atoms are present in five out of nine
sublattices occupied by light elements. The questions are: Can
the structure of a-AlMnSi be specified in more detail? What
kind of bonds exists between the atoms, and where are the
silicon atoms located in the unit cell?
Large crystals of a-AlMnSi have been made in molten
aluminium by a slow cooling between 700 and 600 °C. Pratt
and Raynor [3] have analyzed such crystals and shown that
the crystals’ content of manganese can be reduced by
increasing the content of silicon in the melt keeping the
manganese content constant. Their results indicate that the
number of manganese atoms in the unit cell can be reduced
to 22. Tibballs et al. [4, 5] have analyzed large crystals of
a-Al(Mn,Fe)Si with different content of iron. Their results
show that iron can substitute at least 20 of the manganese
atoms in the unit cell. Furthermore, there is a systematic
change in the content of silicon in a-Al(Mn,Fe)Si. When the
content of iron increases from 0 to 20 wt% Fe, the content of
silicon decreases from 12 to 8 wt%. This observation

© The Minerals, Metals & Materials Society 2017 197

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_27
198
strongly indicates that there is a bonding between
manganese-iron atoms and silicon atoms in the unit cell. The
composition may be controlled by the number of valence
electrons in the unit cell.
Previous work [4, 5] concerning a-Al(Mn,Fe)Si was
concentrated on X-ray diffraction determining the lattice
parameters and microprobe analysis determining the chem-
ical composition. This work is a continuation and concen-
trates on measuring the electrical properties and density of
the crystals. These measurements also include as a com-
parison, some measurements of the hexagonal a1-AlFeSi.
The main purpose has been to determine the atomic content
of the unit cell of these crystals and try to answer the
questions raised above.
Experimental
The alloys were prepared by mixing high purity metals;
99.993% Al, 99.95% Mn, 99.99% Fe, and semiconductor
grade Si to make ingots with weight 50 g. The ingots were
cast in alumina crucibles sealed in quartz ampoules under a
0.25 bar atmosphere of argon. The materials produced were
Al- 7.5 wt% Si—Mn–Fe with different content of man-
ganese and iron as shown in Table 1. The samples were
labelled from 2 to 6. Sample 4 was heated to 950 °C and
annealed for 12 h. Then it was cooled to 690 °C (Ta) and
annealed for 5 h. The third step was a cooling to 630 °C (Tb)
over a period of 20 h and a holding time of 30–40 h. All the
other ingots were heat treated in the same way except that
the second holding temperature (Ta) was varied between 680
and 730 °C as shown in Table 1.
A fraction of the samples was dissolved in butanol, and
the undissolved a-Al(Mn,Fe)Si particles were extracted [6].
An example of a large crystal is shown in Fig. 1. The density
of the intermetallic crystals was determined by pycnometer
using distilled water and a total of 250 mg of large crystals.
The weight was measured by a Sartorius R 200D
microbalance. The pycnometer was immersed in an ultra-
Table 1 Chemical composition Sample no Chemical composition (wt%)
and holding temperatures for
materials of Al–Si–Mn–Fe alloys Si
2 7.5
3 7.5
4 7.5
5 7.5
6 7.5
C.J. Simensen and A. Bjørneklett
sound bath before the measurements in order to remove the
last fraction of air bubbles on the walls and the crystals. The
density of the crystals is equal to:
m
q ¼ qwater  ð1Þ
m  Dm
m = weight of crystals and Dm = difference in weight
between the pycnometer filled with intermetallic crystals and
water and the pycnometer filled with water only. The mea-
surement was carried out at 23 °C with a standard deviation
of 0.1 °C. Each pycnometer measurement of crystals was
repeated out about 20 times giving a standard deviation of
the weight measurement of about 0.3 mg. The result is a
standard deviation of about 20 kg/m3 in the density mea-
surements. We had some problems with the measurements
of material 2, 3 and 5 as some of the crystals fractured during
the ultrasound bath treatment. As a test we measured the
density of pure aluminium, 99.993% Al. The result was
2700 kg/m3 in close agreement with published values [7].
The electrical properties were measured with single
crystals, 2–3 mm long and 0.3 mm wide. The electrical
resistance of a crystal of material 6 was measured by
applying an electrical current of 1A through the crystal using
a 4-electrode apparatus. The electrical resistivity of crystals
was estimated based on the length and cross-sectional area of
the crystal. All four electrodes were attached with a silver
filled epoxy adhesive (Able bond 958-2).
The Seebeck coefficient in crystals of materials 2, 4 and 6
was determined in the following way: A crystal was placed
between two relatively large copper specimens. The contact
between the copper and the crystals was good. The tem-
perature in the copper specimens was measured with a
thermistor (yellow spring instruments with 0.1 °C accuracy)
in each copper specimen situated close to the crystal. The
voltage over the crystal was measured with a voltmeter
(Keithley 199, 1 lV resolution). One of the copper speci-
mens was heated to 100–150 °C, while the voltage across
the crystal was measured continuously. Finally, the Seebeck
coefficient was also measured in crystals of pure a-AlMnSi
Holding temperature (°C)
Mn Fe Ta Tb
0.1 3.0 680 630
1.0 3.0 690 630
1.9 1.9 710 630
3.0 1.0 720 630
3.6 0.4 730 650
A Model for a-Al(Mn,Fe)Si Crystals 199

the hexagonal phase is 3640 kg/m3. All the results are in

Fig. 1 Large crystal of a-Al(Mn,Fe)Si from material 4
with composition Al—9.8 wt% Si—29.2 wt% Mn. These
crystals were made in molten aluminium as described by
Tibballs et al. [1].
Results
The density measurement, and the previous microprobe and
X-ray measurements [4, 5] of the hexagonal a1-AlFeSi from
material 2 are summarized in Table 2 and 3. The density of
agreement with the published data of Black et al. [8, 9] and
show that the number of atoms in the unit cell of a1-AlFeSi
is 237. The largest deviation in our results compared with
Black et al. is in the chemical analysis of silicon and iron.
Our results show that the phase can contain one percent of
manganese.
The densities of the cubic phase in material 3–6 are
summarized in Table 4. The results show that material 4 has
a density of 3620 kg/m3 and the others 3520–3540 kg/m3.
The former value is in agreement with the values published
by Cooper et al. [2, 10], while the latter ones are somewhat
smaller. The difference may be due to the above mentioned
fracturing of crystals into very small pieces. The estimated
number of atoms in the unit cells based on the density, X-ray
diffraction and microprobe analyses, is summarized in
Table 5. They show that the number of aluminium atoms is
between 95 and 101, the number of silicon atoms between
10 and 16, and manganese plus iron between 21 and 24. The
total number of atoms in the unit cell is between 134 and
137. The number of silicon atoms decreases as a function of
the number of iron atoms as shown in Table 5.
The electrical resistance over the length of crystal in
material 6 (low in iron) was of the order 5 mX. Measure-
ment of the crystal size gave an electrical resistivity
approximately equal to 2 lXm. This is close to the elec-
trical resistivity of pure manganese (1.44 lXm).

Table 2 Density and Material no Chemical composition (wt%) Density (kg/m3)

composition of the hexagonal
a1-Al(Fe,Mn)Si Al Si Mn Fe
Particles in no 2 59.3 9.8 0.95 29.9 3640 ± 20
Corby and Black 58.8 8.7 32.5 3665 ± 4
Robinson et al. 58.8 8.7 32.5 3610 ± 20

Table 3 Lattice parameters and Material no Number of atoms in the unit cell Lattice parameters (nm)
atoms in the unit cell of a1-Al(Fe,
Mn)Si Al Si Mn Fe a c
2 168.5 26.2 1.3 41.0 1.2404(14) 2.621(3)
Corby and Black 167.8 23.9 44.9 1.2404(1) 2.6234(3)
Robinson et al. 162.7 23.1 43.4 1.23(1) 2.62 (2)

Table 4 Density, lattice Material no Chemical composition (wt%) Density (kg/m3) Lattice parameter(nm)
parameter and composition of the
cubic phase a-Al(Mn,Fe)Si Al Si Mn Fe
4 62.3 8.3 8.6 20.8 3620 ± 20 1.2585(1)
3 62.3 9.2 14.4 13.1 3520 ± 20 1.2609(1)
5 62.9 10.1 21.0 6.0 3520 ± 20 1.2648(1)
6 59.1 10.7 28.3 1.9 3540 ± 20 1.2657(1)
Cooper et al. 60.9 10.7 28.4 3620 ± 60 1.268(2)
Cooper 60.1 6.6 6.5 26.4 3590 ± 60 1.256(2)
200 C.J. Simensen and A. Bjørneklett

Table 5 Number of atoms in the Material no Number of atoms in the unit cell
cubic a-Al(Mn,Fe)Si phase
Al Si Mn Fe
4 100.5 12.9 6.8 16.2
3 99.5 13.9 11.1 10.0
5 100.1 15.4 16.4 4.6
6 94.7 16.4 22.3 1.5
Cooper and Robinson 100.4 16.9 23.0
Cooper 96.1 10.1 5.1 20.3

Table 6 The Seebeck coefficient Material no Phase Chemical composition (wt%) Seebeck coefficient (lV/K)a
of the AlMnFeSi-phases
Si Mn Fe
Ternary-2 a-AlMnSi 9.8 29.2 0 42
6 a-Al(Mn,Fe)Si 10.7 28.3 1.9 33
4 a-Al(Mn,Fe)Si 8.3 8.6 20.8 35
3 a1-Al(Fe,Mn)Si 9.8 0.95 29.9 12
a
The standard deviation is 2–3 lV/K

Table 7 Atomic coordinates of Sublattice Symmetry Site occupied Percentage of Coordinates

the sub-lattices of a-AlMnSi, no by Si-atoms
cubic space group 200 with x y z
symmetry Pm3 [1, 2] M1 12 Mn 0.3271 0.2006 0
M2 12 Mn 0.1797 0.3085 0.5
A1 6 Al 0.3638 0 0
A2 6 Al 0.1216 0.5 0.5
A3 6 Al + Si 69 ± 19 0.2897 0 0.5
A4 12 Al + Si 55 ± 15 0.1636 0.0997 0
A5 12 Al + Si 42 ± 15 0.3342 0.3990 0.5
A6 12 Al + Si 8 ± 10 0.3319 0.4037 0
A7 12 Al + Si 6 ± 10 0.1205 0.1175 0.5
A8 24 Al 0.1185 0.1892 0.2980
A9 24 Al 0.3897 0.3127 0.1955

Then it was discovered that the materials display the
properties of a semiconductor, refer Table 6. All the mea-
sured materials were n-type semiconductors with a high
Seebeck coefficient. The highest value, 42 µV/K was mea-
sured for the pure a-AlMnSi. The other a-crystals containing
some iron had slightly lower Seebeck-coefficient. The
hexagonal phase is also a semiconductor, but the effect is
much smaller 12 ± 3 µV/K.
Discussion
It is evident from the result that pure a-AlMnSi and also
a-Al(Mn,Fe)Si have a semiconductor nature. (Metals have
Seebeck coefficient close to zero and semiconductors have a
positive or a negative coefficient with some tens of µV/K or
more.) Since these crystals exhibit a relatively strong See-
beck coefficient, the silicon atoms in the unit cell are most
likely arranged in a continuous chain of covalently bonded
atoms. It is expected that some manganese atoms are a part
of this chain and have covalent bonds to the neighbouring
silicon atoms. The aluminium atoms take no part in this
chain as no binary Al–Si phases exist. Therefore the alu-
minium atoms are linked to the manganese atoms by metallic
bonds. The atomic positions of the atoms in the unit cell are
outlined in Table 7 [2]. The percentage of silicon in each
sub-lattice has been determined by Tibballs et al. [1] by
neutron diffraction. These results are also included in
Table 7. About 50% of the atoms in sub-lattices A4 and A5
are silicon. For each of these sub-lattices the silicon atoms
A Model for a-Al(Mn,Fe)Si Crystals 201

can be arranged in six-sided ring around 0,0,0 (A4) and

½,½,½ (A5). Each atom in the ring has one manganese
neighbour that again has four aluminium atoms as neigh-
bours as sketched in Fig. 2. The angle between the silicon
neighbours in the ring is 108.5° using the data of Cooper and
Robertson [2]. This is very close to the tetrahedral angle
109.47° that is the “ideal” bonding angle for covalent bonds
in silicon. The angle between manganese-silicon-silicon
atoms is about 121.5° (Fig. 2). Four of the atoms in the
silicon ring are in a plane parallel to one of the main axes,
and the last two are slightly out of the plane as shown in
Figs. 3 and 4. Each ring can be arranged in 12 different
ways. According to the neutron activation measurements the
last six atoms are placed in sub-lattice A3 (four atoms), one
in sub-lattice A6 and one in sub-lattice A7.
The four Si-atoms on A3 with use of manganese atoms
can link neighbouring silicon atoms on A4. An example is
shown in Fig. 4. The angle between the manganese atoms
and the linking silicon atoms is 125.5°. The linking man-
ganese atom then has four covalent bonds with its two sili-
Fig. 3 Six silicon atoms on A5-sites forming a ring around the ½, ½,
½, position. Each silicon atom is bonded to a manganese atom on site
M2. (Axes unit is lattice parameter of a-AlMnSi)

Fig. 4 A chain of silicon and manganese atoms close to the plane

Fig. 2 The atoms around a silicon atom on an A4 or A5 site. They are z = 0 of the cubic unit cell. The silicon rings around 000, 100 and 010
bonded to two silicon atoms and one manganese atom as illustrated. are linked by manganese atoms on site M1 and silicon atoms on site
The neighbouring manganese atom is linked to one silicon and four A3. The main planes of the silicon rings lie in the xy, xz and yz planes,
aluminium atoms or two silicon and three aluminium atoms respectively, in this example
202 C.J. Simensen and A. Bjørneklett

con neighbours, while the other manganese atom next to the

silicon atom has only two covalent bonds to the nearest
silicon atom. On average three silicon atoms on A3 links
neighbouring silicon rings in the unit cell. The last silicon
atom on A3 is used in connection with a silicon atom on A7
as described below.
The silicon atom on A6 can link one manganese atom on
sub-lattice M1 and one manganese atom on M2 (refer
Table 7). Therefore, this atom can link a silicon ring on A4
to a neighbouring ring on A5. The angle between the con-
necting atoms, Mn(M1)-Si(A6)-Mn(M2), is 117.8° (Fig. 5).
More complex connections are also possible since the silicon
atom on A6 has a silicon neighbour on A3 [1].
The silicon atom on sub-lattice A7 has as neighbours a
manganese atom on M2 and a silicon atom on A3. It is also
relatively close to two manganese atoms on M1 (a distance
0.284 nm). The simplest model is then that the manganese
atoms on M1 and M2 are linked to two silicon atoms making
a Mn(M1)-Si(A3)-Si(A7)-Mn(M2) chain. This arrangement
of atoms can thus link a silicon ring on A4 to a neighbouring
silicon ring on A5. It can be shown that also other
arrangements of linking the rings using silicon on A7, are
possible. The conclusion is that silicon atoms on A6 and A7
are used to link silicon rings on different types of
sub-lattices. An example is shown in Fig. 6.
Fig. 5 One example of a link between the rings on 0,0,0 and ½, ½, ½.
The silicon rings are bonded by means of two manganese atoms and
one silicon atom (A6). The silicon rings are situated on the planes z = 0
and y = 0.5 in this example. (The unit on the axes is the lattice
parameter of a-AlMnSi)
Fig. 6 Another example of a link between the rings on 0,0,0 and ½, ½,
½. These silicon rings are bonded through two manganese atoms and
two silicon atoms (A3 and A7). Here the silicon rings are situated on
the planes z = 0 and z = 0.5
The above described structures of silicon and manganese
atoms can be arranged in a large number of geometrical
configurations. It should be noticed that the geometrical
centers of the silicon rings are 0,0,0 and ½,½,½ making a
body centered system of rings. The rings at the corner of the
unit cell are linked to the center ring by 4 atoms on A3 and
an atom on A6 and an atom on A7 plus several manganese
atoms on M1 and M2. The result of the model is that the
silicon atoms on average occupy 67% of A3, 50% of A4-
and A5 sites and 8.3% of A6 and A7 sites. This model
accounts very well for the observed Seebeck effect, the
neutron diffraction results and other microstructure results
concerning the cubic a-AlMnSi. If so, the ideal number of
atoms in the unit cell is 96 aluminium atoms, 18 silicon
atoms and 24 manganese atoms. A lower number indicate
the presence of vacancies, impurities and other defects. Our
conclusion is that a-AlMnSi is crystal with an average cubic
structure. However, since the positions of silicon atoms and
silicon rings can vary from unit cell to the next, and make
different chains with manganese atoms, the phase does not
have a unique unit cell.
a-AlMnSi crystals have two types of bonds according to
our model. The number of silicon atoms is plotted as a
function of added iron atoms in Fig. 7 [1, 5, 10]. These
results can be interpreted in the following way: When iron is
added to the structure, Fe + Al can substitute for Mn + Si
and keep the total number of electrons constant in the
covalent bonded sub-structure. Since approximately every
second manganese atom is covalent bonded, 8 iron atoms
A Model for a-Al(Mn,Fe)Si Crystals 203

168 aluminium-, 45 iron- and 24 silicon atoms in the unit

cell. Our results indicate that when Mn is added, the number
of silicon increases to keep the number of electrons in the
unit cell constant.
The proposed structure for a-AlMnSi has a cubic struc-
ture with a chain of silicon rings linked by Si- and
Mn-atoms. The silicon rings are almost identical to Si6H6—
rings published by Abersfelder et al. [11]. One difference is
that the latter has silicon rings that are surrounded by
hydrogen atoms instead of manganese atoms. Abersfelder
et al. found that this configuration of silicon atoms is a quite
stable one and is a parallel to aromatic benzene rings.

Acknowledgements The authors would like to thank Dr. Børge

Holme for valuable help with preparing the manuscript.

Fig. 7 Number of silicon atoms in the unit cell of a-Al(Mn,Fe)Si as a

function of the number of iron atoms. (Same units on axes as in Fig. 5)
References

can be added without breaking the chain. When more iron is
added, and the number of silicon in the unit cell becomes
less than 14, it seems that a vacancy on a Mn-site is formed
in order to keep number of electrons in the mentioned sub-
structure constant. When plotting the content of silicon as a
function of iron (Fig. 7), the minimum of silicon in the
structure is 12 atoms. Then there are 2 vacancies on Mn-sites
in the structure. The minimum number of Mn atoms in
a-Al(Mn,Fe)Si is probably about 1 (a1-AlFeSi is formed
when the content of manganese is less than 1%). When the
number of silicon atoms in the structure approaches 12, it
10. M. Cooper, Acta Cryst. 23, 1106 (1967)
becomes difficult to have a continuous chain of covalently
11. K. Abersfelder, A.J.P. White, E.J.F. Berger, H.S. Rzepa, D.
bonded atoms.
The results obtained for the hexagonal phase a1-Al(Fe,
Mn)Si are in excellent agreement with the results by Black
et al. [8, 9]. The phase has according to Corby and Black
1. J.E. Tibballs, R.L. Davis, B.A. Parker, J. Mat. Sci. 24, 2177–2182
(1989)
2. M. Cooper, K. Robinson, Acta Cryst. 20, 614–617 (1966)
3. N. Pratt, G.V. Raynor, J. Inst. Metals 79, 213–232 (1951)
4. H. Thoresen, J. A. Horst, J. E. Tibballs: (SI-report 890222-1, 1991)
5. C. J. Simensen, J. A. Horst, J. E. Tibballs: (SI-report
890222-2,1992)
6. C.J. Simensen, P. Fartum, A. Andersen, Fresenius Z. Anal. Chem.
319, 286–292 (1984)
7. L. F. Mondolfo: Aluminium Alloys. Structure and properties
(Butterworths, London, 1976), pp. 17–18
8. R.N. Corby, P.J. Black, Acta Crystallogr. B 33, 3468–3475 (1977)
9. K. Robinson, Phil. Mag. 44(1953), 1392–1397
Scheschkewitz, A stable derivative of the global minimum on the
Si6H6 potential energy surface. Angew. Chem. 50(34), 7936–7939
(2011)
 Casting Characteristics of High Cerium Content
Aluminum Alloys

David Weiss, Orlando Rios, Zachary Sims, Scott McCall, and Ryan Ott

Abstract
This paper compares the castability of the near eutectic aluminum-cerium alloy system to
the aluminum-silicon and aluminum-copper systems. The alloys are compared based on die
filling capability, feeding characteristics and tendency to hot tear in both sand cast and
permanent mold applications. The castability ranking of the binary Al–Ce systems is as
good as the aluminum-silicon system with some deterioration as additional alloying
elements are added. In alloy systems that use cerium in combination with common
aluminum alloying elements such as silicon, magnesium and/or copper, the casting
characteristics are generally better than the aluminum-copper system. In general,
production systems for melting, de-gassing and other processing of aluminum-silicon or
aluminum-copper alloys can be used without modification for conventional casting of
aluminum-cerium alloys.

Keywords
Aluminum Cerium Casting alloys Intermetallic

Introduction alloy systems can be found in Ref. [1]. Despite their

A new alloy system has been developed that uses cerium as a
primary alloying element at near eutectic compositions.
Additional alloying elements are used, primarily to assist in
the development of room temperature mechanical properties.
The cerium in the alloys forms a primary intermetallic
(Al11Ce3) phase in the Al-rich region of the Al–Ce system,
which provides for excellent retention of mechanical
strength and ductility at high temperatures (200–400 °C).
A detailed description of the microstructure present in the
D. Weiss (&)
Eck Industries, Inc, Manitowoc, USA
e-mail: david.weiss@eckindustries.com
O. Rios
Z. Sims
Oak Ridge National Laboratory, Oak Ridge, USA
S. McCall
Lawrence Livermore National Laboratory, Livermore, USA
R. Ott
The Ames Laboratory, Ames, USA
exceptional mechanical properties, the use of high perfor-
mance alloys in high volume production has been somewhat
restricted by concerns about their casting characteristics. The
casting characteristics of greatest concern are resistance to
hot tearing and adequate fluidity, or mold filling capability.
Good fluidity and hot tear resistance are particularly
important in higher production casting processes, such as
permanent mold or high pressure die casting.
Aluminum alloys that perform well at temperatures of up
to 200 °C typically include copper, nickel or a combination
of the two, along with alloying elements that have other
functions, such as improving heat treat response or grain
refining. Typical chemistries of a number of high perfor-
mance alloys are shown in Table 1. All compositions are
weight percentages of the alloying element.
The addition of copper and magnesium improves strength
and hardness at elevated temperatures, while nickel is also
added to aluminum-copper and aluminum-silicon alloys to
improve hardness and strength at elevated temperature and
to reduce the coefficient of thermal expansion. The solid

© The Minerals, Metals & Materials Society 2017 205

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_28
206 D. Weiss et al.

Table 1 Weight percent Cu Mn Mg Ti Si Ni

chemistry of some high
performance aluminum alloys A206 4.2–5.0 0.20–0.50 0.15–0.35 0.15–0.30 0.05 max 0.05 max
242 3.5–4.5 0.35 max 1.2–1.8 0.25 max 0.7 max 1.7–2.3
336 0.50–1.5 0.35 0.7–1.3 0.25 max 11–13 2.0–3.0

solubility of nickel in aluminum does not exceed 0.04%, so Experimental

it is present as an intermetallic, often in combination with
iron. Additionally, silicon is used to reduce hot shortness and
to improve the fluidity of the alloys [2].
The Aluminum Association comparatively rates alloys on
a scale from 1 to 5 in decreasing order of performance [3].
Those alloys that contain high amounts of copper with little
silicon are generally rated a 3, or average, for fluidity and a
4, or below average, for resistance to hot cracking. Alloy
336 is rated a 1, or excellent, for fluidity because of the high
amounts of silicon in the alloy. The most common cast
alloys such as 356, 357, and 355 all rank excellent for both
fluidity and resistance to hot cracking.
Producing a casting in an alloy that is difficult to cast
raises its cost regardless of alloy cost. As a consequence, the
easier-to-cast alloys are most often specified in spite of the
fact that they are less suitable for some aspects of the pro-
duct, or ferrous alloys are used because of their excellent
high temperature properties, resulting in heavier, less effi-
cient structure.
Initial analysis of the Al–Ce system produced via a powder
metallurgy followed by hot forging showed promising
strengths at temperatures up to 343 °C [4]. A review of the
phase diagram showed a promising eutectic composition at
around 10 wt% cerium that suggested the alloy could be
cast. Figure 1 depicts the Thermo-Calc calculated binary
phase diagram of Al–Ce system. Casting trials were per-
formed using a permanent mold that contained the standard
ASTM B108 test bar geometry. This mold was heated using
electrical cartridge heaters, which maintain the minimum
set-point temperatures to within 10 °C. The casting alloys
were prepared in 25 kg batches using P1520 ingot with the
composition shown in Table 2. Melting was done under
nitrogen cover gas. Commercial cerium metal (Molycorp)
with >99% purity was added to achieve binary compositions
of 6, 8, 10, 12 and 16% cerium. The alloy was not degassed
and was poured into the mold heated to 400 °C using a
casting temperature of 750°.

Fig. 1 Binary aluminum-cerium

phase diagram as calculated using
Thermo-Calc
Casting Characteristics of High Cerium Content Aluminum Alloys
Table 2 Weight chemistry Si
percent of the base alloy used in
this study P1520 0.11
When casting alloys containing 6% silicon or more at the
indicated mold and metal temperatures, the test bar set easily
fills and good test bars are produced. Alloys containing less
silicon require additional superheat to either the mold or the
metal to fill consistently. At compositions up to 10% cerium,
the mold filled completely and the production of sound bars
was consistent with those produced with alloys containing
6% Si. At 12% cerium, mold filling capability declined and
the metal temperature was adjusted upwards by 25 °C to
achieve complete fill. Figure 2 shows that at 16% cerium,
the mold did not fill completely at a mold temperature of
425 °C and a casting temperature of 775 °C. The incomplete
mold filling is due to the rapidly increasing melting tem-
perature above the eutectic point for the alloy. It should be
noted that none of the test bars showed any evidence of hot
tearing.
A second trial was conducted using the same materials
and processing parameters, but utilizing a step plate mold
and a hot tearing mold to estimate feeding characteristics and
Fig. 2 Partial fill test bar mold with Al–16Ce
207
Fe Total others Aluminum
0.17 0.09 Remainder
susceptibility to hot tearing. Images of castings produced are
shown in Figs. 3 and 4. Overall castability of the studied
compositions appears to be in line with currently available
commercial alloys. As a comparison, hot-tear molds and
step-plates were cast from A206. From observations of A206
versus identical casting of Al–Ce alloy, A206 appears to
have larger and more pronounced macroscopic defects pre-
sent than did the castings of Al–Ce alloys.
In general, Al–Ce alloys near the eutectic composition
had good to excellent casting characteristics. However, the
room temperature mechanical properties were not high
enough for many commercial applications nor did the alloys
have a positive response to heat treatment. See Table 3. The
T6 cycle given was 538 °C for 90 min, quenched in H2O,
and then aged at 154 °C for 3 h.
Twenty additional alloys were produced using Al–8Ce as
a base composition with additives of Si, Mg, Cu, Zn, Ni, Ti,
Mn or Fe. Except for Mg, the addition of these alloying
elements in excess of 1% reduced die filling capability even
though many of the alloys had improved mechanical prop-
erties. For ternary Al–Ce–Mg alloys yield strength increased
with increasing magnesium levels without a noticeable
reduction in castability up to the tested level of 10% mag-
nesium. Mechanical properties for three of these alloys is
shown in Table 4.
Pilot Production
Since the Al–Ce–Mg alloys have both good castability and
good mechanical properties, a 320 kg heat of an Al–10Mg–
8Ce alloy was produced to determine suitability of standard
foundry processing parameters on metal quality and
mechanical properties. Aluminum 535 was used as the base
material with a chemistry as shown in Table 5. The ingot
was weighed and melted and an additional 3.15 wt% mag-
nesium was added and stirred into the melt using a rotary
impeller running at 180 rpm and the pre-cerium chemistry
was evaluated. Slightly more than 10% of the added mag-
nesium was lost during the alloying process. Additional
magnesium was added with the cerium for a final magne-
sium composition of 10.09% and a calculated cerium con-
tent of 8.01%. No grain refiners were used. The alloy was
degassed using 5% SF6 in nitrogen for 40 minutes to a
density of 2.49 g/cm3. High magnesium alloys can be dif-
ficult to degas, often requiring multiple degassing cycles to
achieve specified gas levels. Sigworth describes an alloy
208
Fig. 3 X-Ray image of hot tear
castings produced in Al–8Ce
alloy
correction factor that can be utilized to quantify the effects of
alloying elements on hydrogen solubility of the melts and
estimated degassing times [5]. For example, 356 has a cor-
rection factor (C) of 0.67 and 535 has a correction factor of
1.18. The authors are unaware of published correction fac-
tors for 10% magnesium but the hydrogen solubility is very
high (see Fig. 5) compared to other commercial alloys and C
would be expected to be higher. According to Sigworth, the
rate of hydrogen removal is proportional to C2. While there
are no published correction factors for Ce, the success of a
standard degassing time implies that Ce will reduce hydro-
gen solubility and therefore decrease the correction factor
when compared to high magnesium alloys.
A number of commercial castings were poured using
patterns and permanent molds that were gated for 200 and
D. Weiss et al.
300 series alloys and are shown in Figs. 6 and 7. The gating
was not modified to pour the Al–Ce. The casting quality was
acceptable and equivalent to that produced in the production
alloys. Test bars were produced from the production batch of
material and tested to determine if the properties met those
of the smaller batches of experimental material. The tensile
strength from the pilot production was 3.5% higher than the
experimental heats. Examination of test bars revealed lower
oxide levels than previously produced. A total of 20 tensile
bars from the pilot production lot have been tested at room
temperature with properties of 235 ± 2 MPa tensile,
192 ± 4 MPa yield and 1% elongation.
250 kg of alloy was held for 17 h at 750 °C. The mag-
nesium chemistry was checked at 9.78% or a 3.1% loss over
that interval. This is a smaller than expected magnesium loss
Casting Characteristics of High Cerium Content Aluminum Alloys 209

Fig. 4 X-Ray image of step castings produced in Al–8Ce alloy. The right hand image was made from a casting using a copper chill

Table 3 Room temperature Tensile, as cast Yield, as cast % E, as cast Tensile, T6 Yield, T6 % E, T6
mechanical properties (MPa) of
binary Al–Ce alloys Al–16Ce 144 68 2.5 118 78 3.5
Al–12Ce 163 58 13.5 132 48 26.5
Al–10Ce 152 Test Error 8 129 46 24.0
Al–8Ce 148 Test Error 19 122 59 26.6
Al–6Ce 103 30 25 103 33 33.5
210 D. Weiss et al.

Table 4 Room and elevated Tensile Yield %E Tensile 260 °C Yield 260 °C %E 260 °C
temperature mechanical
properties (MPa) of ternary Al–8Ce–4Mg 189 107 3 Not Tested
Al–Ce–Mg alloys Al–8Ce–7Mg 195 151 2 134 121 4
Al–8Ce–10Mg 227 186 1 137 130 4

Table 5 Starting composition of Si Fe Cu Mn Mg Ti

alloy 535 before magnesium and
cerium additions 535 0.098 0.091 0.041 0.159 6.85 0.016

Fig. 5 Comparison solubility

curves of hydrogen in aluminum
alloys

Fig. 6 Automotive cylinder head

castings produced in Al–8Ce–
10Mg alloy
Casting Characteristics of High Cerium Content Aluminum Alloys
Fig. 7 Rotary engine rotor
castings produced in Al–8Ce–
10Mg alloy
given the holding time and the lack of a protective atmo-
sphere. The reasons for this unusual magnesium stability is
being investigated.
Conclusions
A number of test pieces and complicated castings have been
produced in the Al–Ce alloy systems. All of the data and
experience to date indicate that Al–Ce or Al–Ce–Mg have
castability equivalent to 300 series alloys. Other alloy
additions have generally diminished castability but show
promise with additional work. The use of production pro-
cessing equipment resulted in better mechanical properties
than the earlier development heats because of the more
effective removal of oxides. Unexpected results that require
further study include the apparent reduced solubility of
hydrogen in alloys containing cerium and the role of cerium
on the stabilization of magnesium in Al–Mg–Ce alloys.
Acknowledgements This research was sponsored by the Critical
Materials Institute, an energy Innovation Hub funded by the U.S.
211
Department of Energy, Office of Energy Efficiency and Renewable
Energy, Advanced Manufacturing Office and Eck Industries, Inc. Work
at ORNL and LLNL was performed under U.S. Department of Energy
contracts DE-AC05-00OR22725 and DE-AC52-07NA27344. Work at
the Ames Laboratory was supported by the Department of Energy
under Contract No. DE-AC02-07CH11358.
References
1. Z.C. Sims et al., Cerium-Based, Intermetallic-Strengthened Alu-
minum Casting Alloy: High-Volume Co-product Development.
JOM 68(7), (1940–1947)
2. J.R. Davis (ed.), Aluminum and Aluminum Alloys (ASM Interna-
tional (Materials Park, OH, 1993), pp. 40–46
3. The Aluminum Association, Standards for Aluminum Sand and
Permanent Mold Castings, 15th edn. (2008)
4. W.M. Griffith, R.E. Sanders, G.J. Hildeman, in Elevated Temper-
ature Aluminum Alloys for Aerospace Applications. High-strength
powder metallurgy aluminum alloys, proceedings of a symposium
sponsored by the powder metallurgy committee of the metallurgical
society of AIME, 17–18 February 1982
5. G.K. Sigworth, Best Practices in Aluminum Metalcasting (Amer-
ican Foundry Society, Schaumberg, Illinois, 2014), pp. 59–62
 In Situ Observation of Fragmentation
of Primary Crystals by Ultrasonic Cavitation
in Water

Feng Wang, Iakovos Tzanakis, Dmitry Eskin, Jiawei Mi,

and Thomas Connolley

Abstract
Ultrasonic melt processing is a promising technique for microstructural refinement in
castings. Several mechanisms have been proposed for the observed effects, including
cavitation-induced nucleation, activation of substrates and fragmentation. Until now,
however, real-time experimental observations which could clarify any of the above
mechanisms are very limited. For the first time we directly observed the fragmentation of
primary crystals formed in alloys by ultrasonic cavitation. The primary crystals were
extracted from real Al alloys and subjected to ultrasonic processing in water with in situ
high-speed filming. The recordings of fragmentation of the primary crystals allowed us to
observe the different mechanisms of fragmentation, depending on the mechanical properties
and morphology of the primary crystals. The collapse of cavitation bubbles in water is less
violent than that in liquid aluminum due to the lower cavitation threshold, viscosity and
surface tension. Therefore the fragmentation mechanisms for the primary crystals observed
in water should also be present for the same primary crystals in the more violent cavitation
situation in liquid aluminum.

Keywords
Aluminum alloy Ultrasonic processing Primary crystals Fragmentation mechanism
Cavitation In-situ high speed filming

F. Wang (&)
D. Eskin

Brunel Centre for Advanced Solidification Technology (BCAST),
Brunel University London, Uxbridge, UB8 3PH, UK Introduction
e-mail: feng.wang@brunel.ac.uk
D. Eskin Ultrasonic melt processing (USP), i.e., the application of
e-mail: dmitry.eskin@brunel.ac.uk ultrasonic vibrations to the processing of liquid or
I. Tzanakis semi-liquid metals and alloys, is a promising technique for
Faculty of Technology, Design and Environment, Oxford Brookes improving the quality of castings due to significant benefi-
University, Wheatley Campus, Wheatley, OX33 1HX, UK
cial microstructural changes, e.g., the refinement of grains
e-mail: itzanakis@brookes.ac.uk
and primary crystals [1–3]. However, ultrasonic technology
D. Eskin
has not yet found widespread applications in the casting
Tomsk State University, Tomsk, 634050, Russia
industry. This is largely due to the lack of in-depth under-
J. Mi
standing of the mechanisms that control the reported effects
School of Engineering, University of Hull, Hull, East Yorkshire
HU6 7RX, UK induced by USP. The influence of USP on the microstructure
e-mail: j.mi@hull.ac.uk mainly arises from the phenomena that occur during the
T. Connolley propagation of high intensity ultrasound waves in the liquid
Diamond Light Source Ltd, Harwell Science and Innovation melt. Two of the most important phenomena are: (1) acous-
Campus, Didcot, OX11 0DE, UK tic cavitation, i.e. the formation, growth and implosive
e-mail: thomas.connolley@diamond.ac.uk

© The Minerals, Metals & Materials Society 2017 213

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_29
214
collapse of cavitation bubbles and (2) acoustic streaming, i.e.
the formation of a steady flow driven by acoustic wave
propagation and cavitation zone pulsation [1, 2, 4–7].
Based on these phenomena, a wide variety of mecha-
nisms has been proposed to clarify the refinement effect
resulting from USP. In general, these mechanisms can be
broadly classified into two theories: (i) the
cavitation-enhanced nucleation theory and (ii) the
cavitation-induced fragmentation theory [4, 5, 7]. The
cavitation-enhanced nucleation theory and related mecha-
nisms are well covered elsewhere [8, 9]. In this paper we
focus on the cavitation-induced fragmentation [1, 2, 7] that
assumes that the shockwaves or/and microjets generated by
bubble collapse exert forces and produce localized erosion
on solid phase which leads to the fragmentation of such solid
phase. The solid fragments are then distributed throughout
the melt via acoustic streaming and hence multiply the
number of crystals. Although many experiments based on
dedicated design and advanced characterization have made
dramatic progress in understanding of the mechanisms
underlying the USP, they mostly produced indirect evidence.
Direct evidence is of great significance for confirming the
models and suggested mechanisms. One of the most
straightforward ways to obtain such direct evidence is by
direct visualization of the solidification process in the pres-
ence of USP. In fact, a number of attempts [10–18] have been
made to study the effect of ultrasound on solidification process
in situ and in real time. In terms of the experiment techniques
and materials, they can be grouped into two major categories:
(i) optical imaging of transparent analogue alloys and
(ii) synchrotron X-ray imaging of real metallic alloys. Early
in situ observations [10, 11] of the solidification of transparent
analogue alloys under the influence of ultrasound have shown
that the nucleation is indeed facilitated by ultrasonic vibration
and that the fragmentation of growing dendrite is closely
related to the oscillation of quasi-steady bubbles and the
collapse of transient bubbles. Images and videos from a recent
study [12] on the breakage of calcite crystals suspended in a
saturated CaCO3 solution have demonstrated that the collapse
of cavitation bubble clusters causes the fracture and destruc-
tion of suspended calcite crystals. Most recently, synchrotron
X-ray imaging has been extensively applied to the in situ
study of various aspects of solidification of real metals and
alloys, including the in situ investigations of solidification
under the effect of ultrasound [19–21]. In particular, Tan et al.
[15] observed shockwaves and enhanced flows in a Bi-8 wt%
Zn alloy. However, there are few reports on the in situ
observation of direct interaction between cavitation bubbles
with the solid (either dendrites or primary crystals) using the
synchrotron X-ray imaging technique.
In the present work, a feasible and effective experimental
methodology was developed to directly observe the inter-
action between cavitation bubbles and the primary crystals
F. Wang et al.
formed in aluminum alloys in situ and in real time. The
primary crystals with different mechanical properties and
morphology were first extracted from different Al alloys and
then subjected to ultrasonic processing in water with in situ
high-speed imaging. Based on the recorded images, the
mechanisms of cavitation-induced fragmentation are dis-
cussed in the light of the properties and morphology of
primary crystals.
Experimental Methodology
Materials and Sample Preparation
Primary Al3Ti, Si and Al3V were selected for examination as
three representative primary crystals formed in Al alloys. In
order to obtain these primary crystals, samples (20 mm
20 mm  15 mm) were first cut from an Al-0.4 wt% Ti
alloy solidified in a graphite crucible and commercial
Al-20 wt% Si and Al-10 wt% V master alloys (KBM
Master Alloys B.V.) and then were deep-etched by a 10 wt%
NaOH water solution for about 2 h. The detailed casting
conditions and sampling positions for the Al-0.4 wt% Ti
alloy can be found in the Ref. [22]. Following that, the
deep-etched samples were examined in a scanning electron
microscope (SEM, ZEISS SUPRA 35VP) to observe the
primary crystals. Figure 1a shows a typical SEM image of
an Al-0.4 wt% Ti sample after deep etching. As we can see,
the primary Al3Ti crystals clearly stick out from the Al
matrix surface with part of the crystals embedded in the Al
matrix. Similar to primary Al3Ti crystals, primary Si and
Al3V crystals were also observed to protrude from the Al
matrix surface after deep-etching of samples cut from the
Al-20 wt% Si and Al-10 wt% V master alloys respectively.
Experimental Setup and Procedures
After deep etching, the sample was gently rinsed and fixed
by adhesive to the bottom of a small transparent plastic tank
(80 mm  60 mm  40 mm) close to the front wall. The
plastic tank was then filled with distilled water and placed on
a movable stage for ultrasonic processing. The USP was
performed with an ultrasonic processor UP200S (Hielscher,
24 kHz, adjustable input power from 40 to 200 W) con-
nected to a titanium sonotrode with a tip diameter of 1 mm.
The sonotrode tip was positioned around 5 mm above the
top surface of the sample. After the USP, the sample was
again examined by SEM. Figure 1b presents a typical SEM
micrograph of the same position of the same sample in
Fig. 1a. A simple comparison of Figures (a) and (b) clearly
shows the primary Al3Ti crystals were fragmented by
ultrasonic processing as highlighted by dash lines.
In Situ Observation of Fragmentation of Primary Crystals … 215

Fig. 1 Typical SEM micrographs of the primary Al3Ti crystals a deeply-etched samples before USP; b deeply-etched samples after 10-s USP in
water

The interaction between the cavitation bubbles and the
protruding primary crystals was recorded with a high-speed
camera (Phantom V7.3), which has a capability of taking up
to 222, 222 frames per second (fps). The camera was also
equipped with either a 4  (Schneider) or a 10  (Sill)
macro lens. A high-power light source (Karl Storz
Power LED 175) was utilized as front illumination for the
high-speed camera. The choice of front illumination is
because the primary crystals protrude with inclined angles
and they normally reflect light which makes it possible to
have a bright image of the primary crystals by appropriately
adjusting the projection angle of the light source.
A schematic diagram showing the experimental setup is
displayed in Fig. 2.
Results and Discussion
Fragmentation of Primary Al3Ti Crystals
Figure 3 shows a series of images recorded as a primary
Al3Ti crystal was fragmented by an oscillating cavitation
bubble. For brevity, only a few images were selected. The
first frame (t = −55,500 µs) shows a primary Al3Ti crystal

Fig. 2 Scheme of the

experimental setup consisting of:
(1) deep-etched sample, (2)
plastic tank, (3) ultrasonic
processor and sonotrode, (4)
zoom lens, (5) high-speed
camera, and (6) high-power light
216
Fig. 3 Images of an oscillating cavitation bubble causing fragmentation of a primary Al3Ti crystal. The field of view is 1349.12  1349.12 µm2
and the images were recorded at 36,036 fps
of dendritic-plate morphology (dimen-
sions: 450 µm  350 µm  the thickness, which was
unmeasurable) illuminated by properly adjusting the
high-power light source. The outline of the primary Al3Ti
crystal is highlighted by a dash line. The detailed mor-
phology and dimensions of such primary Al3Ti crystals can
be found in the Ref. [22]. A pre-existing crack was also
observed in the primary Al3Ti crystal as indicated by the
arrow in the image. Upon ultrasonic processing, a bubble
was nucleated and started oscillating underneath the primary
Al3Ti crystal. The oscillation of this bubble began to bend
the primary Al3Ti crystal continuously and it took about
2000 frames = 55,500 µs (1332 acoustic cycles) for the
pre-existing crack in the primary Al3Ti crystal to grow as
indicated in the second frame (t = 0 µs), where a part of the
bubble expanding out of the primary Al3Ti crystal is also
highlighted. After that, the crack began to propagate quickly
and it took only another 5 frames = 138.75 µs for the crack
to grow to a length which is sufficient to allow the
F. Wang et al.
fragmentation of the primary Al3Ti crystal as shown in the
third frame (t = 138.75 µs). After the fragmentation, the
oscillating bubble continued to push the crystal fragment,
which leads to the tilling of the crystal fragment as implied
by the changing contrast (from brighter in the 5th frame to
darker in the 8th frame) of the crystal image because its
angle relative to the illumination light was changing. In the
meantime, as the bubble was no longer constrained by the
primary Al3Ti, it started moving, which, in combination with
the acoustic streaming, pushed the crystal fragment away. As
a consequence, the crystal fragment was not only rotating
but also flowing in the water as illustrated from 9th to 12th
frames. The remaining part of the primary Al3Ti crystal was
also highlighted by the dash line 9th to 12th frames. in the It
is noted that the movement speed of the crystal fragment is
slow in this case as it took 524 frames = 14,541 µs for the
crystal fragment to flow to the position shown in the last
frame. The rough velocity estimated without considering the
movement in the direction perpendicular to the image plane
In Situ Observation of Fragmentation of Primary Crystals …
is only 0.05 m/s. From the above series of images, we can
suggest that the fragmentation mechanism of this primary
Al3Ti crystal belongs to the fatigue fracture due to propa-
gation of a pre-existing crack in the primary Al3Ti crystal to
a critical length as a result of the cyclic effect of an oscil-
lating cavitation bubble. This is in contrast to our common
knowledge [23, 24] that primary Al3Ti is brittle at room
temperature and should fail in a more brittle way.
In addition to the fragmentation by bubble oscillation via
the mechanism of fatigue fracture, another way of frag-
mentation of primary Al3Ti crystal by a flowing bubble
cloud was also recorded. This is a sudden brittle fracture (not
shown here) similar to that described below for Si.
Fragmentation of a Primary Si Crystal
Figure 4 shows a series of images illustrating a flowing
bubble cloud chipping a bit off a primary Si crystal. Fig-
ure 4a presents a well-faceted block of primary Si crystal
with one bright facet and on dark facet. This morphology of
primary Si after deep etching away the Al matrix agrees with
the common morphology of primary Si in hypereutectic Al–
Si alloys [25]. A bubble cloud came down from the sono-
trode to the primary Si crystal as seen at the top of Fig. 4b.
With the bubble cloud passing the primary Si crystal, it
blocked the view of camera as shown in Figs. 4c–e. After
the view was cleared, a bit of the primary Si crystal disap-
peared from the faceted block with the trace of the bit being
Fig. 4 Images of a primary Si crystal being chipped by a flowing bubble cloud. The field of view is 552.96  552.96 µm2 and the images were
recorded at 36,036 fps
217
indicted by the arrow in Fig. 4f. However, in the following
frame, i.e. Figure 4g, the bit completely disappeared leaving
a clear cleavage surface as further shown in Fig. 4h. With
taking into account the brittleness of Si at room temperature,
we suggest the fragmentation by brittle fracture due to the
collapse of bubble cloud.
Fragmentation of a Primary Al3V Crystal
Figure 5 shows a sequence of images with a typical frag-
mentation of a secondary branch of a primary Al3V dendrite.
A well-grown dendrite of the primary Al3V phase is clearly
seen with one of the branching secondary arms protruded
towards the camera as indicated by an arrow in Fig. 5a.
Moreover, a bubble cloud flowing downwards is also
detected with its outline highlighted at the top of Fig. 5a. As
the bubble cloud approached the primary Al3V dendrite, the
branch indicated by the arrow was broken off the primary
Al3V dendrite as shown in Fig. 5b. The blurriness of the
fast-moving branch as pointed by the arrow in Figs. 5c–e is
because of the high speed of the branch and the relatively
large exposure time (=25.75 µs). In addition, the detached
branch also travelled along the direction perpendicular to the
image plane and hence went out of focus. The average
velocity of the detached branch over the frames from (a) to
(e) was approximately calculated to be 2 m/s which is
larger than the normal acoustic streaming flow velocity
(maximum 1 m/s) [1]. This indicates that the detachment of
218
Fig. 5 Images of a secondary branch of a dendritic primary Al3Vcrystal being fragmented by a bubble cloud. The field of view is
552.96  552.96 µm2 and the images were recorded at 36,036 fps
the secondary branch off the primary Al3V dendrite was
probably due to the collapse of the bubble cloud which
resulted in such a high velocity of the detached branch. It was
also noted that the primary Al3V trunk slightly bent and then
restored its original position, under the effect of bubble cloud.
This is also indicated by the dash line arrow in the images.
Conclusions
High-speed imaging was used for an in situ study of the
dynamic interaction between cavitation bubbles and primary
crystals formed in Al alloys. A simple but efficient method
was developed based on deep etching of different Al alloys
containing the primary crystals and ultrasonic processing of
these deep-etched samples in water. Three typical primary
crystals, i.e. Al3Ti, Si and Al3V, with different morphology
were investigated. By analyzing the images extracted from
the videos, different fragmentation mechanisms were
F. Wang et al.
revealed. In general, there are two major mechanisms by
which the primary crystals are fragmented by the ultrasonic
cavitation bubbles. The first fragmentation mechanism is a
slow process via fatigue failure as result of bubble oscilla-
tion. The oscillating cavitation bubbles bend the primary
crystals in a high-frequency cycle which causes the cracks in
the primary crystals to develop to a critical length and hence
results in the fragmentation. The other mechanism is a
sudden process due to the collapse of bubble cloud. The
pressure produced upon the collapse of bubble cloud vio-
lently fragments the primary crystals. The exact mechanism
and its quantification for a specific primary crystal depend on
its mechanical properties and morphology and needs to be
investigated further.
Acknowledgements The authors acknowledge the financial support
from UK Engineering and Physical Science Research Council (EPSRC)
for the Ultra-Cast project (grant EP/L019884/1, EP/L019825/1,
EP/L019965/1). The authors are also grateful to Diamond Light Source
Ltd for the loan of high speed camera.
In Situ Observation of Fragmentation of Primary Crystals …
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 The Enhancement of Mechanical Properties
of A356 Alloy Solidified at Lower Cooling Rate
via Effectively Grain Refinement

Yijie Zhang, Shouxun Ji, and Zhongyun Fan

Abstract
For A356 alloy, solidification with relative lower cooling rate will result in coarse grain size
and lower mechanical properties. In this case, Al5Ti1B mater alloy was not the effective
one to refine the A356 alloy. In present study, the effective grain refiner for A356 alloy was
developed. Experimental results showed that the equiaxed grains were obtained with
modified A356 alloy, rather than the dendritic grains of A356 refined by Al5Ti1B master
alloy. Compared to the A356 alloy refined by 0.2 wt%Al5Ti1B, the yield strength, ultimate
tensile strength and elongation of modified A356 alloy were increased by 4 MPa,
30.6 MPa, and 4.5% respectively. The value of yield strength, ultimate tensile strength and
elongation of modified A356 alloy were 182.3 MPa, 278.3 MPa and 8.2%. The significant
improvement of mechanical properties was ascribed to the effective nucleation of a-Al and
the morphology evolution of eutectic Si.

Keywords
Mechanical properties Grain refinement A356 alloy

Introduction
A356 aluminium alloy containing about 7 wt% Si (all the
percent was weight percentage other specified), 0.3% Mg
was widely used for automobile industry, such as produc-
tions of car wheel, engine block, chassis and so on, due to its
excellent castability, mechanical and physical properties. To
reduce the casting defects, improve the tensile strength and
elongation and ensure the quality of castings, 0.2% addition
of Al5Ti1B master alloy into A356 melt was necessary
before pouring [1–13]. Some research reported that the
content of Si higher than 3% will poisoning the grain
refinement of Al5Ti1B. The different kind of refiner of
Al3Ti3B and Al2.5Ti2.5B [10] was studied to refiner the
A356 alloy. However, the Al5Ti1B still was the dominate
one and has been reported and testified that it was the best
Y. Zhang (&)
S. Ji
Z. Fan
Brunel Centre for Advanced Solidification Technology (BCAST),
Institute of Materials, Brunel University London, Uxbridge,
Middlesex, UB8 3PH, UK
e-mail: yijiezhang6@gmail.com
grain refiner for Al alloy since 1960s. Many works had been
done to reveal the refinement mechanisms and to improve
the refinement efficiency. The common ideas about the
refinement were that the efficiency of grain refinement was
determined by the potency of nuclei and growth restriction
factors. To assess the grain refinement results of refiner, the
testing methods of TP-1 [14] was always employed
according to the different purpose. The cooling rate of these
methods was about 3.5 °C/s or high than this. However, in
casting process of real components, different thickness of
castings will cause different cooling rate. Sometimes, the
cooling rate was lower than 2.5 °C/s and in this case the
Al5Ti1B grain refiner was not act as efficiency any
more. Thus the performance of grain refinement was
depends on the cooling conditions, and will result in the
non-homogeneous of mechanical properties. Take the car
wheel as an example, the properties on casting with 5 mm
thickness can achieve 200 MPa, 8% for yield strength and
elongation respectively. But the properties on casting with
25 mm thickness were only 160 MPa, 2% for yield strength
and elongation. The difference between two kinds of

© The Minerals, Metals & Materials Society 2017 221

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_30
222
thickness of components during solidification was the
cooling rate. Components with thicker wall means that the
lower cooling rate and longer solidification time. Therefore,
there is a high demand to develop a grain refiner for
lower cooling rate application and this kind of refiner should
have a good refinement performance on normal cooling
conditions.
In this investigation, the aim was to study the grain
refinement at lower cooling rate and to develop the novel
grain refiner basing on the fundamental understanding.
Experimental
The composition of new grain refiner contained 2.2%Ti, 1%
B and 1%Mg (refined as Al2.2Ti1B-S), which was prepared
by Mixed Salt Method via reaction among molten Al,
K2TiF6 and KBF4 basing on the weight ration of Ti and B to
form TiB2 particles. The synthesis process included two
step: the first one was to synthesis TiB2 particles via reaction
at about 850 °C for 30 min. Then remove the slag and add
Mg into melt and to form MgAl2O4 phases via keeping melt
at 850 °C for about 1 h.
To check the grain refinement performance of refiner, the
special mould was employed in present study. The dimen-
sion of the mould was seen in Fig. 1. The A356 alloy con-
tained 6.9%Si, 0.3%Mg and 0.12%Fe was used to assess the
grain refinement which was supplied by Norton Aluminium.
A356 alloy was melted in graphite-grey crucible by resis-
tance furnace. After 1 h of homogenisation, the melt was
subjected to degassing, during which argon was introduced
Fig. 2 The macro grain size of A356 a without grain refinement, b refined by 0.2%Al5Ti1B, c refined by 0.2%Al2.2Ti1B-S
Y. Zhang et al.
Fig. 1 The mould used for solidification assessment at relative lower
cooling rate
into the melt by a commercial rotatory degasser at 500 rpm
for 3 min and the top surface of the melt was covered by
commercial granular flux. The melt was subsequently
homogenised in the furnace at about 725 °C for 30 min.
After skimming, the 0.2% addition of refiner was conducted
and slow stirred needed to keep grain refiner disperse uni-
formity in the melt for about 20 s after addition was com-
pleted melting. The melt was held for 5 min and then was
poured into the special mould preheated to 450 °C for grain
size assessment and poured into ASTM standard mould
(ASTM B557-15) to obtain tensile samples. As a compar-
ison, the addition of 0.2%Al5Ti1B into A356 melt was also
conducted with the same procedure. The Al5Ti1B master
alloy was supplied by LSM.
All testing samples were subjected to T6 heat treatment
(solution at 540 °C for 8 h, quenched into cold water and
ageing at 170 °C for 8 h). The metallographic samples were
prepared by a standard technique. Anodization of samples
The Enhancement of Mechanical Properties of A356 Alloy …
into 4% HBF4 water solution for 1 min at 20 V was
employed to observe the grain size of materials via Zeiss
optical microscopy. Field-emission scanning electron
microscopy (FE-SEM, SUPRA 35VP, Carl-Zeiss Company)
equipped with an energy dispersive X-ray spectroscopy
(EDS) was also used for microstructure analysis.
Results and Discussion
Figures 2 and 3 showed the macro grain size and micro grain
size of A356 alloy without and with refinement respectively.
It can be seen that both grain refiner can refine A356 alloy in
present study. The Al2.2Ti1B-S refiner has better refinement
performance than that of Al5Ti1B refiner. The original grain
size of A356 without refinement was about 1100 lm. With
refinement of Al5Ti1B, the grain size of A356 was
Fig. 3 The micro grain size of A356 alloy a without grain refinement, b refined by 0.2%Al5Ti1B, c refined by 0.2%Al2.2Ti1B-S
223
decreased to about 600 lm. However, with refinement of
Al2.2Ti1B-S, the grain size of A356 was further decreased
to about 400 lm. This means that the Al2.2Ti1B-S was
more efficiency on A356 refinement than the commercial
Al5Ti1B master alloy.
Figure 4 indicated the Si morphology of A356 alloy
without and with grain refinement at as-cast state. From
Fig. 4, it can be seen that without refinement, the mor-
phology of Si was coarse and laminated. The length of
laminate Si was about 80 lm. After refinement with
Al5Ti1B, the morphology of Si was become short lightly, its
average length was about 50 lm. With refined by
Al2.2Ti1B-S, the morphology of Si was very fine and its
size was about 10 lm. After T6 heat treatment, the Si was
rounded to reduce the concentration of stress and promotion
of microcracking, therefore to benefit the elongation and
tensile strength. Compassion of Si morphology at T6 state
224
Fig. 4 The microstructure of A356 at as-cast state a without grain refinement, b refined by 0.2%Al5Ti1B, c refined by 0.2%Al2.2Ti1B-S
with and without refinement, it can be seen from Fig. 5 that
A356 with Al2.2Ti1B-S refiner had the fine and smaller Si
of about 5 lm in diameter. However, the shape of Si of
A356 without refinement was rod-like and its size was about
20 lm in length. This indicates that the A356 with
Al2.2Ti1B-S refinement had better mechanical properties.
The tensile properties of A356 alloy with and without
refinement were shown in Table 1. It can be seen from
Table 1 that the Al5Ti1B had limited refinement effect on the
improvement of tensile strength and elongation. But the
Al2.2Ti1B-S refiner can enhance the ultimate tensile strength
(UTS) and elongation significantly. Compared to A356
without refinement, the UTS was increased by 30.6 MPa and
elongation was increased by 4.5% respectively. This was
another convinced proof that the A2.2Ti1B-S can refine
A356 efficiently at lower cooling rate than Al5Ti1B refiner.
Y. Zhang et al.
The improvement of tensile properties of A356 alloy after
refinement was ascribed to the fine grain size and the
modification of Si morphology. For Al5Ti1B refiner, the
potency nuclei was TiB2 particles with the mono-atom layer
of TiAl3 [15]. In the presence of Si higher than 3%, the Ti, Si
and Al prefer to form TiSiAl intermetallic and therefore
reduce the potency of TiB2 as the efficient nuclei of a-Al.
This was the main reason that the Al5Ti1B can not refine
Al–Si alloy. In present study, to make TiB2 become potency
nuclei of primary a-Al, the MgAl2O4 was synthesized on the
TiB2 surface as replacement of TiAl3 layer. The MgAl2O4
was testified that it always existed in Al alloy and can refine
a-Al very well [16]. As for the refinement mechanisms of
new developed refiner, more research work should be carried
on to reveal the potency and efficiency of nuclei and growth
restriction factors.
The Enhancement of Mechanical Properties of A356 Alloy … 225

Fig. 5 The microstructure of A356 at T6 state a without grain refinement, b refined by 0.2%Al5Ti1B, c refined by 0.2%Al2.2Ti1B-S

Table 1 The tensile properties Materials YS (MPa) UTS (MPa) Elongation (%)
of A356 alloy at T6 state with and
without refinement A356 178.3 247.7 3.7
A356 refined by Al5Ti1B 180.2 256.5 4.6
A356 refined by Al2.2Ti1B-S 182.3 278.3 8.2

Conclusions References

The efficiency grain refiner for A356 alloy had been developed
successfully. The experiment results indicated that the ultimate
tensile strength and elongation can increased by 30.6 MPa and
4.5% respectively. The significant improvement of mechani-
cal properties was ascribed to the effective nucleation of a-Al
and the morphology evolution of eutectic Si.
1. K.G. Basavakumar, P.G. Mukunda, M. Chakraborty, Influence of
grain refinement and modification on microstructure and mechan-
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Charact. 59, 283–289 (2008)
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Al–Si alloy (A356) by melt thermal treatment. J. Mater. Process.
Technol. 141, 29–34 (2003)
226
3. C. Limmaneevichitr, W. Eidhed, Novel technique for grain
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 Secondary Aluminum Alloys Processed
by Semisolid Process for Automotive
Application

F. D’Errico and D. Mattavelli

Abstract
OEMs manufacturers of aluminum based safety components for automotive sector are used
to require low percentage of Fe as contaminant, since it can be responsible of very high
brittle microstructure due to formation of acicular Fe-compounds. Lowest Fe percentage is
achieved by alloying primary aluminum, instead of secondary aluminum obtained on
recycling marketplace. On the other hand, any aluminum alloys fabricated starting from
primary aluminum achieves very high environmental impact, due to very high CO2
equivalent emitted during the early extractive stage. In order to reduce total global warming
potential of finished components, recycling alloys would be preferred, but metallurgy
solutions are necessary to control Fe-contaminants. According to recent advancements,
Fe-compounds in recycled aluminum could be controlled throughout semisolid processes,
where the stirring phase of a semisolid slurry would produce fragmentation Fe-compounds.
In this work, investigation about key process parameters has been performed to correlate
microstructural features to mechanical properties in presence of Fe-compound. Among
various process parameters, stirring time and solid fraction are most important key
parameters to control to obtain fine globular microstructure. Tensile tests have been
performed showing promising results (yield strength about 300 MPa and ultimate tensile
stress about 330 MPa). Stirring stage in semisolid process allows reduction of average size
of Fe-compounds, thus producing an increase in percentage elongation and toughness,
namely the main requirements in automotive sector for widespread use of low-cost and
low-environmental impact aluminum alloys.

Keywords
Semisolid Aluminum alloys Recycling Rheocasting Automotive

Introduction push substantial mass reduction onboard. Large and complex

shape components are manufactured by a variety of pro-
Weight reduction in transportation industry is nowadays duction processes, mostly used are high pressure die casting
crucial for reduction of greenhouse gases emitted over entire and gravity casting [4–6]. When casting processes are used
life cycle of vehicles [1–3]. Aluminum alloys have been to manufacture safety components for automotive sector,
employing for recent years in automotive and rail industry to Al-based alloys are fabricated by alloying primary alu-
minum, namely starting from aluminum ingots which
F. D’Errico
directly come from bauxite. This choice is due to the fact
Politecnico di Milano, Milano, Italy
e-mail: fabrizio.derrico@polimi.it alloying recycled aluminum that comes from recycling
process could introduce in metal some impurities such as
D. Mattavelli (&)
InnSight, Milano, Italy iron and manganese left by recycling process. Such impu-
e-mail: d.mattavelli@innsight.eu rities are so detrimental for the toughness of final component

© The Minerals, Metals & Materials Society 2017 227

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_31
228
as they can form hazardous needles like brittle phases highly
distributed in metal matrix [7–12]. On the other hand, pri-
mary aluminum which is directly extracted from mine-ores
can be obtained throughout Bayer and Hall-Herault process,
that is an energy consuming process with high environ-
mental impact [13–15]. If on one hand, weight saving by
putting onboard lighter aluminum components instead
heavier ones can pursue strategy of saving fuel consumption
and pollutant emissions per mile for any internal combustion
engine vehicle, such benefit could not be fully achieved if a
negative net balance for the total CO2 emitted is accounted
by comparing the total emissions produced over manufac-
turing phases with CO2 emission cut for light solution. Most
specifically, using primary aluminum alloys in place of
secondary aluminum alloys allows 95% net saving energy
primary power resource, i.e. electricity, and 80% reduction
of total greenhouse gases emissions, avoiding any type of
chemicals [14, 16].
The brittle and needle-like Fe-based phases that can form
in secondary aluminum alloys cause embrittlement of final
components, not adequate for any type of safety components
in automotive industry [17–20].
In this work, semisolid process has been studied and
experimentally adopted to fabricate metallographic speci-
mens under different conditions. Main scope of this work has
been studying how most important effects on microstructural
parameters can be correlated to some measureable and
easy-to-control process parameters like stirring time, solid
fraction of the semisolid slurry and Fe content. In parallel, a
further experimentation has been conducted by use of a
pre-industrial semisolid pilot plant. In the latter case, sam-
ples have been fabricated by injecting semisolid slurry at
high pressure into mold-die. Results of this experimentation
has focused on exploring weather secondary aluminum
alloys processed via-semisolid process could be comparable
in terms of strength and ductility with primary aluminum
alloys produced by traditional casting process.
Semisolid Metal Processes
Semisolid metal processes are casting processes that exploit
rheological properties of metals within their interval of
solidification [21–26]. Fluid dynamics defines two types of
fluids: Newtonian and non-Newtonian fluids. The first ones
are such fluids which obey to the Newton’s law:
s ¼ l_c
where s is the shear stress in the fluid, l is the viscosity and c_
is the shear rate applied. Therefore, for a Newtonian fluid, if
temperature and pressure are constant, the same occurs for
its viscosity, namely ratio between shear stress and shear
F. D’Errico and D. Mattavelli
rate. Non-Newtonian fluids are characterized by a type of
constitutive equation as follows:
s ¼ f ðc_ Þ
Such fluids can be divided in two main categories
depending on their rheological behavior, if it is or not
directly correlated to time. For such a type of fluids, the
apparent viscosity parameter can be defined, and it corre-
sponds to the slope of the curve shear stress versus shear
rate, for each shear rate applied. By this way, it is possible to
classify the time-dependent fluids into two sub-categories:
• Thixotropic fluids: those fluids whose apparent viscosity
decreases meanwhile shear stress is applied;
• Rheopectic fluids: those fluids whose apparent viscosity
increases while shear stress is applied.
Such fluids whose behavior is non-time dependent can be
classified in three sub-categories:
• Pseudoplastic fluids: fluids whose apparent viscosity
decreases as stress applied increases;
• Dilatant fluids: fluid whose apparent viscosity increases
as stress applied increases;
• Bingham plastics: fluids whose viscosity is constant and
to non-zero values of applied shear rates correspond
non-zero value for shear stress.
Generally speaking, a semisolid metal slurry is a metal
which is maintained during cooling stage within interval of
solidification temperature and shows thixotropic and pseu-
doplastic behavior [22–25]. This means that, by applying a
shear stress to slurry, the more is the duration of shear stress,
the less will be the apparent viscosity of the semisolid slurry.
Moreover, the more is the intensity of the shear rate, the less
will be the apparent viscosity.
These physic characteristic had lead to some industrial
advantages, compared with traditional casting process
[27–29], as the absence of porosity in final cast part. This is
due thanks to the low viscosity and laminar flowing of the
thixotropic metal that can be injected into mold-die by
pressure avoiding any turbulence, thus avoiding air entrap-
ment. This benefit allows to design and realize in practice
complex geometry with very thin sections. Furthermore, less
shrinkage of semisolid state metal allows to reduce
exceeding material, instead of traditional casting processes
which requires exceeding material to make shrinkage defects
localize outside the net part. Due to insignificant porosity
level in semisolid parts, such a material can be heat treatable
without any risk of surface blistering. Less temperature
employed during injection phase means low risks of thermal
shocks and also energy-saving over entire process.
Secondary Aluminum Alloys Processed by Semisolid Process …
For recent two decades, three industrial semisolid pro-
cesses have been developing, someone at industrial stages,
some others at pre-industrial stage:
• Thixoforming: is a process that concerns to fabricate
semifinished billet with globular microstructure. These
billets can be subsequently heated up to temperatures
corresponding the desired solid fraction, thus the semi-
solid mass can be injected into a die. The high cost of
semifinished material (i.e. the globular structure
semifinished billet) is too high for main industry cost
targets, so this process has been slowly abandoned;
• Thixomolding: is a process adopted just for magnesium
alloys. Very similar to plastic injection molding, this
process uses a rotating screw inside a barrel which is
heated up to temperature within interval of solidification.
This can create proper conditions (i.e. shear rate and
temperature) for obtaining semisolid slurry. Most inno-
vative feature, the process itself starts from fully solid
state feedstock (as chips or granular material) introduced
in the barrel. The semisolid low-viscosity slurry, as it has
been prepared in the barrel, is finally injected into a mold.
• Rheocasting: a most desirable process for industries due
to its simplicity, it consists in melting the whole mass of
metal in a separated furnace, spilling out part of the liquid
in a crucible were semisolid slurry is prepared by pro-
gressively cooling down the mass while a vigorous stir-
ring action is applied. As the right solid fraction is
achieved, the slurry is poured in a shot slave and finally
injected into a mold.
In this work, a rheocasting process with mechanical
stirring has been used in both laboratory and pre-industrial
scale experimentation.
Intermetallic Phases in Aluminum Secondary
Alloys
As previously referred, aluminum alloys produced by pri-
mary aluminum is recognized by any Life Cycle Assessment
as very pollutant material, so that carbon footprint of fabri-
cation stage cannot be positively balanced with fuel-saving
[1–5]. Thus the main paradigm recently introduced in
transport sector powered by fossil fuels is that a trade-off
shall be identified, since being aluminum alloys part of
viable strategy for weight saving in transportation sector,
most beneficial effects could be betrayed due to high envi-
ronmental impact of fabrication phase [30]. The easiest
solution, in this sense, could be substituting use of primary
aluminum with recycled aluminum: on the other hand, alu-
minum from recycling has too much high percentage of Fe
impurities, that would be responsible for intermetallic phases
229
that compromise the mechanical properties of the component
[18–20]. The main problems is due to Fe-compounds shape,
as they disperse into matrix in form of small acicular pla-
telets that cause high stress rising at the tip. This leads to
brittle behavior with severe ductility and toughness decrease
which is not suitable for structural safety components.
The alloy phases which are of interest in the present work
are actually placed at the corner of the ternary phase diagram
of Al–Si–Fe system alloy. Two are the most important
phases, namely:
• s5: called also a-AlFeSi, has a composition Fe2Al7.4Si.
Its structure is hexagonal but recent studies have reported
a cubic structure for it. This can be due at the presence of
trace of copper or manganese which stabilize the cubic
structure;
• s6: also designated as b-AlFeSi, has a composition
FeAl4.5Si. Its structure is not yet clear because different
type of analysis show different results.
In this work two different alloys have been studied in
order to the investigate microstructural difference due to
different Fe percentage.
Experimental Procedures
Two experimental campaigns have been performed. The first
was carried out by using a laboratory-scale plant in which
metallographic samples was produced without using any
injection system; the second one has been performed by
using a pre-industrial pilot plant capable to produce tensile
specimens.
Procedures Using the Laboratory-Scale Plant
The laboratory-scale plant used to produce metallographic
samples by semisolid way is made of a 6 kg aluminum
capacity, 3 kW power crucible furnace, capable to reach
more than 1000 °C. A rotating helix driven by an 0.75 kW
electric motor has been used for the stirring unit.
The parameters under investigation was: (a) the Fe con-
tent of the aluminum alloys, (b) the stirring time and (c) the
solid fraction calculated by the temperature set during
semisolid slurry formation, and before spilling out.
The experimental conditions employed in this work are
described below:
• Fe-content: the values chosen was of 0.4% for the alloy
named “A” and 0.8% for the alloy named “B”;
• stirring time: this parameter was varied on three levels
stirring the alloy for 10, 20 and 30 s;
230
• solid fraction: this parameter was varied on three level
too. The levels chosen for this parameter was 0.15, 0.30
and 0.45 corresponding respectively to the temperatures
of 610, 600 and 585 °C.
The experimental procedure consists in raise selected
alloy at melting temperature, turn off the furnace to control
liquid to cool down to semisolid temperature that has been
set. Achieved the temperature set by experiment plan, the
rotating helix starts stirring semisolid mass in order to form
the globular semisolid slurry. The samples are therefore
spilled out at the above mentioned temperatures and solidi-
fied outside the crucible in a small open mold.
Samples produced at different temperature have been
extracted without re-melting entire mass. Once finished the
first replicate, the mass was melted again and the missing
material was added in the crucible. As re-melted all the
material, the procedure was conducted for others two times
with different stirring time.
As all the experimental condition was carried out three
times for the alloy with lower content of iron, the crucible
and the helix was cleaned and then the crucible was filled
with the alloy with higher content of iron. All the procedure
was finally replicated to reach all the experimental condition
three times.
The sample thus obtained was polished and prepared for
metallographic microscope investigation. For each sample,
three micrographies have been taken for scanning electron
Fig. 1 SEM image of secondary
aluminum alloy microstructure
F. D’Errico and D. Mattavelli
microscope analysis in terms of local chemical composition
and length of the intermetallic platelets.
Procedures Using the Pre-industrial Pilot Plant
A pilot plant was used to produce tensile specimens
according to the ASTM-E8 standards in order to analyze
mechanical properties of the material in different conditions.
The pilot plant is constituted by a vertical hydraulic press
capable to produce 1500 kN injection force and 8000 kN
clamping force. On the basement, a hydraulic unit controls
the closing of the mold-die and the injection of the slurry by
hydraulic piston. Two rotating heating stations are located for
preparation and injection of the semisolid slurry. Specifically,
while in one single station semisolid slurry is prepared by
mechanical stirring, in the other separate station the semisolid
slurry is injected by the piston into the mold die.
Tensile specimens has been produced in four different
experimental conditions. The different experimental condi-
tion was obtained using the two different alloys called “alloy
A” and “alloy B”. After the production of the specimens
with the two different alloys, another factor is introduced: a
heat treatment of solubilization was carried out to investigate
the effect of T6 heat treatment on the mechanical properties
of these alloys produced by semisolid way. The tensile tests
on this specimens was carried out and data about ultimate
tension strength, yield strength, Young’s modulus and
Secondary Aluminum Alloys Processed by Semisolid Process … 231

Fig. 2 Main effect plot of UTS

percent elongation at break was gathered. Finally, the frac- mechanical properties. Analysis of variance has been con-
ture surfaces was analyzed at scanning electron microscope ducted on all the parameters. A phase identification has been
to investigate the morphology of fracture. performed by using backscattered electron method.

Results and Discussion Phase Identification

Main technological parameters which have direct influence Phases in the alloy has been identified on both samples
on the alloys microstructure have been investigated, as well produced by use of laboratory scale plant and those pro-
as the effect of alloy composition and heat treatment on the duced by the pre-industrial pilot plant. The phase indicated

Fig. 3 Main effect plot of

percent elongation at fracture
232
Fig. 4 SEM image of fracture
surface of tensile specimen
in Fig. 1 as (1) is a-aluminum phase. The phase indicated
with (2) is an eutectic aluminum-silicon phase that has been
formed during the mass solidification, while the brightest
phases indicated with (3) are resulted to be b-AlFeSi phase.
Length of Intermetallic Phase
The length of the platelets formed by the intermetallic phase
b-AlFeSi has been measured for all the experimental con-
ditions of the experimentation carried out on the laboratory
scale plant. The platelets has been measured taking a picture
in three different field for each metallographic sample. The
pictures thus took has been analyzed by mean of the soft-
ware Image Pro Plus. All the platelet length was collected
and the five larger for each sample was averaged to obtain an
indication of the maximum length of the platelet.
An ANOVA has been conducted to distingue the effect of
the factors on the thus defined parameter.
The results indicate that the content of iron and the solid
fraction affect the maximum length, while the stirring time has
no influence. In particular, the length of the platelets increase
as both the iron content and the solid fraction increases. These
lengths range from a minimum of 26.4 ± 4.5 µm in the
condition of low content of iron and low solid fraction to a
maximum of 163.4 ± 35.6 µm in the condition of high
content of iron and high solid fraction. The high standard
deviation in this condition could be due to the high temper-
ature variability in the crucible at high solid fraction.
F. D’Errico and D. Mattavelli
Mechanical Properties of Tensile Specimens
The mechanical properties of the tensile specimens produced
by the pre-industrial pilot plant has been pointed out by
tensile tests conducted at room temperature. UTS and the
percentage elongation at break have been gathered for all the
experimental conditions.
As it emerges from data result, the ultimate tensile strength
is not significantly influenced by Fe content (Fig. 2). The
heat treatment instead affects positively this parameter with a
UTS of 214 ± 77 MPa in the treated condition versus a UTS
of 134 ± 44 MPa in the non-treated condition. In some
specimens has been found a highly level of defects like
porosities due to mistakes in the process set up such as gas
entrapment. For this reason, the standard deviation is so high.
The percent elongation at fracture shows a very brittle
material, due to the high level of porosity found (Fig. 3).
Anyway, this parameter is negative affected from both the
iron content and the heat treatment. As it emerges, the more is
the iron content, the longer are the intermetallic platelets. The
longer are the platelets, the higher is the notch sensitivity that
induces stress rising at the tip of the platelet. This is the main
cause of brittleness for the aluminum alloy studied, as well
for other type of aluminum with high Fe contaminant per-
centage. On the other hand, conventional heat treatment
performed to increase mechanical properties, negatively
affects the ductility of the material, too, because nanometric
precipitates form during treatment that decreases the so small
resources of plasticity of material.
Secondary Aluminum Alloys Processed by Semisolid Process …
The morphology of the fracture surface of the tensile
specimens has been analyzed at the scanning electron
microscope (Fig. 4). The analysis revealed the presence of
many intermetallic platelets on the fracture surface. The
shape of these platelets was flat and chopped. The edges
were very sharp and this could cause the decrease in
mechanical properties of the material.
Conclusions
Thanks to backscattered electron analysis of the phases
distributed in microstructure of semisolid aluminum alloy
tested, it has been pointed out such a phase disperses into
matrix as flat b-AlFeSi phase platelets. The length of these
platelets varies depending on the Fe content of the alloy and
the solid fraction. As both iron content and solid fraction
increase, the length of the intermetallic platelets increases
too.
The results on static mechanical properties shown that
strength (i.e. UTS, YS) has been not affected by the Fe
content, specifically for Fe range considered in this work.
The heat treatment, instead, shown slight improvements in
UTS, but, on the other hand, it is worth noticing it produces
negative effect on the ductility. This parameter was nega-
tively affected also by the iron content in the alloy.
Accordingly to literature, experiment results shown that
aluminum secondary alloy are brittle material. The experi-
mental procedure and semisolid-process shall be improved
to finely study two further parameters, cooling speed of the
liquid-to semisolid change status and speed agitation rate of
semisolid slurry, as they are parameters authors consider
fundamental for controlling Fe-enriched compound dimen-
sion in industrial up-scale process.
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 Integrated Casting-Extrusion
(ICE) of an AA6082 Aluminium Alloy

Shohreh Khorsand and Yan Huang

Abstract
An integrated casting-extrusion is proposed as a novel method for producing profiles of
light alloys at low cost and high efficiency. Such a process has multiple advantages,
including use of solidification heat, removing the multiple steps in conventional processes
and eliminating casting defects. Integrated cast-extrusion experiments have been carried out
using an AA6082 aluminium alloy, under usual casting conditions and 360 °C extrusion
temperature. Experimental results revealed that deformation structure dominated in the
as-cast-extruded state with a uniform microstructure and that, upon heat treatment, a
uniform distribution of Mg2Si precipitations was obtained. EBSD measurements showed
that, after T6-5h heat-treatment, a fine grain structure with an average grain size of 75 µm
and well developed high angle grain boundaries was successfully achieved. The hardness
of the alloy reached to 116 HV after 5 h aging at 180 °C, which is comparable to that
reported for the same alloy processed by conventional routines.

Keywords
Aluminium alloy Cast-extrusion Microstructure Mechanical properties

Introduction casting and extrusion into a single process for producing

Wrought aluminium alloys are widely used in aerospace and
automobile industries owing to its light weight, corrosion
resistance, high stiffness and excellent specific strength [1].
Casting and forming operate separately in industrial practice.
Forming processes such as forging and extrusion are nor-
mally carried out at elevated temperatures using billets
prepared from casting ingots. In one hand, heat treatment,
machining and reheating increases the overall manufacturing
cost and energy consumption. In other hand, conventional
manufacturing processes contain multiple steps which sig-
nificantly increase overall processing time and make prop-
erties controlling difficult. This research aims to integrate
S. Khorsand (&)
Y. Huang
BCAST, Brunel University London, London, UB8 3PH, UK
e-mail: Shohreh.Khorsand@brunel.ac.uk
Y. Huang
e-mail: Yan.Huang@brunel.ac.uk
components of aluminium alloys for automotive industry
and other structural applications. Integrating casting and
forming into a single process represents the possible shortest
manufacturing route for metalworking, offering energy,
material and cost savings. Such novel integration has mul-
tiple benefits: (a) making best use of the solidification heat;
(b) eliminating the multiple steps in conventional operations;
(c) minimizing casting defects associated with rapid cooling
such as excessive residual stresses; (d) increasing the range
of extrusion temperature; and (e) allowing manipulation of
new heat treatment schemes. As a result, the consumed
material, energy and overall manufacturing cost are at their
minimum with uncompromised or improved product quality.
This process integration is different from other approaches
that use hot ingots as forming billets to save energy but
casting and forming are performed on different equipment. It
is also different from semisolid moulding [2], squeeze
casting [3, 4] and high pressure die casting [5, 6] which
involve limited or nil plastic deformation. This process has

© The Minerals, Metals & Materials Society 2017 235

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_32
236 S. Khorsand and Y. Huang

been carried out using an AA6082 aluminium alloy, under

usual casting conditions and 360 °C extrusion temperature.
Microstructural evaluation and mechanical properties of the
obtained materials were also investigated.

Experimental

In the present investigation, an AA6082 aluminium alloy

was used for integrated casting-extrusion (ICE) process. The
chemical composition of the alloy is given in Table 1 and
the ICE process is shown schematically in Fig. 1.
An AA6082 ingot was firstly melted 700 °C and held for
30 min in an electric resistance furnace. Then the molten
alloy was poured at 680 °C into a cylinder steel mould,
which was heated to 300 °C prior to the pouring. The mould
Fig. 1 Schematic illustration of integrated casting extrusion (ICE) pro-
cess, a casting and b extrusion steps
Table 1 Chemical composition of the investigated alloy (wt%)
is made of H13 steel with a diameter of 50 mm and depth of
Si Mg Mn Cu Fe Cr Zn Al
100 mm and painted with BN on the internal wall. In the
0.94 0.5 0.4 0.02 0.2 0.02 0.02 Bal.
process, casting and extrusion was performed consecutively

Fig. 2 SEM micrographs of 6082 alloy after ICE process; a as-deformed cross section, b as-deformed longitudinal section, c aged cross section
and d aged longitudinal section
Integrated Casting-Extrusion (ICE) of an AA6082 … 237

in a single apparatus, in which the casting mould was also with dendritic structures, which were actually destructed. This
used as the extrusion chamber as shown in Fig. 1. can be seen from the microstructure on the longitudinal sec-
Extrusion started when solidification was completed and tion of the extruded rod (Fig. 2b, d). On the cross section the
the billet was cooled down to the predetermined extrusion intermetallic phases are observed to be homogenously dis-
temperature. Extrusion was carried out at a temperature of tributed (Fig. 2a, c). It is likely that they were produced by the
about 360 °C and the extrusion product was a rod of 10 mm fragmentation of needle-shaped particles during extrusion and
in diameter. Heat treatment was performed for some selected as a result, the reduction size of larger particles took place.
samples. The samples were solution treated at 530 °C for 2 h Overall, the materials flow and microstructure was uniform on
and water quenched, followed by artificial aging at 180 °C both longitudinal and cross sections.
for 5 h. Figure 3 displays SEM micrographs of 6082 aluminium
The microstructures for both as-cast/extruded and heat alloy produced by ICE together with its EDS analysis.
treated samples were characterized by optical microscope, As shown in Fig. 3b, the EDS results of the particles
high-resolution transmission electron microscope and revealed that such particles had a composition of Al-9.4at.%
field-emission scanning electron microscope (FE-SEM). Fe-8.75at.%-Si-7.4at.%Mn. The X-ray diffraction patterns of
Longitudinal and cross sections of the samples were ano- samples obtained after ICE in both as-deformed and aged
dized in Barker’s solution, 5 mL HBF4 (48%) in 200 mL conditions are shown in Fig. 4.
water, and then examined with an optical microscope (Zeiss, It is clear that the main phases of the alloy are a-Al,
Jena, Germany), under polarized light. Electron backscat- Al9Fe0.9Mn2.1Si and Mn4Si7. The characteristic peaks on the
tered diffraction (EBSD) images were obtained using an spectrum represent high intensities and are well matched
FE-SEM (equipped with an energy dispersive X-ray spec- with JCPDS cards (a-Al, No. 00-001-1180, Al9Fe0.9Mn2.1Si,
troscopy, SUPRA 35VP, Carl-Zeiss Company, Jena, Ger-
many) operated at a voltage of 15 keV, working distance of
15 mm, a tilt angle of 70° and a step size of *1 µm. Thin
foils for TEM were mechanically ground and punched into
3 mm discs with an average thickness of less than 100 lm.
The discs were subsequently ion beam thinned using a Gatan
precision ion polishing system (PIPS) at 5.0 kV and at an
incident angle of 4°. TEM was carried out on a JEOL 2100F
(JEOL Ltd. Tokyo, Japan) operated at 200 kV. The X-ray
patterns of the specimens were recorded by a D8 advanced
Bruker X-ray diffractometer (Bruker Corporation, Billerica,
Massachusetts, United States) with CuKa radiation in the
range of 30–90° using a step size of 0.05° and a counting
time of 1 s per step. XRD patterns were analysed by using
X’Pert High Score software.
Hardness measurements were performed on a Buehler
5101 Vickers hardness tester. At least 5 measurements were
made on one sample and the hardness values presented were
averaged over individual data.

Results and Discussion

Typical SEM micrographs of as-cast/extruded and aged

AA6082 alloy after ICE process in both cross and longitudinal
sections are given in Fig. 2. In conventional casting, a wide
variety of coarse Fe-containing intermetallic phases can be
formed between dendrites [7] and their geometrical features
depend mainly on the cooling rate and the Fe to Si ratio in the
alloy [8]. However, the as-cast/extruded structure for the
present study bears only little casting features but dominated
by deformation structure and the intermetallic particles are Fig. 3 a SEM micrograph of 6082 aluminium alloy after ICE process
therefore aligned in the extrusion direction rather than in line along with b EDS analysis of 1
238
Fig. 4 X-ray diffraction patterns of the 6082 aluminium alloy
No. 00-042-1206 and Mn4Si7, No. 01-072-2069). The EDS
results (Fig. 3) and X-ray diffraction patterns (Fig. 4) show
that both as-deformed and aged samples consist of
Al9Fe0.9Mn2.1Si and Mn4Si7 fine particles and there is no
evidence of other coarse phases in the microstructure, which
is considered as an advantage of the current process. The
Fig. 5 Optical micrographs of 6082 alloy after ICE process; a as-deformed cross section, b as-deformed longitudinal section, c aged cross section
and d aged longitudinal section
S. Khorsand and Y. Huang
average particle size of these intermetallic was less than
3 µm. Coarse intermetallic phases are usually observed in
the aluminium alloys, and exhibit detrimental effect on
mechanical properties on account of its brittle nature [6].
However, according to load-bearing mechanism [9], well
distributed fine and spherical particles endure a proportion of
applied force imposed under practical applications. There-
fore, the uniform distribution of very fine intermetallic
phases in both cross section and longitudinal section can be
considered as an advantage of ICE process.
Figures 5 and 6 show OM and EBSD/OIM micrographs
of as-deformed and aged samples on both cross and longi-
tudinal sections. Two significantly different grain mor-
phologies were observed in as-deformed and aged alloys.
The cross section of the as-deformed sample had equiaxed
grains while the longitudinal section was characterized by a
fibrous microstructure consisting of grains elongated in the
extrusion direction. This feature is considered as a typical
microstructure of aluminium alloys after extrusion.
EBSD/OIM micrographs of the alloy after ICE process,
Fig. 6a, b, show that as-deformed alloy is mainly consisting
Integrated Casting-Extrusion (ICE) of an AA6082 …
Fig. 6 EBSD/OIM maps of 6082 alloy after ICE process; a as-deformed cross section, b as-deformed longitudinal section, c aged cross section
and d aged longitudinal section
of low angle grain boundaries. However, partial recrystal-
lization can be seen in the microstructure. Dynamic recrys-
tallization (i.e. DRX) usually takes place during straining
when the deformation temperature is above *0.5 Tm [10].
However, it does not occur in aluminium alloys and the
recrystallization is considered to have occurred during slow
cooling after extrusion. The microstructure of the aluminium
after aging consisted of equiaxed Al grains in cross section
and elongated grains in longitudinal section (Figs. 2 and 5).
EBSD measurements showed that the aged AA6082 sample
contains a large amount of HAGBs. The average grain size
of aged alloy is 26 µm while the average grain size of
as-deformed alloy is 75 µm. These characteristics, i.e. larger
grain size and higher amount of HAGBs in aged alloy,
shows that static recrystallization occurred during heat
treatment process. The term recrystallization is commonly
used to describe the replacement of a deformation mi-
crostructure by new grains during annealing; this is referred
to as static recrystallization (SRX) [10, 11]. Static recovery
(SRV) takes place during the early stages of annealing and is
responsible for the development of recrystallization nuclei as
fine dislocation-free crystallites. These grow by means of the
long-range migration of the boundaries, which consume the
strain hardened microstructure [11]. The driving pressure for
the growth of such new grains is the stored energy associated
239
with the dislocations and sub-boundaries produced during
prior straining. In the early stages of SRX, the nuclei are
outlined by low-angle boundaries, the misorientations of
which gradually increase until they attain values typical of
high-angle boundaries (HABs) [12]. During annealing, the
microstructure is characterized by a mixture of increasing
amounts of recrystallized grains and decreasing amounts of
strain hardened grains. Such a process is sometimes referred
to as discontinuous static recrystallization (dSRX) [11, 13].
TEM micrographs of samples after ageing are shown in
Fig. 7. Mg2Si precipitations with two different size scales are
formed in the microstructure. The precipitation of the
metastable precursors of the equilibrium b(Mg2Si) phase
occurs in one or more sequences, which are quite complex.
The precipitation sequence for 6082 alloy, which is gener-
ally accepted in the literatures [14–17], is: SSSS ! GP
zones ! b″ ! b′ ! b. The most effective hardening phase
in order to achieve maximum strength for these types of
materials is b″. According to Fig. 7a, b, b″(Mg2Si) and b′
(Mg2Si) are distributed in some grains while there are other
grains covered with b(Mg2Si) phase, Fig. 7c, d.
These precipitations can significantly improve the hard-
ness of the alloy, as demonstrated in Fig. 8.
A remarkable increase was observed in the hardness of
the AA6082 alloy after 5 h aging, 117 HV, which was 2.6
240
Fig. 7 HRTEM micrographs of aged 6082 alloy after ICE process in 2 magnifications; a, b b″ and b′ and c, d b precipitations
times greater than the values obtained for the as-deformed
state (45 HV). The hardness values obtained ICE process is
close to the values for conventionally extruded bars of the
Fig. 8 Variation of the hardness of 6082 aluminium alloy versus aging
time
S. Khorsand and Y. Huang
same alloy [1, 6]. In general, the hardness of the as-deformed
alloy is mainly due to the strain hardening (dislocation
strengthening and grain boundary strengthening mechanism)
[18]. It is important to note that the higher hardness of the
aged alloy in this work does not result from the mentioned
mechanisms (dislocation and grain boundary strengthening
mechanisms). This is mainly attributed to the role of nano
precipitations in strengthening of matrix by the Orowan
strengthening mechanism. Orowan mechanism corresponds
to the interaction of the precipitations and dislocations in
which precipitations pin dislocations resulting in bowing
dislocation around particles and create Orowan rings. Fur-
thermore, during the hardness test, precipitations act as a
barrier to dislocation movement, increasing the hardness
[19, 20].
Conclusions
In the present investigation, a novel integrated cast-extrusion
process was tested using an AA6082 aluminium alloy. The
microstructures were examined and mechanical properties
tested for the as-deformed and heat treated samples. The
conclusions drawn from the results can be summarized as
follows:
Integrated Casting-Extrusion (ICE) of an AA6082 …
1. The integrated casting extrusion (ICE) was successfully
applied on the AA6082 alloy as a metal working process.
2. The as-cast/extruded samples showed a uniform mi-
crostructure and uniform material flow pattern.
3. Homogeneous distribution of intermetallic particles with
an average size of 3 µm was achieved in both cross and
longitudinal sections after heat treatment. The formation
of b″(Mg2Si), b′(Mg2Si) and b(Mg2Si) precipitations
was verified by HRTEM characterization.
4. The hardness of the aluminium alloy, being 47 HV in the
as-cast/extruded state, was improved by 2.6 times after
aging, to being 117 HV.
Acknowledgements The authors acknowledge financial support from
Brunel Research Catalyst Fund and Dr. L. Zhou for her assistance.
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 On Porosity Formation in Al–Si–Cu Cast Alloys

F.H. Samuel, A.M. Samuel, H.W. Doty, and S. Valtierra

Abstract
The aim of the present work was to investigate the metallurgical parameters controlling
porosity formation in Al–Si–Cu alloys, through a study of the microstructural character-
istics of directionally solidified 319.2 alloys as a function of iron content, Sr addition
(250 ppm), and solidification rate. The iron levels selected varied from 0.12 to 0.8 wt%,
and cover the range of Fe levels found in commercial casting alloys. The use of an
end-chilled mold provided different solidification rates along the height of the same casting,
with DAS values that varied from *15 to 85 lm, corresponding to levels of 5, 10, 30, 50
and 100 mm above the chill end. The amount of iron present in the alloy affects the size of
the beta-iron Al5FeSi platelets and their distribution, particularly at low solidification rates.
Addition of strontium leads to fragmentation of co-eutectic or post-eutectic beta-iron
platelets.

Keywords
Al–Si–Cu cast alloys Fe and sr content Solidification rate Porosity formation

Introduction solute segregation, primary particles of binary Al–Fe and

Commercial unalloyed aluminum and aluminum alloys
contain a considerable amount of iron and silicon as impu-
rities or alloying additions. Commercial aluminum alloys,
which have up to 1% of iron and silicon, can be considered
ternary alloys. As the solid solubility of iron in aluminum is
less than 0.05% at equilibrium, nearly all iron in aluminum
alloys forms second-phase particles. Both iron and silicon
have partition coefficients less than unity, and accordingly
segregate to the liquid between the Al dendrite arms during
the course of solidification. Therefore, when considering the
F.H. Samuel (&)
A.M. Samuel
Université Du Québec à Chicoutimi, Chicoutimi,
QC G7H 2B1, Canada
e-mail: fhsamuel@uqac.ca
H.W. Doty
General Motors Materials Engineering,
823 Joslyn Ave, Pontiac, MI 48340, USA
S. Valtierra
Nemak, S.a, P.O. Box 100Garza Garcia, N.L 66221, Mexico
ternary Al–Fe–Si phases, and even silicon can form during
casting of an aluminum-rich alloy.
Certain alloying elements may be added to aluminum
alloys to improve their mechanical properties and/or avoid
the effect of some undesirable impurity elements. The most
detrimental element is iron, and its presence in aluminum
alloys is increased as a result of the usage of recycled alloys.
Iron forms a number of brittle intermetallic phases [1–3], the
most detrimental being the b-Al5 FeSi phase, which reduces
the alloy ductility and fracture toughness. Existing in the
form of thin platelets that appear as needles in the
microstructure, the size of these b platelets is controlled by
the iron content and the solidification conditions of the alloy.
Different measures adopted to neutralize the harmful effect
of the b-iron phase include rapid solidification [4], addition
of neutralizers such as Mn, Co, and Cr [5, 6], melt superheat,
Sr modification [7, 8] and non-equilibrium solution heat
treatment [9]. The a-Al15(Fe,Mn,Cr)3Si2 phase, due to its
compact script-like morphology is less harmful to the
mechanical properties.

© The Minerals, Metals & Materials Society 2017 243

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_33
244
Metallographic studies have shown that pores are nucle-
ated along the long sides of the b platelets. However, in spite
of the harmful effect of these b platelets as pore nucleation
sites, their presence also appears to limit pore growth [10,
11]. Strontium is commonly added to Al–Si alloy melts to
modify the silicon eutectic, but also affects the amount and
distribution of porosity that results in the casting. In addition,
Sr also results in the fragmentation and dissolution of the
b-Al5FeSi phase platelets [12, 13]. Apparently, during
solidification, Sr addition leads to local segregation of iron in
certain areas, such that the Fe/Si ratio is >1, which favors
precipitation of iron in the form of the compacted
a-Al8Fe2Si phase [14]. Villeneuve and Samuel [15] reported
that the addition of a sufficiently high concentration of Sr
(*350 ppm) to Al-13 wt% Si–Fe alloys breaks down the
b-needles into small, thin fragments through (i) splitting of
the needles into two halves, and (ii) fragmentation due to Si
rejection. Dissolution of the b-phase occurs by decomposi-
tion of b-Al5FeSi into Al6Fe and Si particles.
Control of the iron level is thus technically important,
especially where the production of critical components is
concerned. The present study was undertaken to investigate
the combined effect of solidification rate and iron content on
porosity formation in 319-type Al–Si–Cu cast alloys.
Experimental Procedure
The chemical composition of the Al–Si–Cu alloy used in the
present work is listed in Table 1. Castings were carried out
using (i) a refractory end-chilled mold, and (ii) a preheated
graphite mold. The former provided directional solidification
that allowed obtaining a range of dendrite arm spacings
along the height of the casting block above the chill end. The
hot graphite mold provided close-to-equilibrium solidifica-
tion conditions and allowed enough time for solidification
and growth of the precipitating phases, which facilitated
examination and phase identification using electron probe
microanalysis.
A schematic diagram of the rectangular shaped end-chill
mold and the casting produced from it (dimensions:
65  130  230 mm) is shown in Fig. 1. In order to obtain
directional solidification, the four walls of the mold are made
of refractory material, and the bottom is a water-chilled
copper base. The main reason for using this mold is that the
solidification time varies along the mold height, which leads
to a wide range of dendrite arm spacings (DASs).
Table 1 Chemical composition Alloy Element (wt%)
of the Al–Si–Cu base alloy used
in this study Si Cu
A319.2 6.06 2.98
F.H. Samuel et al.
The molten metal was poured into the mold through
ceramic foam filter discs fitted into the riser to avoid incident
inclusions. The mold was preheated at 150 °C to drive out
moisture. The water (that circulates in the copper chill) was
turned on the moment the liquid metal had half-filled the
mold. Such an arrangement produced ingot blocks with
solidification rates that decreased with increasing distance
from the chill end, resulting in microstructures that exhibited
varying dendrite arm spacing values, ranging from 15 to
85 lm, along the height of the cast block.
Thermal analysis was also carried out on the A319.2
alloys containing 0.2 and 0.8% iron, in both the unmodified
and Sr-modified conditions. In this case, the ingot pieces
were melted in a 1.5 kg capacity SiC crucible, using an
electrical resistance furnace. The melting temperature was
kept at 750° ± 5 °C. The molten metal was poured into a
600 °C preheated cylindrical graphite mold (100 mm length
and 60 mm diameter) to obtain close-to-equilibrium solidi-
fication conditions. The temperature-time data was collected
using a high speed data acquisition system linked to a
computer with an acquisition rate of 10 readings/s.
Table 2 lists the various alloys/castings that were pre-
pared from the base alloy. With respect to the alloy codes,
the prefix A represent the A319.2 base alloy; F represents
Fe, while the numbers 1, 2, 4, 6 and 8 correspond to Fe
levels of 0.12, 0.2, 0.4, 0.6 and 0.8%, respectively. The
suffix S in any code implies that the alloy has been
Sr-modified. Specimen blanks were sectioned from the cast
blocks at the selected heights of 5, 10, 30, 50 and 100 mm
above the chill end (presented in the text by the suffix 0, 1, 3,
5, and C, respectively), corresponding to DAS values
ranging between *15 and *85 µm. Samples (20 mm
30 mm) were cut from the central part of each blank, close
to the thermocouple tip, mounted in bakelite and polished to
a fine finish (1 lm diamond paste).
Quantitative measurements of the dendrite arm spacing,
the b-Al5FeSi platelets (or needles as they appear on the
sample surface under a microscope), percentage porosity and
pore characteristics and were made using an optical
microscope-Clemex image analyser system. In each case, a
certain number of fields (about 50 fields/sample) were
examined for each sample (“field” representing the field of
view of the optical microscope and covering an area of
2.2608  104 lm2 at 500 magnification), selected so as to
cover the entire area of the sample in a regular, systematic
fashion. Phase identification was carried out using the gra-
phite mold-cast samples, employing scanning electron
Mg Fe Mn Zn Ti Sr Al
0.002 0.12 0.023 0.006 0.007 0.0003 Bal.
On Porosity Formation in Al–Si–Cu Cast Alloys 245

Fig. 1 Schematic diagram of

a end-chill mold, and b end-chill
mold casting showing specimen
blank sectioning. All dimensions
are in mm

Table 2 Chemical compositions Alloy code Element (wt%)

and codes of the various alloys
used in the present study Si Fe Cu Mn Mg Cr Sr Al
AF2 6.83 0.264 3.46 <0.00050 <0.00500 <0.00055 <0.00013 89.4
AF2S 6.36 0.254 3.56 <0.00050 <0.00611 <0.00050 0.0519 89.73
AF4 6.84 0.466 3.56 <0.00050 <0.00500 0.0007 <0.00010 89.02
AF4S 6.19 0.42 3.43 <0.00050 <0.00500 0.0058 0.0345 89.88
AF6 5.29 0.667 3.56 0.0013 <0.00500 <0.00061 <0.00095 90.42
AF6S 6.09 0.638 3.41 0.0007 <0.00500 0.001 0.0342 89.77
AF8 5.31 0.851 3.68 0.0021 <0.00500 0.0008 <0.00010 90.1
AF8S 6.14 0.847 3.43 0.0015 <0.00500 0.0015 0.0344 89.49

microscopy (SEM) and energy dispersive/wavelength dis- leads to a substantial improvement in mechanical properties
persive spectroscopy (EDS/WDS). [12, 14].

Results and Discussion b-Al5FeSi Platelet Size

The dendrite arm spacing (DAS) is a microstructural mani-
festation of the solidification rate of a solidifying sample: the
higher the solidification rate, the finer the DAS of the sample
microstructure, and vice versa. In fact, DAS is often pre-
ferred to the solidification rate as an indicator of the solidi-
fication conditions of the casting, as it is easier to measure,
and incorporates the influence of other solidification
parameters as well. A finer DAS refines and disperses the
porosity as well as second phase constituents (e.g., the b-iron
phase) more evenly. This refinement of the microstructure
The data obtained from the b-Al5FeSi platelet measurements
were plotted in the form of histograms for both unmodified
and Sr-modified alloys. Figure 2 depicts these histograms,
showing the average b platelet lengths obtained as a function
of distance from the chill end (viz., solidification rate) in the
two cases. The results may be summarized as follows.
In regard to the solidification rate, it may be seen that the
higher the solidification rate (i.e., at 5 and 10 mm distance
from the chill end), the shorter the b-platelet average length
in both unmodified and Sr-modified alloys (e.g., 31.02 lm
246
Fig. 2 Effect of solidification
rate on the average b-platelet
length observed in a unmodified,
and b Sr-modified A319.2 alloys
for AF4-0 alloy versus 143.14 lm for AF4-C alloy, and
27.58 lm for AF4S-0 alloy versus 137.71 lm for AF4S-C
alloy). There are two possible explanations: (i) the iron
content may be over the saturation limit, and that the excess
will increase with solidification rate; (ii) a higher cooling rate
will also result in a smaller DAS, and the overall refinement
of the microstructure will result in the precipitation of finer
b-particles.
At higher cooling rates, the effect of Sr addition on the
b-platelet length is not very obvious, and the effect due to
cooling rate is stronger than that due to Sr modification. At
lower cooling rates, the b-platelet lengths in the higher
Fe-level alloys are longer in the Sr-modified alloys than in
the unmodified alloys. In this case, addition of strontium
may reduce the b-needle nucleation sites. Consequently, the
b-iron phase must precipitate at a smaller number of sites,
resulting in the precipitation of needles that are larger
compared to those in the unmodified alloys. This observa-
tion is in contrast to the observations of Shabestari and
F.H. Samuel et al.
Gruzleski [16] who reported that for slow solidification rates,
Sr causes fragmentation of the b-needles and a 47% reduc-
tion in volume (that is transformed into sludge).
It can also be observed from Fig. 2, that the higher the Fe
content, the longer the b-platelet lengths, especially at the
lowest solidification rate (cf. 117.72 µm for AF2-C alloy
with 204.75 µm for AF8-C alloy- see Table 2 for alloy
code). This observation is in accordance with the work of
Villeneuve and Samuel [15] who observed that an increased
iron content results in the precipitation of long thick
needles/platelets of the b-Al5FeSi intermetallic phase.
Figure 3 show plots of the b-platelet density versus
solidification rate for the A319.2 alloys in the unmodified
and Sr-modified conditions. While the two cases appear to
be essentially similar, certain features may be highlighted:
1. The difference in the b-platelet densities between the
various alloys is more evident at the higher solidification
rates, and after a DAS of *43 ± 4 lm corresponding to
On Porosity Formation in Al–Si–Cu Cast Alloys 247

Fig. 3 Effect of solidification

rate on the b-platelet density in A Alloy
A319.2 alloys
2500 AF2
AF2S
2000
AF4

Density (No/mm2)
1500 AF4S
AF6
1000
AF6S

500 AF8
AF8S
0
0 20 40 60 80 100 120
Distance from chill end (mm)

the 30 mm level above the chill end, the density remains
more or less the same irrespective of the Fe content of the
alloy, or whether it is modified or not.
2. For the various Fe levels, the modified alloys exhibit
highest b-densities at the highest Fe level (0.8%). At
lower Fe levels, no clear distinction can be made.
The presence of a sufficiently high concentration of Sr
leads to a breakdown of the b-platelets into smaller, thinner
fragments via two mechanisms: (i) splitting of the
needle/platelets into two halves through the formation of
longitudinal cracks, enhanced greatly by the brittle nature of
the b-iron phase, and (ii) fragmentation due to Si rejection;
on account of this, there is an effective increase in the
density, with the addition of Sr, compared to the unmodified
case [17]. At low solidification rates, the iron intermetallics
grow to large sizes, and thus particle density is reduced to a
minimum.
It has been observed by Villeneuve and Samuel [15] that
Sr addition only affects small b-needles. This phenomenon is
more pronounced in high Fe-containing alloys. On the other
hand, large b-needles are seen to persist, even after Sr
addition or solution heat treatment. This would explain the
collective features of the b-iron intermetallic density plot in
Fig. 3.
Figures 4 and 5 show the microstructure of the AF2 and
AF2S alloy samples obtained at the highest solidification
rate (5 mm above the chill end). In Fig. 4, very fine
b-needles are observed in the microstructure, often at the
interface of the a-Al dendrites or eutectic Si particles, indi-
cating that they precipitated in a co-eutectic or post-eutectic
reaction. The fine eutectic Si particles in Fig. 5 show that the
alloy is well modified.
The optical micrograph of Fig. 6 shows the microstruc-
ture exhibited by the AF8-C alloy sample (high Fe—low
solidification rate condition). Two distinct types of
b-Al5FeSi platelets (or needles) are observed: large
pre-eutectic b and smaller co-eutectic or post-eutectic b,
corresponding to their sequence of precipitation with respect
to the Al–Si eutectic reaction. The acicular eutectic Si par-
ticles indicate the unmodified nature of the alloy. Figure 7
shows the corresponding microstructure of the AF8S-C alloy

Microstructure

The microstructures of selected A319.2 alloy samples

obtained from the various alloys examined in Sect. 3.1 will
be presented here to complement the quantitative results
described above, with respect to the influence of alloy
composition and solidification conditions on porosity for- Fig. 4 Microstructure of AF2-0 alloy sample (5 mm from the chill
mation in these alloys. end)
248
Fig. 5 Microstructure of AF2S-0 alloy sample (5 mm from the chill
end)
Fig. 6 Microstructure of AF8-C alloy sample (100 mm from the chill
end)
sample, the Al–Si eutectic now exhibiting a well modified
structure.
The difference in the b-Al5FeSi platelet sizes is related to
the rate of diffusion of the iron atoms with respect to the
temperature at which the two platelet types precipitate.
Mascré [18] confirmed that due to their size and shape, the
pre-eutectic b-Al5FeSi are the most harmful to the
mechanical properties. Due to the feedability problems
related to the platelet-like nature of the b-phase, the occur-
rence of porosity is often observed in association with these
platelets. In the case of the modified alloy sample AF8S-C,
Fig. 7, while the eutectic Si regions are well modified, the
effect of Sr on the fragmentation and dissolution of the
b-platelets was observed for the smaller sized/thinner b
particles (see arrows), whereas the large pre-eutectic b
remained unaffected. The persistence of such massive
b-platelets in the microstructure provides a good indication
F.H. Samuel et al.
Fig. 7 Microstructure of AF8S-C alloy sample (100 mm from the chill
end)
of why the properties of alloys containing Fe levels of 0.8%
or higher cannot be improved by any means, and hence why
such alloys should be rejected.
Porosity Characteristics
Figure 8 shows the important porosity characteristics for the
A319.2 alloys as a function of Fe content and solidification
rate. The following observations may be noted: the lowest
percentage porosity and lowest maximum pore area appear at
0.4 wt% Fe, whether the alloy is modified or not. Lower of
higher Fe contents increase the amount of porosity formed.
At the highest cooling rate, the effect of Fe is not that obvi-
ous. An increase in cooling rate decreases both percentage
porosity and maximum pore size observed in all the alloys,
since less time is available for hydrogen to diffuse into the
interdendritic regions of the partially solidified metal,
resulting in a smaller pore size. Furthermore, the higher
temperature gradients present at higher solidification rates
tend to limit the length of the mushy zone, to make feeding
easier and retard porosity formation. When Sr is added, the
porosity level is increased on account of two factors, one of
them being the formation of strontium oxide (particles or
films), due to the high affinity of strontium for oxygen. These
oxides are always observed associated with microporosity.
Secondly, the addition of Sr can lower the surface tension, an
effect which would facilitate pore nucleation and result in
increased porosity in modified alloys.
Taylor et al. [19, 20] studied the role of iron (0.1–1 wt%)
in the formation of porosity in non-grain-refined, unmodified
Al-5.2%Si–1.2%Cu–0.5%Mg alloy and observed that i) the
total porosity was minimized at 0.4 pct Fe; (ii) a localized
shrinkage-porosity defect (termed “extended defect”) devel-
oped at high iron concentrations; and (iii) there was a change
On Porosity Formation in Al–Si–Cu Cast Alloys 249

6900
a
Average area
4600

(μm²) 2300 Sr=400

Sr=0

0
0 20 40 60 80 100
52
Average length

39
(μm)

26
Sr=400
13 Sr=0

0
0 20 40 60 80 100
1120
Max length (μm)

840

560
Sr=400
280 Sr=0

0
0 20 40 60 80 100
600000
500000
Max pore area

400000
(μm²)

300000
200000
Sr=400
100000
Sr=0
0
0 20 40 60 80 100
2
1.6
porosity (%)
Percentage

1.2
0.8
0.4 Sr=400
Sr=0
0
0 20 40 60 80 100

Distance from the chill end (mm)

Fig. 8 Effect of cooling rate and iron content on the porosity parameters: a 0.2%, b 0.4%, c 0.6%, and d 0.8%
250 F.H. Samuel et al.

8400
b
Average area 5600
(μm²) Sr=400
2800
ppm

0
0 20 40 60 80 100
100
Average length

75

50
(μm)

Sr=400
25 ppm

0
0 20 40 60 80 100
840
Max length (μm)

560

280 Sr=400 ppm

Sr=0

0
0 20 40 60 80 100

168000
Max pore area (μm²)

112000

56000
Sr=400 ppm
Sr=0
0
0 20 40 60 80 100

1.6
Sr=400
porosity (%)

1.2 ppm
Percentage

0.8

0.4

0
0 20 40 60 80 100

Distance from the chill end (mm)

Fig. 8 (continued)
On Porosity Formation in Al–Si–Cu Cast Alloys 251

900 c
Average area 600
(μm²)
Sr=400
300 ppm

0
0 20 40 60 80 100

120
Average length

90
(μm)

60
Sr=400
30 ppm

0
0 20 40 60 80 100

520
Max length (μm)

390

260
Sr=400
130 ppm

0
0 20 40 60 80 100

18900 Sr=400
Max pore area

ppm
12600
(μm²)

6300

0
0 20 40 60 80 100
2.8
Percentage porosity

Sr=400
2.4
ppm

2
(%)

1.6

1.2
0 20 40 60 80 100

Distance from the chill end (mm)

Fig. 8 (continued)
252 F.H. Samuel et al.

Distance from the chill end (mm)

Fig. 8 (continued)
On Porosity Formation in Al–Si–Cu Cast Alloys
in porosity characteristics from a discrete pore morphology at
0.1%Fe levels to zones of sponge-like interdendritic porosity
at higher Fe levels. They suggested that the mechanism by
which iron causes such porosity defects may be related to the
solidification sequence of the alloy. Using a phase diagram
approach and calculated segregation lines on the liquidus
projection of the ternary Al–Si–Fe phase diagram, they pro-
posed that when solidification proceeds directly from the
primary (a-Al) field to the ternary Al–Si-bAl5FeSi eutectic
point, the porosity is minimized at the critical iron content,
whereas when solidification takes place via the binary
Al-bAl5FeSi eutectic, higher porosity levels are obtained.
Large b needles are binary b which forms prior to the ternary
eutectic, while small b needles are ternary b, and are the first
component of the ternary eutectic to form.
At critical Fe contents, the b-phase solidifies as the initial
component of the ternary eutectic. At higher Fe levels, the
b-phase is already well developed when ternary eutectic
solidification commences, whereas at lower Fe levels, it
forms as a component of the ternary eutectic only after the
binary Al–Si eutectic is formed. Each of these solidification
paths leads to different variations in microstructural perme-
ability, i.e., interdendritic feedability and, hence, porosity
formation. At the critical Fe level, the smaller ternary b do
not block interdendritic liquid flow, whereas below and
above this level, larger binary b block the interdendritic
regions, causing higher porosity levels.
Comparing the present results with those of other
researchers [11, 19–23] minimum porosity levels are also
observed at 0.4 pct Fe levels in the A319.2 alloy. As the
casting methods employed in the two studies are different,
only a qualitative comparison can be made. As both alloy
fluidity and maximum b-platelet size were found to increase
with increasing iron content in the A319.2 alloys, it is sug-
gested that the competition between these two factors deter-
mines the actual porosity observed at a particular Fe level.
As b-platelet measurements in the present work were
focused on the largest b needles observed in the
Fig. 9 a Presence of SrO
particles in sample sectioned at Oxide particles
100 mm above the chill
end-arrow points to SrO particles
within the pore; b high
magnification electron image of
SrO particles inside the pore
253
microstructure (these being assumed to cause the greatest
hindrance to feedability), we cannot really comment upon
the effect of small versus large b needles. Nevertheless, both
Taylor et al.’s point of view and ours essentially relate the
amount of porosity formed to the permeability or ease of
liquid flow through the interdendritic regions during the
course of solidification.
In order to understand the role of oxides on the porosity
parameters, another set of casting was made. In this case, the
molten metal was not degassed (hydrogen con-
tent *0.25 ml/100 g Al). Figure 9a exemplifies the size and
shape of the pores observed in Sr-modified alloy sectioned at
100 mm above the chill end and reveals that the size could
be several times that obtained from well degassed metal
(hydrogen content *0.08 ml/100 g Al) As can be seen a
large number of oxides is present within the pore. These
strontium oxide particles are clearly viewed in the high
magnification electron image of Fig. 9b.
The formation of both gas and shrinkage pores on
b-Al5FeSi platelets were also demonstrated using samples
sectioned from graphite mold (no degassing was applied in
this case). Figure 10a, taken from high hydrogen-containing
A319.2-0.8%Fe alloy, shows a gas pore nucleated on a
b-Al5FeSi platelet, having a round shape typical of gas
pores. The hydrogen content of the alloy melt was
0.25 ml/100 g Al. The higher magnification image of
Fig. 10b reveals this more clearly. The flattened dendrites
observed inside the pore indicate that this is a gas pore.
Figure 10c shows how the growth of the gas pore is limited
by the b platelets (needles) on either side of the pore.
Figure 11 shows how shrinkage porosity occurs due to
the b-platelets, particularly when they are branched (see
circled area). The platelets form in the interdendritic chan-
nels during solidification, and cause physical restrictions to
the movement of compensatory feed liquid, giving rise to
shrinkage porosity Thus in spite of the fact that the
b-platelets act as pore nucleation sites, their presence can
also limit pore growth.
SrO particles
254 F.H. Samuel et al.

β-platelet

(a)

Fig. 11 SEM micrograph showing an example of how branched

b-platelets can cause shrinkage porosity

2. Addition of strontium leads to fragmentation of

co-eutectic or post-eutectic b-Al5FeSi platelets. How-
ever, the effect of Sr diminishes with the increase in Fe
concentration.
3. Although branching of the b-Al5FeSi platelets leads to
(b)
porosity formation, on the other hand, the platelets also
limit pore growth.
4. In general, porosity parameters (percentage porosity,
maximum pore area and maximum pore length) increase
with increase in average maximum b-platelet lengths.
5. Unmodified alloys show better correlations between
porosity and iron content, than the Sr modified alloys.
This can be attributed to the formation of strontium oxides
(particles or films) in the Sr- containing alloys which also
provide nucleation sites for porosity formation.
6. In the case of un-degassed alloys, the porosity parameters
could be ten times that observed in degassed alloys,
(c) under same working conditions.

Fig. 10 SEM micrographs showing how a, b the b-Al5FeSi platelets

(arrowed) nucleate gas porosity, and c limit pore growth c in high
hydrogen-containing A319.2-0.8% Fe alloy (hydrogen level:
0.25 ml/100 g)
Conclusions
1. The size of b-Al5FeSi platelets and their distribution are
greatly affected by the amount of iron present, particu-
larly at low cooling rates.
References
1. L.A. Narayanan, F.H. Samuel, J.E., Gruzleski, “Crystallization
behavior of iron-containing intermatllic compounds in 319 Alu-
minum alloy”. Metall. Mater. Trans. A. 25A, 1761–1773 (1994)
2. R.S. Rana, R. Purohit, S. Das, Review on the influence of alloying
elements on the microstructure and mechanical properties of
aluminum alloys and aluminum alloy composites. Int. J. Sci Res.
Publ. 2, 1–7 (2012)
3. L. Lu, A.K. Dahle, Iron-rich intermetallic phases and their role in
casting defect formation in hypoeutectic Al–Si alloys. Metall.
Mater. Trans. A A36, 819–835 (2005)
On Porosity Formation in Al–Si–Cu Cast Alloys
4. S. Lee, B. Kim, S. Lee, Prediction of solidification paths in
Al-Si-Fe ternary system and experimental verification: part II.
Fe-containing eutectic Al-Si alloys. Mater. Trans. 52(6), 1308–
1315 (2011)
5. G. Gustafsson, T. Thorvaldsson, G.L. Dunlop, The influence of Fe
and Cr on the microstructure of cast Al-Fe-Si alloys. Metall. Trans.
A 17A, 45–52 (1986)
6. P. Ashtari, H. Tezuka, T. Sato, “Influence of Sr and Mn additions
on intermetallic morphologies in Al-Si-Cu-Fe cast alloys”. Mater.
Trans. 12, 2611–2616 (2003)
7. Y. Awano, Y. Shimizu, Non-equilibrium crystallization of AlFeSi
compound in melt-superheated Al-Si alloy castings. AFS Trans.
98, 889–895 (1990)
8. A.M. Samuel, H.W. Doty, F.H. Samuel, “Influence of melt
treatment and solidification parameters on the quality of 319.2
Endchill Aluminum Castings,” in Proceedings of 4th International
Conferences on Molten Aluminum Processing, Orlando, Florida,
12–14 Nov 1995, pp. 261–294
9. M. Sha, S. Wu, L. Wan, S. Lu, Effect of heat treatment on
morphology of Fe-Rich intermetallics in hypereutrctic Al-Si-Cu-Ni
alloy with 1.26 pct Fe. Metall. Mater. Trans. A 44A, 5642–5652
(2013)
10. N. Roy, A.M. Samuel, F.H. Samuel, Porosity formation in Al-9 Wt
Pct Si-3 Wt Pct Cu alloy aystems: metallographic observations.
Metall. Mater. Trans. A 27A, 415–429 (1996)
11. M.A. Moustafa, Effect of iron content on the formation of
b-Al5FeSi and porosity in Al-Si eutectic alloys. J. Mater. Process.
Technol. 209, 605–610 (2009)
12. A.M. Samuel, H.W. Doty, S. Valtierra, F.H. Samuel, Relationship
between tensile and impact properties in Al–Si–Cu–Mg cast alloys
and their fracture mechanisms. Mater. Des. 53, 938–946 (2014)
13. E. Tilová, M. Chalupová, L. Hurtalová, M. Bonek, L.A.
Dobrzański, Structural analysis of heat treated automotive cast
alloy. J. Achievements Mater. Manufact. Eng. 47(1), 19–25 (2011)
255
14. J.E. Gruzleski, B.M. Closset, The treatment of liquid
aluminum-silicon alloys, American Foundrymen’s Society Inc,
Des Plaines (U.S.A, IL, 1990)
15. C. Villeneuve, F.H. Samuel, Fragmentation and dissolution of
b-Al5FeSi phase during solution heat treatment of Al-13%Si-Fe
alloys. Int. J. Cast Met. Res. 12(3), 145–160 (1999)
16. S.G. Shabestari, J.E. Gruzleski, The kinetics of formation and
growth of complex intermetallic compounds in aluminum-silicon
alloys. Cast Metals 6(4), 241–251 (1994)
17. Z. Ma, “Effect of Fe-intermetallics and porosity on tensile and
impact properties of Al-Si-Cu and Al-Si-Mg cast alloys”, Ph.D.
Thesis, Université du Québec à Chicoutimi, Canada, 2003
18. C. Mascré, «Influence du fer et du manganèse sur les alliages du
type de l’A-S13 (Alpax),» Fonderie, 108 (Jan. 1955), pp. 4330–
4336
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formation of porosity in Al-Si-Cu-based casting alloys: part II.
A phase-diagram approach. Metall. Mater. Trans. A 30A, 1651–
1655 (1999)
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formation of porosity in Al-Si-Cu-based casting alloys: part III.
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(1), 47–50 (2015)
 Part VII
Aluminum Alloys, Processing and Characterization:
Characterization
 Algorithm for Finding the Correlation Between
the Properties of Wrought Aluminum Alloys,
the Chemical Composition and the Processing
Parameters

Varužan M. Kevorkijan, Branko Hmelak, Peter Cvahte, Sara Hmelak,

Vukašin Dragojević, Uroš Kovačec, Marina Jelen, and Darja Volšak

Abstract
The successful industrial modeling of wrought aluminum alloys with the desired
combination of properties is based on finding the surjective and inverse correlation
T(C, PP) $ P between the properties, P, of the final product and the different technological
paths T(C, PP) capable of providing it (and vice versa). Here, C represents the chemical
composition of the alloy and PP is the processing parameters. The algorithm presented in
this work is based on the functional equivalency of two different technological paths, T1
and T2, able to provide the same combination of properties, written as P(T1) = P(T2),
where P(T1) and P(T2) represent the properties obtained using the various paths T1 and T2
in vector space. The selection of the best among the functionally equivalent technological
paths, T, was performed by applying the minimum-cost criterion. The cognitive computing
of the real data confirmed the promising industrial potential of such a modeling for
high-strength and recycling-friendly wrought aluminum alloys.

   
Keywords
Aluminium Wrought alloys Modelling Composition-Properties Cognitive
computing

Introduction aluminum alloys, focusing on the desired performance—and

To remain competitive with other advanced materials, e.g.,
high-strength steels, in solutions with “the proper materials
in the proper place”, wrought aluminum alloys must provide
superior functional and cost-effective solutions. To achieve
this it will be necessary to design and develop new, wrought
V.M. Kevorkijan (&)  P. Cvahte  V. Dragojević  U. Kovačec
M. Jelen  D. Volšak
Impol Aluminum Industry, Partizanska 38, 2310 Slovenska
Bistrica, Slovenia (EU)
e-mail: varuzan.kevorkijan@impol.si
B. Hmelak  S. Hmelak
Alcad, Zg. Bistrica 4, 2310 Slovenska Bistrica, Slovenia (EU)
e-mail: branko.hmelak@alcad.si
not on the exact chemical composition [1]. The fundamental
changes in the design of advanced, wrought aluminum
alloys would be the introduction of new chemical compo-
sitions with broader intervals of concentration for the critical
alloying elements, i.e., iron and silicon, as well as other
alloying elements and trace elements [2]. However, for the
successful formulation of these new alloys, experimentally
established relations between the changes in chemical
composition and the processing (heat treatment and form-
ing), on the one hand, and the particular properties, on the
other, are necessary [3].
In this paper an algorithm for finding the correlation
between the properties of wrought aluminum alloys, the
chemical composition and the processing parameters will be
presented and validated.

© The Minerals, Metals & Materials Society 2017 259

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_34
260
The Main Principles of Modeling
Recycling-Friendly Alloys
Modeling the Chemical Composition
From the point of view of modeling, it is important to note
that in the functional correlation between a selected alloy
property, e.g., the tensile strength (TS), and the composi-
tional and processing variables, all the variables appear as
intervals with a normal (Gaussian) distribution.
Therefore, we can write:
TS ðl; rÞ ¼ f ½C1 ðl1 ; r1 Þ; . . .; Cn ðln ; rn Þ;
ð1Þ
P1 ðp1 ; H1 Þ; . . .; Pm ðpm ; Hm Þ
where Ci ðli ; ri Þi ¼ 1; 2; . . .; n represents the concentration
intervals with a Gaussian distribution of concentrations for

alloying element in a wrought aluminum alloy of standard
the individual alloying elements, while Pj pj ; Hj j ¼
1; 2; . . .; m represents the individual processing parameters
that are also given as intervals with a Gaussian distribution.
Here, li and pj are the mean or expectation of the distri-
bution of the individual variable (concentration or process-
ing parameter), while ri and Hj represent the standard
deviations of the concentrations and the processing param-
eters, respectively.
The complexity in the formulation of non-standard com-
positions of wrought aluminum alloys in order to achieve the
desired combination of properties is mainly in the large
number of variables involved in the methodical development
of the properties and the proper combination of properties.
The only useful strategy in an industrial environment is “data
mining”, performed on the existing results of the chemical
analysis and the measurement of the mechanical properties
from the regular quality control of wrought aluminum alloys
and the corresponding semi-products, in combination with
the parameters of the heat treatment and forming. These data
are available, but only collected for alloys having the stan-
dard composition. As a result, the question is: how can we
use these values to extrapolate to the alternative, i.e.,
non-standard, compositions?
If the correlation between the properties and the corre-
sponding technological path (chemical composition and
technological parameters) is known within the standard
intervals, then the values obtained by the extrapolation from
the existing data can apply for tailoring the composition
and/or properties of non-standard aluminum alloys.
For the practical application of such an extrapolation
cognitive computing technique it is important to ensure that
the extrapolated values are sufficiently reliable, i.e., that they
are comparable with the experimental findings. To achieve
this, it is reasonable to validate the cognitive modeling by
creating the interpolated values of the mechanical properties
and after that, if these fit well with the experimental findings
V.M. Kevorkijan et al.
for the standard compositions, to apply the same method-
ology for extrapolating the properties of an alloy of the
non-standard composition. The basic idea of the process is
illustrated in Fig. 1. Note that the increasing of the upper
concentration limits of the alloying elements, outside of the
standard compositions, should be limited to just below some
critical value: in practice, typically less than 20%. Under
these boundary conditions, the extrapolated values of the
alloy’s properties, caused by the non-standard alloy com-
position, provide a reliable prediction of the alloy’s prop-
erties, and are suitable for industrial use.
Modeling the Concentration Intervals
Let us consider that the concentration of the particular
composition is Cðl; rÞ. In the wrought aluminum alloy with
the alternative composition, the concentration of that par-
ticular element will be C0 ðl0 ; r0 Þ. The precondition for the
same level of uniformity and reproducibility, i.e., the same
level of quality, is the same (or similar) standard deviation.
Therefore, we can write:
r0  r ð2Þ
In addition, the standard deviation in the alloy with the
alternative composition should be lower than critical:
r0 \rcritical ð3Þ
At the same time, let us denote the average concentration of
the alloying element in the alloy of the standard composition
with µ, and the average concentration of the same alloying
TS
Values measured on alloys of standard composiƟon
Interpolated values calculated for modelled alloys of standard
composiƟon
Extrapolated values calculated for modelled alloys of non-standard
composiƟon
Fig. 1 Schematic presentation of the alloy properties modeling
process based on experimentally measured values of the tensile
strength (TS): the first step in the modeling is the calculation of the
interpolated values of the TS for various standard compositions. The
final step is the calculation of an extrapolated value of TS for an alloy
of the non-standard composition
Algorithm for Finding the Correlation …
element in the alloy having the alternative composition with
µ′.
In order to enable a higher replacement of primary alu-
minum and alloying elements with scrap, it should be:
l0 [ l
Figures 2 and 3 present some of the ways of formulating
alternative concentrations for the selected alloying element.
The first option (the example b in Fig. 2) is based on
increasing the average concentration of the alloying element
without changing its minimum concentration. Of course, the
result of such a formulation of the alternative concentration
interval is an increase of the average concentration and the
maximum allowed concentration, while the minimum
allowed concentration remains the same, as is evident in
Fig. 2. In that case, the increase of the standard deviation is
the same as the increase of the average concentration of the
alloying element.
The second option, as presented in Fig. 3 (example b), is
an increase of the average concentration of the alloying
element, keeping its standard deviation constant. The con-
sequences of that are changes to the minimum, maximum
and the average concentrations of the alloying element, as
shown in Fig. 3, with the composition b. An advantage of
this way of tailoring the alternative concentration interval is
in preserving the same (i.e., comparable) degree of quality,
i.e., the alloy’s uniformity and the reproducibility of its
properties.
Finally, we can simultaneously increase both the average
concentration of the alloying element and its standard
deviation, which corresponds to the composition c in Fig. 3.
Such a solution enables fully independent changes to all the
Fig. 2 An example of a non-standard concentration interval with the
same left-edge concentration (b) as in the standard one (a). The
left-edge of the non-standard concentration interval was designed by
following the rule: l  r ¼ l0  r0 . Consequently, the right-edge is
defined as l0 þ r0
261
ð4Þ
Fig. 3 Possibilities for designing non-standard concentration intervals
starting from the standard one. a Standard concentration interval with
an average concentration of the alloying element, µ, and the standard
deviation, r; b Non-standard interval with an increased average
concentration of the alloying element, µ′, and the same standard
deviation, r; c Non-standard interval with an already increased average
concentration, µ′, and an additionally increased standard deviation, r0
variables and freedom in tailoring an alternative
composition.
It is important to note that the same principles are also
applicable in formulating the intervals (minimum and max-
imum values) for all the other variables, i.e., the different
processing variables or parameters involved in the modeling
of the selected properties of the recycling-friendly alloys.
Mathematically, this is expressed by Eq. 1, in which all the
variables and the tensile strength (TS) on the right-hand side
of the equation appear as Gaussian intervals. It is important
to note that the parameters of the Gaussian distribution of
UTS, on the left-hand side of Eq. 1, are prescribed by the
customer, while all the other variables, appearing on the
right-hand side of Eq. 1, are formulated by the producer of
the alloy.
In order to enable the highest possible replacement of the
primary aluminum and the alloying elements with scrap,
while maintaining the value of UTS inside the required
interval UTS ðl; rÞ, it will be necessary to formulate some
more scrap-friendly compositions. This is usually done by
increasing the average concentrations and the standard
deviations of some of the alloying elements and, especially,
the impurities. However, in this case it is important to ensure
a production process with “narrower” processing parameters
(i.e., a lower standard deviation), which is, in practice, not an
easy task. The opposite solution—narrowing the intervals of
the concentrations of the alloying and trace elements (i.e.,
impurities)—significantly reduces the possibilities for
introducing scrap, which is the current situation in many
wrought-aluminum-alloy casting houses.
262 V.M. Kevorkijan et al.

Table 1 Numerically predicted YS TS A Si Fe Cu Mn Mg Cr Ti

alternative compositions of the (MPa) (MPa) (%) (%) (%) (%) (%) (%) (%) (%)
modified AA6082 alloy in the
as-cast state to provide the desired A1 85 178 17 0.861 0.216 0.042 0.551 0.641 0.103 0.037
combination of mechanical A2 85 224 17 0.975 0.220 0.056 0.544 0.705 0.129 0.034
properties
A3 117 224 17 1.093 0.220 0.056 0.551 0.763 0.139 0.030
A4 117 178 17 0.979 0.216 0.043 0.558 0.699 0.113 0.033
B1 85 178 9 0.963 0.217 0.044 0.564 0.673 0.121 0.034
B2 85 224 9 1.077 0.221 0.058 0.558 0.737 0.148 0.030
B3 117 224 9 1.195 0.221 0.058 0.565 0.794 0.158 0.026
B4 117 178 9 1.081 0.217 0.045 0.571 0.731 0.131 0.030

The additional details of the modeling methodology can

be found in Ref. [3].

A Case Study

The main purpose of the case study was to validate the

Fig. 4 Experimentally tested compositions of the AA6082 alloy in the
as-cast state, with the corresponding mechanical properties. The
boundary compositions (from A1 to B4) are extrapolated from Table 1
Algorithm
In principle, the modeling of wrought aluminum alloys with
the desired combination of properties is based on finding the
surjective and inverse correlation T(C, PP) $ P between the
properties, P, of the final product and the different techno-
logical paths T(C, PP) capable of providing it (and vice
versa). Here, C represents the chemical composition of the
alloy and PP is the processing parameters. The algorithm
presented in this work is based on the functional equivalency
of two different technological paths, T1 and T2, able to
provide the same combination of properties, written as
P(T1) = P(T2), where P(T1) and P(T2) represent the prop-
erties obtained by the various paths T1 and T2 in vector
space. The selection of the best among the functionally
equivalent technological paths, T, was performed by
applying the minimum-cost criterion.
algorithm developed in this investigation.
As a first step, “data mining” was applied to obtain the
results of standard, room-temperature tensile tests and the
corresponding concentrations of the alloying elements for
the 120 different production lots of the AA 6082 alloy. All
the measurements were performed in the as-cast condition.
The as-cast state was selected in order to exclude the influ-
ence of the subsequent processing steps (homogenization,
heat treatment and forming) on the correlation between the
concentration of the alloying elements and the selected
mechanical properties. All the measurements of the ultimate
tensile strength, the yield strength and the elongation were
performed using standard, room-temperature tensile tests.
The bars with a standard geometry for the tensile tests were
machined perpendicular to the direction of the individual
billet casting. The chemical compositions of the samples
were analyzed using optical emission spectroscopy
(OES) with an average accuracy of ±10 ppm.
Next, based on the accumulated data obtained under the
constant, as-cast processing parameters, the property-
composition correlation was established following the
methodology of cognitive computing. Finally, the property-
composition correlation established previously was applied
for the cognitive modeling of the alternative standard and
some non-standard alloy compositions.
The validation of the property-composition correlation
was performed by computing the properties of randomly
selected samples taken from the 120 different production lots
of AA 6082 and vice versa, by computing the chemical
composition of the samples with known mechanical prop-
erties. In both cases the matching was better than 90%.
The standard compositions, modeled to provide the
desired combination of properties, are reported in Table 1. In
Algorithm for Finding the Correlation …
addition, all 120 compositions used to establish the
composition-properties correlation, including the 8 boundary
compositions computed by the model, are plotted in Fig. 4.
The collected results show that even slight differences in
the initial chemical compositions of the individual alloys
cause, in the as-cast state, significant changes in the indi-
vidual and the combined mechanical properties. It is
important to note that under the constant parameters of
melting and casting, the initial, as-cast processing state of the
alloy is a function of the concentrations for the seven
alloying elements (i.e., variables) considered in this study,
Table 1. However, for the samples taken from any subse-
quent stages of processing, the number of variables increases
rapidly, involving not only the concentrations, but also the
various processing parameters. The complete validation of
the algorithm, involving not only chemical composition but
also all the relevant processing parameters, will be carried
out as part of a continuation of this work.
The experimentally determined dependence of the
mechanical properties of the AA6082 alloy on the changes in
the alloy compositions, as illustrated in Fig. 4, confirms that
the property-composition correlation is surjective and inverse.
In other words, the same combination of mechanical proper-
ties could be ensured by applying various alloy compositions,
but, in contrast, from the known alloy properties it is not
263
possible to calculate the alloy composition as a functional
dependence of the alloy properties. However, by applying the
cognitive computing performed on a sufficient number of
experimentally determined values, either the chemical com-
position or the mechanical properties can be predicted with
high accuracy, sufficient for most industrial applications.
Conclusion
A cognitive algorithm for finding the correlation between the
properties of wrought aluminum alloys, the chemical com-
position and the processing parameters was developed and
validated on the AA 6082 alloy.
References
1. S. K. Das, Light Metals 2006, ed. T. J. Galloway (Warrendale, PA:
TMS, 2006) pp. 911–916
2. V. Kevorkijan, Modeling of alternative composition of recycled
wrought aluminum alloys. JOM 65(8), 973–981 (2013)
3. V. Kevorkijan et al., Light Metals 2015, ed. M. Hyland (Warren-
dale, PA: TMS, 2015) pp. 237–244
 Analysis of an Aluminium Alloy Containing
Trace Elements

Christian J. Simensen, Stephan Kubowicz, Børge Holme,

and Joachim S. Graff

Abstract
The microstructure of an Al–Si–Mn–Fe alloy was determined using SEM and Tof-SIMS.
The trace elements detected were chlorides and a minute content of fluorides. Potassium
was found in large cracks along boundaries. Sn was found on the surface of a-Al(Mn,Fe)Si,
on grain boundaries and as separate particles. Small Pb-Sn particles were detected close to
grain boundaries. The a-Al(Mn,Fe)Si-particles were 1–5 lm in size and gave pronounced
Mn- and Fe-peaks in Tof-SIMS, while silicon did not. SEM-analysis showed that the phase
had the composition (wt%): 59Al-12Si-17Mn-12Fe. Separate Tof-SIMS analyses of the
matrix and these particles showed that the particles were sputtered at a slower rate than the
matrix. The sensitivity factor (Sx/Al) was lower in the particles as compared to the matrix.
These observations were explained by the fact that intermetallic phases are substantially
harder that the Al-matrix, and that the Si-atoms and a fraction of the Mn and Fe atoms are
covalently bonded in a-Al(Mn,Fe)Si-particles.

Keywords
Aluminium alloys SEM Tof-SIMS Covalent bonding Microstructure

Introduction
SINTEF has recently acquired a Tof-SIMS (Time-of-flight
Secondary Ion Mass Spectrometry) instrument for analysis
of materials. One well suited task for using this instrument is
analysis of trace elements in aluminium alloys. Therefore, a
material of alloy AA5005 modified with tin, lead and bis-
muth was studied. The sample was homogenized for 12 h at
630 °C in order to obtain regular grains. The material turned
out to be heavily oxidized, but some of the oxide layer on the
surface had peeled off. The “naked” aluminium surface was
analyzed in some detail.
The composition of the material was initially determined
using an emission spectrograph. It was (wt%): 97.5%
C.J. Simensen (&)
S. Kubowicz
B. Holme (&)
J.S. Graff
SINTEF Materials and Chemistry, P.O.Box 124 Blindern, 0314,
Oslo, Norway
e-mail: Christian.J.Simensen@sintef.no
B. Holme
e-mail: Borge.Holme@sintef.no
Al-0.18%Mg-0.39%Si-0.96%Mn-0.42%Fe-0.21%Zn-0.15%
Cu-0.037%Sn-0.016%Pb-0.013%Bi. The annealed metal
was analyzed by a SEM (Scanning Electron Microscope)
equipped with an EDS-analyzer (Energy Dispersive X-ray
Spectroscopy), and finally with Tof-SIMS. The main pur-
pose was to locate and determine trace elements and measure
the larger intermetallic phases. A secondary question was: Is
it possible to use SIMS for quantitative analysis on such
samples?
Experimental Procedure
SEM imaging and analysis was made using a FEI Nova
NanoSEM 650, equipped with an Xmax50 EDS from
Oxford Instruments. Tof-SIMS analysis was performed
using a Physical Electronics TRIFT V nanoTOF instrument
equipped with a 30 keV Ga+ source, and an O2+ gas gun for
sputtering. The primary ion beam (Ga+) was set to the
unbunched mode to be optimized for high lateral resolution.

© The Minerals, Metals & Materials Society 2017 265

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_35
266 C.J. Simensen et al.

Fig. 1 Tof-SIMS images from

area A with sub-areas ROI 1 and
ROI 2 shown in the Mn-intensity
map (left). The corresponding
secondary electron image is
shown at the right

The nanoTOF had a secondary electron detector which of 68.0 lm2 from the matrix were selected and analyzed.
allowed SEM-like images to be made of the analyzed region The total area analyzed was 882.3 lm2 (Fig. 1).
(e.g. Fig. 1 right). Both positive and negative ions were
detected with an analyzed area of 20 lm
20–100 lm

100 lm in size. The following positive ion isotopes were Results
analyzed: 1H, 6Li, 11B, 23Na, 24Mg, 27Al, 30Si, 39K, 40Ca,
48
Ti, 55Mn, 56Fe, 58Ni, 60Ni, 63Cu, 65Zn, 116Sn-120Sn, SEM Investigation
206
Pb-208Pb, 209Bi, along with the negative ion isotopes 19F
and 35Cl. In one case, an ROI (Region Of Interest) of The metal was covered by an uneven oxide layer of
34.8 lm2 with a-Al(Mn,Fe)Si-particles and a reference ROI Al–Mg–O after the homogenization (Fig. 2). However,

Fig. 2 SEM-image from a larger

area than Fig. 1, with the
Al-matrix (grey) that contains
bright 1–5 lm a-Al(Mn,Fe)Si
particles and small, whitish
tin-particles. The “naked” Al is
surrounded by Al–Mg-oxide
(black with grey patches). Dark
regions in the Al matrix indicate
grain boundaries
Analysis of an Aluminium Alloy Containing Trace Elements 267

Fig. 3 Two bright

a-Al(Mn,Fe)Si particles in the
upper left part of area A with
even brighter tin-particles near an
aluminium grain boundary. Some
dark pits show remnants of
particles that have disappeared.
A thin Sn-layer on a grain
boundary is situated between the
two a-particles

some of the oxide had peeled off so we could analyze

directly the aluminium in small areas. SEM-analyzes of the
matrix revealed that the concentrations were less than
0.1–0.3 wt% for all elements, except manganese which had
a concentration of about 0.4 wt% in solid solution.
There were 1–5 lm large Al–Mn–Fe–Si crystals with
small Sn-particles, 0.1–0.5 lm, in the surface (Figs. 2 and
3). Most of these intermetallic particles were a-Al(Mn,Fe)Si
which has a cubic structure with 23–24 atoms of Fe + Mn in
the unit cell of 138 atoms [1, 2]. Analyses of these particles
gave the composition (in wt%) (Fig. 4): 59Al—12Si—17Mn
—12Fe (unit cell: 96 Al-atoms, 18 Si-atoms, 14 Mn-atoms, Fig. 4 Measured concentrations of elements in several a-Al(Mn.Fe)Si
10 Fe-atoms). A small fraction of the particles had more iron particles. For small particles, some of the Al signal comes from the
matrix, which reduced the apparent concentrations relative to Al
in the unit cell: 62Al—9Si—14Mn—15Fe (atoms: 100 Al,
14 Si, 11 Mn, 12 Fe). Tin was also detected as separate
particles (Fig. 2), and in lead-crystals containing a substan- 1–4 lm, contained Mn, Fe and Si (Figs. 6 and 7). The
tial amount of tin (Fig. 5). Si-peak in the mass spectrum was quite weak as compared
with the peaks of Mn and Fe. This phase is a-Al(Mn,Fe)Si.
A second group of particles was salt crystals with size 0.3–
Tof-SIMS Analysis 2 lm (Figs. 8 and 10). There were mixed chlorides of
Na-K-Mg, some KCl, and a few NaF-particles. A third
Several areas were analyzed using Tof-SIMS. Groups of particle type was Sn-particles, 0.3–1 lm in size (Fig. 9). The
intermetallics and trace element particles were detected, as fourth type was Pb-particles of which some contained a
shown in Figs. 6, 7, 8, 9 and 10. The larger particles, substantial amount of tin (Fig. 9). Bismuth was chiefly
268 C.J. Simensen et al.

Fig. 5 Area B with a “large”

a-Al(Mn,Fe)Si particle, some
long cracks, and a few bright Sn
and Pb particles. The top region is
part of the thick, uneven oxides
that surrounded the Al-area

Fig. 6 Tof SIMS concentration

map of Mn (pink) overlaid on a
secondary electron image (left).
The white particles are tin.
Corresponding Fe map (right) on
a dark background. The common
presence of Mn and Fe shows the
position of a-Al(Mn,Fe)Si
particles in area A

found in solid solution, and the concentration varied some- intensities of Mn and Fe were high in a-Al(Mn,Fe)Si, while
what. Finally, K was also detected in cracks in area B the intensity of Si was surprisingly low. Simensen and
(Fig. 10). The intensity of K increased as the sputtering Söderwall [3] have shown that for SIMS-data, the concen-
proceeded into the cracks. In these regions, there was little F tration Cx of impurity element x in an aluminium matrix is:
or Cl present (not shown).
The a-Al(Mn,Fe)Si particles were analyzed in more detail Ix CAl fAl
Cx ¼

ð1Þ
by selecting areas with these particles (area A). The exper- IAl Sx=Al fx
imental data are listed in Table 1, showing that the
Analysis of an Aluminium Alloy Containing Trace Elements
Fig. 7 Tof-SIMS concentration map of Si in area A. Si is also present
in solid solution, but the intensity of Si is slightly higher in the outlined
a-Al(Mn,Fe)Si particles, compare to Fig. 6
Fig. 8 Tof-SIMS concentration maps showing salts of Na, K, Mg, Cl
and F in area A. Mg is not present in all of the Na + K-rich particles.
Three of the particles are chlorides, the others are fluorides. (The image
Fig. 9 Tof-SIMS concentration maps from area A, showing Sn-particles and Sn in solid solution. Pb is also mainly present in particles, while Bi is
more evenly distributed and therefore mostly in solid solution
269
where fx is the abundancy factor of isotope x, Sx/Al is the
relative sensitivity factor of element x in the aluminium
matrix, Ix is the observed intensity of isotope x. The con-
centration of element x in particles of a-Al(Mn,Fe)Si is
correspondingly:
Ixp CAlp fAl
Cxp ¼

ð2Þ
IAlp Sxp=Alp fx
where the subscript p is for elements in the particles. The
relative sputtering rate (b) between the hard intermetallic
phase and the matrix is:
vp IAlp CAl
b¼ ¼
ð3Þ
vAl IAl CAlp
where vp and vAl are the sputtering velocities in the particles
and in the Al-matrix, respectively. The relative sputtering
rate can be estimated by comparing the observed intensities
of Al in the two phases, corrected for the known concen-
trations of Al in the matrix and particle, as shown in Eq. (3).
This calculation assumes that the ionization probability for
Al is the same, thus that the “matrix effect” is small in this
case. The amount of iron in solid solution in AA5005 at
to the right has been cropped somewhat since the imaged region shifted
between the analyses of positive and negative ions.)
270 C.J. Simensen et al.

Fig. 10 Tof-SIMS concentration

maps from area B showing K in
cracks and in salt particles, partly
overlapping with Na. (Compare
with Fig. 5 which shows the same
area)

630 °C is 0.02 wt%Fe [4–6]. The observed concentration of
manganese in solid solution is 0.4 wt% Mn. The estimated
equilibrium content of Si in solid solution is 0.33 wt% Si
and that of manganese is 0.49 wt% Mn at 630 °C [5, 6]. The
results of the calculations using Eqs. (1) and (2), are sum-
marized in Tables 1 and 2. The Sensitivity factor Sx/Al is
larger in the matrix than in a-Al(Mn,Fe)Si. The difference is
large for silicon and iron and none for manganese. The
sputtering rate in the intermetallic phase a-Al(Mn,Fe)Si is
lower than in the matrix (b = 0.91). This number was
determined from Eq. (3) using the intensities of aluminium
in the matrix and in the intermetallic particles, and the
composition of the particles as determined by the SEM-
measurements. That b is less than 1 is expected, since the

Table 1 Tof-SIMS analysis of area A

Isotope Intensity in total area Intensity in ROI 1a Intensity in ROI 2a fx(%) Cx (wt%) Cxp (wt%)
Particles Matrix Matrix a-Al(Mn,Fe)Si
27
Al 18,880,346 10,412,257 18,875,166 100 97.48 59
30
Si 18,067 16,724 18,626 3.1 0.327 12
55
Mn 105,200 778,166 25,155 100 0.488 17
56
Fe 26,526 219,419 5452 91.7 0.020 12
a
The numbers for ROI 1 and ROI 2 are scaled up to match the total area so that numbers can be compared directly
Intensities given as number of counts

Table 2 Determination of sensitivity factors

Isotope Sensitivity factor Sx/Al Relative sputtering velocity: b
In matrix In a-Al(Mn,Fe)Si
27
Al 1.0 1.0 0.91
30
Si 9.5 0.26
55
Mn 0.27 0.29
56
Fe 1.54 0.11

Table 3 Tof-SIMS analysis of trace elements in area A

Element Cx (wt%) fx (%) Ix in the total area Sx/Al
120
Sn 0.037 32.9 40,887 17.4
208
Pb 0.016 52.4 2595 4.6
209
Bi 0.013 100 17,075 6.8
Analysis of an Aluminium Alloy Containing Trace Elements
intermetallic particles are much harder than the matrix, and
since the sputtering rate will depend on the hardness of the
phase.
Analysis of the trace elements in area A showed that the
sensitivity factor for Sn, Pb and Bi was relatively high
(Sx  5–17) as shown in Table 3. It was assumed that the
soft particles of Sn and Pb were sputtered at the same rate as
aluminium in these calculations.
Discussion
This work has demonstrated that the material investigated
had small amounts of particles containing trace elements.
One important particle group is chlorides of Na, Mg, K
and/or Ca. More surprising was that Sn-precipitates formed
heterogeneously on intermetallic particles and also on grain
boundaries. Small Pb and Pb-Sn-particles were also present.
Finally, small a-Al(Mn,Fe)Si particles were detected.
According to our results, this intermetallic phase sputters at a
9% lower rate than the Al-matrix if we assume that the
ionization probability is the same for Al in both phases. In
the Tof-SIMS analysis, the a-particles gave different sensi-
tivity factors than the matrix. The most probable explanation
for this is as follows: Al-atoms and other elements in
the matrix form metallic bonds. The Al-atoms in
a-Al(Mn,Fe)Si-particles also have metallic bonds. However,
Simensen and Bjørneklett [7] have shown that the cubic
a-AlMnSi and a-Al(Mn,Fe)Si phases have high Seebeck
coefficients. Thus, these particles contain covalently bonded
chains of Si–Mn–Fe atoms. According to the model [7], the
Si-atoms form “rings” of 6 atoms around the 000 and ½ ½ ½
positions in the unit cell. These rings are linked together by
Mn (or Fe) and Si atoms. This sub-lattice has strong covalent
bonds that give a high Seebeck coefficient. When this
intermetallic phase is sputtered, our results show that the
covalent Si-atoms are much less likely to be ionized, giving
a relatively low Si+-signal. (The signal from entire rings of
Si6+ was also extremely low.) The conclusion is that the
271
analyses of phases with Tof-SIMS depends both on the type
of bonds between atoms and on the hardness of the phase.
Thus, both the general sputtering rate of particles relative to
the matrix and the matrix effect with different ionization
probabilities will influence the relative sensitivity factors.
The sensitivity factor of silicon changed from 9 in the matrix
to 0.3 in a-Al(Mn,Fe)Si. Surprisingly, manganese showed
virtually no difference in the sensitivity factor between
matrix and particles, while iron did (Table 2). Thus, iron
seems to be covalently bonded in a-Al(Mn,Fe)Si, while
manganese is not. This may be explained in the following
way: Iron has one electron more than manganese in the outer
shell, a smaller atomic radius (aMn = 161 pm versus
aFe = 156 pm) and reduces the lattice parameters of a-Al
(Mn,Fe)Si [1, 2]. Since the iron atoms have a tighter con-
nection to the silicon atoms and there are 10 Fe atoms in
each unit cell of
a-Al(Mn,Fe)Si, then all the sites with covalent bonding to
silicon atoms may be occupied by iron atoms, while the
manganese atoms are metallically bonded.
References
1. J.E. Tibballs, R.L. Davis, B.A. Parker, J. Mater. Sci. 23, 2177–2182
(1989)
2. J.E. Tibballs, J.A. Horst, C.J. Simensen, Precipitation of a-Al(Fe,
Mn)Si from the melt. J. Mater. Sci. 36, 937–941 (2001)
3. C.J. Simensen, U. Södervall, Quantitative analysis of aluminium
alloys using SIMS. Z. Metallkunde 93, 322–329 (2002)
4. A. Oscarsson, W.B. Hutchinson, H.-E. Ekström, D.P.E. Dickson, C.
J. Simensen, G.M. Raynaud, A comparison of different procedures
of determination of Iron in solid solution in aluminium. Z. Mkde 78,
600–604 (1988)
5. K. Tang, Calculations of solubility of elements in Al alloys using
Thermocalc
6. J.O. Andersson, T. Helander, L. Höglund, P.F. Shi, B. Sundman,
Thermo-Calc and DICTRA, computational tools for materials
science. Calphad 26, 273–312 (2002)
7. C.J. Simensen, A. Bjørneklett, A model for a-AlMnSi and
a-Al(Mn,Fe)Si, To be published in the proceedings of the
TMS-conference 2017 in San Diego
 Determination of Aluminum Oxide Thickness
on the Annealed Surface of 8000 Series
Aluminum Foil by Fourier Transform Infrared
Spectroscopy

Özlem İnanç Uçar, Ayten Ekin Meşe, Onur Birbaşar, Murat Dündar,
and Durmuş Özdemir

Abstract
Aluminum foil produced with prescribed thermomechanical processing route develop oxide
film. Alloy chemistry and annealing practices, particularly its duration and exposed
temperature, determine the characteristics of the oxide film. The magnitude and
characteristics of the oxide film may impair surface features leading to serious problems
in some applications, such as coating, printing and in some severe cases failure in
formability. Therefore, it is important for the rolling industry to be able to monitor the oxide
formation on the foil products and quantify its thickness. Well known methods to measure
an oxide thickness that is in the order of nanometer, require meticulous sample preparation
techniques, long duration for measurements and sophisticated equipment. However, in this
study, a simple and rapid grazing angle attenuated total reflectance infrared
(GA-ATR-FTIR) spectroscopic method combined with chemometrics multivariate calibra-
tion has been developed for the oxide thickness determination which is validated with x-ray
photoelectron spectroscopy (XPS). 3000 and 8000 series aluminum foil materials which
were produced by twin roll casting technique were used in this study. Foil samples were
annealed at various different temperatures and annealing times in a laboratory scale furnace.
Immediately after collecting GA-ATR-FTIR spectra, the 3000 series alloy samples were
sent to a laboratory where XPS reference oxide thickness measurements had been
performed. Partial Least Squares (PLS) method was used to develop a multivariate
calibration model based on FTIR spectra and XPS reference oxide thickness values in order
to predict the aluminum oxide thickness. The correlation coefficient of XPS reference oxide
thickness values versus grazing angle ATR-FTIR based PLS predicted values was found as
0.9903 the standard error of cross validation (SECV) was found to be 0.29 nm in range of
4.9–14.0 nm for Al2O3. In addition, the standard error of prediction (SEP) for the validation
set was 0.24 nm with the model generated with three principal components (PCs).

Keywords
Twin roll casting Oxide film 8000 series aluminum alloy Fourier transform infrared
spectroscopy

Ö.İ. Uçar
O. Birbaşar (&)
M. Dündar

Assan Alüminyum San. ve Tic. aS, Tuzla, 34940, Istanbul, Turkey
e-mail: onur.birbasar@assanaluminyum.com
A.E. Meşe
D. Özdemir
İzmir Yüksek Teknoloji Enstitüsü Fen Fakültesi Kimya Bölümü,
Urla, 35430, İzmir, Turkey
D. Özdemir
OBA Kemometrik Yazılım Eğitim ve Danışmanlık Hiz.,
İZTEKGEB, A6 no:1/F, Urla, 35430, İzmir, Turkey

© The Minerals, Metals & Materials Society 2017 273

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_36
274
Introduction
With increasing production and consumption amounts, alu-
minum is the leader in the metallurgy of non-ferrous metals.
Development of processes for aluminum and its alloys can
be attributed to several of its properties. One of the pro-
duction techniques of foil and sheet aluminum alloys is
twin-roll casting (TRC). This production method has been
used for almost 50 years in the aluminum industry. In
twin-roll casting, molten metal is fed into two water-cooled
rotating rolls, where it solidifies, and then rolled, producing
sheet directly from the melt. A wide range of thicknesses and
widths can be produced by twin-roll casting [1, 2].
Aluminum sheets with a thickness below 200 µm are
described as foils. Coils are cast by utilizing twin roll casting
technology (TRC) then subjected to various annealing and
rolling practices to obtain foil materials. There are many
applications of foils such as: thermal insulations, fin stocks,
semi-rigid containers, household foils etc. 8000 series alu-
minum alloy is one of the typical alloy used for foil pro-
ductions [3, 4].
Although raw aluminum alloys generally covered with a
very thin natural oxide layer, the thickness of oxide layer on
the surface of aluminum is tend to grow significantly with
increasing temperature [5–7]. One of the steps in the manu-
facture of aluminum foil is an annealing operation which is
used to impart ductility to the foil and to remove lubricants
from the surface of the foil. Although it develops an oxide
layer on the surface, alloy chemistry, annealing atmosphere,
annealing temperature and its duration have significant
influence on the composition and characteristics of oxide
layer [8]. The thickness of oxide layer formed on aluminum
alloy has a significant importance in adhesion and wetting
characteristics as well as corrosion resistance [9, 10]. Pres-
ence of oxide layer on foil surface creates serious problems
for some specific applications of aluminum foils in certain
industries such as food packaging where the deep drawing
application is critical and brazing applications in industry
where wetting characteristic on the aluminum surface directly
affect the mechanical bonding and heat transfer systems.
The thickness of end-product is crucial and usually it
should be lower than 50 Å, especially for brazing applica-
tion. To determine accurate measurement of 50 Å or lower
thickness of oxide later, more sophisticated techniques are
needed. Although sophisticated techniques like x-ray pho-
toelectron (XPS) [11, 12] and transmission electron micro-
scopy (TEM) [13] are suggested in academic area for both
Table 1 Chemical composition Element, wt%
of the foil
Alloy Si
8000 series 0.16
Ö.İ. Uçar et al.
determination and characterization of oxide thicknesses,
these methods take extended period of time and expensive.
Present study investigates the oxide formation on the
surface of aluminum foil for 8000 series alloy produced by
industrial annealing practices. A series of samples were
prepared from 3000 and 8000 series alloys in a laboratory
scale annealing furnace under different annealing parameters
(time, temperature) to determine the oxide thickness. In
order to develop partial least squares (PLS) chemometrics
calibration models, x-ray photoelectron spectroscopy
(XPS) were used for the reference analysis of oxide thick-
ness measurements on 3000 series samples. The models
generated with 3000 series samples were used to determine
oxide thicknesses of 8000 series alloys based on infrared
spectroscopic method combined with PLS multivariate
calibration.
Experimental Studies
8000 series alloy samples gathered from the final thickness
of the production were investigated in order to characterize
the surface properties. The alloy is continuously strip cast by
an industrial scale twin roll caster. As-cast strip was pro-
cessed to final foil gauge according to the processing route
for producing container foil. The production process consist
of homogenization annealing at a certain strip thickness,
cold rolling, foil rolling and soft annealing at the final
thickness respectively. Chemical composition of the 8000
series alloy is given in Table 1.
To observe the effect of nitrogen and air annealing on the
oxide formation, coils were soft annealed under two different
atmosphere in an industrial scale furnace. After annealing
operation foil samples were investigated by employing
scanning electron microscope (SEM). Surface roughness
(Ra) of the sample was measured on five different regions of
both samples via non-contact optical profilometer.
To determine aluminum oxide thickness which is formed
in the nanometer range on the surface of aluminum foil
products, FTIR spectroscopy and PLS multivariate calibra-
tion approaches are applied on a series of samples prepared
under laboratory conditions. Foil samples gathered from the
serial production before soft annealing operation, were
annealed at 200, 250, 300, 350, 400, 450 and 500 °C for
various annealing times (1, 3, 5, 8 h) in air atmosphere.
In order to develop PLS multivariate calibration models, a
data set which was gathered from a previous study were
Fe Cu Mn Ti
1.43 0.03 0.63 0.01
Determination of Aluminum Oxide Thickness … 275

used. The data set contains 20 samples of 3000 series alloy
of which XPS reference analysis of aluminum oxide (Al2O3)
had been conducted by Prof. Dr. Şefik SÜZER (Bilkent
University, Department of Chemistry). The 20 samples were
subjected to five different annealing temperature (300, 350,
400, 450 and 500 °C) and four different annealing time (1, 3,
5 and 8 h). Table 2 shows the reference oxide measurements
of these 20 samples.
Grazing Angle Attenuated Total Reflectance (GATR)-
FTIR spectra of 20 samples were recorded by using Perkin
Elmer Spectrum 100 FTIR Spectrometer coupled with
GATR accessory in the wavenumber range of 4000–
600 cm−1. The fact that XPS analysis of oxide thickness is
quite time consuming and expensive, it was decided to use
PLS models generated with 3000 series alloy which com-
position is similar to 8000 series aluminum alloy foil
samples.
Results and Discussion
The macro images of the foil materials which were annealed
in two different atmospheres during production are given in
Fig. 1. It is clearly seen that the foil surface annealed in air
atmosphere looks different from the other one. Foil material
annealed in nitrogen atmosphere shows a uniform surface
appearance without any visually observable oxidation.
However, foil annealed in air atmosphere has white stains at
the edges which were formed due to the oxidation during
annealing. This heterogeneity on the foil surface leads to
different surface tension conditions to appear on the oxidized
areas.
To make further studies, oxidized regions were examined
via the scanning electron microscope comparatively with the
foil having no oxidation (sample on the left in Fig. 1). As
seen in Fig. 2, secondary electron images reveal that the
oxidation leads to degradation on the foil surface (Fig. 2a,
c). The oxidized foil sample surface partially shows micro
holes and an uneven surface appearance as compared to the
non-oxidized sample (Fig. 2b, d).
The average results of surface roughness measurements
show that the oxidized sample and non-oxidized sample
exhibit a surface roughness (Ra) values of 0.388 and 0.221,
respectively. This observation is consistent with results of
SEM images.
Homogeneous distribution and the amount of the lubri-
cant on the foil surface is critical for deep drawing appli-
cations [14]. The oxide film formations on the foil surface
creates serious problems for some specific applications in
which a lubricant is applied and foil is deep drawn to con-
tainers. Oxidized surfaces of the foil can affect the proper
application of lubricant due to having different roughness
profiles and resulting surface tension. Also, surface rough-
ness plays an important role during forming process [15]. An
increase in the roughness parameters of the foil may change
the friction conditions between die surface and foil. Because
of these reasons, the magnitude of oxide layer formed on the
foil surface is very crucial for similar applications.
After completing XPS reference analysis studies, multi-
variate modelling studies were conducted to determine the

Table 2 Al2O3 thicknesses of 20 Thickness of Al2O3 (nm) Annealing time, h

samples belong to 3000 series of
aluminum alloys determined by Annealing temperature, °C 1h 3h 5h 8h
XPS method 300 4.9 5.1 5.3 5.5
350 5.5 5.8 6.2 6.6
400 6.6 7.1 7.4 8.0
450 8.0 9.0 10.0 11.0
500 11.0 12.0 13.0 14.0

Fig. 1 The macro photographs

of the foil materials annealed in
two different atmosphere
(nitrogen and air)

Annealed in nitrogen atmosphere Annealed in air atmosphere

276 Ö.İ. Uçar et al.

(a) (b)

(c) (d)

Fig. 2 Secondary electron images of aluminum foil surfaces. a, c Foil surface annealed in air atmosphere. b, d Foil surface annealed in nitrogen
atmosphere

0.5 As can be seen from Fig. 3, raw FTIR spectra of the

0.45 samples exhibits serious baseline shift problems and there-
0.4 fore spectra must be baseline corrected before further anal-
0.35 ysis. The fact that the baseline of the spectra shows
Absorbance

0.3 somewhat nonlinear trend, a second order polynomial

0.25 baseline function was fitted to each spectrum and this
0.2 baseline spectrum were then subtracted in order remove
0.15 baseline offset. Figure 4 shows the baseline corrected FTIR
0.1 spectra of the 3000 series alloy samples.
0.05 As seen from Fig. 4, after baseline correction, absorbance
0 peak around 950 cm−1 was become apparent in relation to
3500 2500 1500 500 the reference oxide thickness values given in Table 2. At this
Wavenumber (cm -1) point, one might consider using a simple least squares
approach to develop calibration model for the oxide thick-
Fig. 3 Grazing Angle ATR-FTIR spectra of the 20 samples from 3000
series alloy ness. However, the spectra have some shift on the
wavenumber scale at the peak maxima and this cause
deviation from linearity at the peak maxima. Partial least
thickness of Al2O3 based on FTIR spectroscopy. Figure 3 squares (PLS) is well known factor based calibration method
shows Grazing Angle ATR-FTIR spectra of the 3000 series which is used for complex multivariate problems [16–18].
alloy samples which are given in Table 1. A modified version of the PLS algorithm which was
Determination of Aluminum Oxide Thickness … 277

implemented in MATLAB Programming environment was With the use of the PLS multivariate calibration method
used to develop multivariate calibration model for the Al2O3 quite successful model was developed for the Al2O3 thick-
thickness determination from FTIR spectra. For this, 17 ness determination based on Grazing Angle ATR-FTIR
samples from Table 2 were used to construct calibration set spectroscopy without tedious and time consuming reference
and the remaining 3 samples were used to construct inde- XPS analysis. As seen from Fig. 5, the correlation coeffi-
pendent validation set for 3000 series aluminium alloy. cient of the reference oxide thickness values vs. PLS pre-
Modelling is done with a leave-one-out cross validation in dicted values was around 0.99 and the standard error of cross
the calibration set and the model was also tested with the validation (SECV) was found to be 0.29 nm in an interval of
independent validation set. Figure 5 shows reference vs. 4.0–16.0 nm. In addition, the standard error of prediction
predicted plot of Al2O3 thickness. (SEP) for the validation set was 0.24 nm with the model
generated with three principal components (PCs).
In order to test the predictive performance of the PLS
0.05 multivariate calibration model for the Al2O3 thickness
determination, a total of 28 samples of 8000 series of alu-
0.04 minium alloy which were annealed at seven different tem-
perature (200, 250, 300, 350, 400, 450 and 500 °C) and four
0.03
Absorbance

different annealing times (1, 3, 5, 8 h) in air were used.

0.02 Figure 6 shows the baseline corrected Grazing Angle
ATR-FTIR spectra of the 28 samples annealed in air atmo-
1000 950 900 850 800
0.01 sphere from 8000 series alloy.
When compared with the Fig. 4 which gives the 3000
0
4 0 0 0 3 5 0 0 3 0 0 0 2 5 00 2 0 0 0 1 5 0 0 1 0 0 0 500 series alloy baseline corrected FTIR spectra, the 8000 series
-0.01 alloy baseline corrected FTIR spectra shows some differ-
Wavenumber (cm-1) ence. However, the general appearance of the main absor-
bance peak around 950 cm−1 corresponding Al2O3 is quite
Fig. 4 Baseline corrected Grazing Angle ATR-FTIR spectra of the
3000 series alloy samples
similar in both Figs. 4 and 6. This similarity in FTIR spectra
of both 3000 and 8000 series alloys makes it possible to use
the PLS model generated with 3000 series samples in the
prediction of oxide thickness of the 8000 series alloy sam-
16 ples. Table 3 shows the predicted Al2O3 thickness of 8000
y = 0.9903x + 0.0803 series alloy annealed in air atmosphere. As seen from
PLS Prediction Results of Al2O3 thickness (nm)

R² = 0.9903 Table 3, annealing atmosphere at various temperature and

14 time settings generated aluminium oxide thickness values
ranging from 4.23 to 14.36 nm. Although the Al2O3 thick-
ness prediction values given in Table 3 are in good agree-
12 ment with the XPS reference analysis of the 3000 series

10 0.06

0.05

0.04
8
Calibration 0.03
Absorbance

Validation 0.02
6 1000 900 800
0.01

0
4 3600 3100 2600 2100 1600 1100 600
-0.01
4 6 8 10 12 14 16
-0.02
Reference XPS results of Al2O3 thickness (nm) Wavenumber (cm-1)

Fig. 5 Reference versus predicted plot of Al2O3 thickness by using Fig. 6 Baseline corrected Grazing Angle ATR-FTIR spectra of the
PLS method 8000 series alloy samples annealed in air atmosphere
278 Ö.İ. Uçar et al.

Table 3 PLS predicted Al2O3 Annealing time (h) Annealing temperature

thickness of 8000 series alloy
annealed in air atmosphere 200 °C 250 °C 300 °C 350 °C 400 °C 450 °C 500 °C
1 4.26 4.79 5.59 6.43 8.01 12.57 13.15
3 4.23 5.31 5.87 7.39 9.81 12.78 14.36
5 4.61 4.89 5.93 8.31 11.47 12.42 14.18
8 4.78 5.38 6.48 8.39 9.58 11.88 14.05

alloy samples, future studies should be done to further val-
idate and improve the method, since only 3000 series Al
alloy samples were used for model construction and
validation.
Conclusions
An increase in the surface roughness of the foil creates serious
problems for some specific applications such as deep drawing
of the foil, lacquering and printing. Annealing in air atmo-
sphere can cause oxidation on the foil surface and increases
surface roughness of the material. However, the results
demonstrated that oxide thickness is greatly affected by
annealing temperature rather than annealing time. On the
other hand, annealing in nitrogen atmosphere is expected to
protect material surface from the air oxidation as seen from
production sample surfaces shown in Figs. 1 and 2. However,
pilot scale nitrogen atmosphere annealing is currently under
study and the results will be presented in a further report.
Successful PLS multivariate calibration model was
developed for the Al2O3 thickness determination based on
Grazing Angle ATR-FTIR spectroscopy. Determination of
aluminum oxide thickness on the annealed surface of 8000
series aluminum foil by Fourier transform infrared spec-
troscopy coupled with PLS multivariate calibration model
reveals that aluminium oxide thickness values are found to
be ranging from 4.23 to 14.36 nm.
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 Using Guard Bands to Accommodate
Uncertainty in the Spark AES Analysis
of Aluminum or Aluminum Alloys When
Determining Compliance with Specified
Composition Limits

Thomas Belliveau, Denis Choquette, Olivier Gabis, Michael Ruschak,

John Sieber, Albert Wills, and Rebecca Wyss

Abstract
Every pound of aluminum or aluminum alloys cast and sold is certified to meet The
Aluminum Association Inc. registered limits or other specified composition limits.
Certification of aluminum and aluminum alloys to specified composition limits is typically
done using Spark-Atomic Emission Spectrometry (Spark-AES) following the procedures in
ASTM International (ASTM) E716 Standard Practices for Sampling and Sample
Preparation of Aluminum and Aluminum Alloys for Determination of Chemical Compo-
sition by Spectrochemical Analysis and ASTM E1251 Standard Test Method for Analysis
of Aluminum and Aluminum Alloys by Spark–AES. Spark-AES laboratories at major
aluminum production facilities normally have excellent analytical practices and follow
strict quality control protocols to provide the best results possible. However, every
measurement has an associated uncertainty and the measurement of composition using
Spark-AES is no exception to the rule. This paper provides a brief discussion of:

1. The uncertainty inherent in the elemental analysis of aluminum and aluminum alloys by
Spark-AES.
2. The benefits of using guard bands to set internal operating limits, which are offset from
specified composition limits.

T. Belliveau
Novelis, Atlanta, USA
e-mail: Thomas.Belliveau@novelis.adityabirla.com
D. Choquette
Rio Tinto, London, UK
e-mail: denis.choquette@riotinto.com
O. Gabis
Wagstaff, Spokane Valley, USA
e-mail: olivier.gabis@wagstaff.com
M. Ruschak (&)
R. Wyss
Alcoa, Pittsburgh, USA
e-mail: Michael.Ruschak@alcoa.com
R. Wyss
e-mail: rebecca.wyss@alcoa.com
J. Sieber
NIST, Gaithersburg, USA
e-mail: john.sieber@nist.gov
A. Wills
Sapa, Rosemont, USA
e-mail: albert.wills@sapagroup.com

© The Minerals, Metals & Materials Society 2017 279

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_37
280 T. Belliveau et al.

3. A model of the risk for sale of out-of-specification product based on the analysis
uncertainty relative to the specified composition limits.
4. The main sources of uncertainty of Spark-AES and their potential causes.

Keywords
Aluminum Chemical composition Guard bands Spark-AES Uncertainty

Terms E716, and analyzing the samples using Spark Atomic

Emission Spectrometry (Spark-AES) according to ASTM
• Bias—The difference between the average value of the E1251. The goal is always to provide accurate quantitative
test results and an accepted reference value. results, but uncertainty occurs in all Spark-AES measure-
Note: Bias is the total systematic error as contrasted to ments, even when using properly calibrated instruments and
random error. There may be one or more systematic error the best possible sampling, sample preparation and analysis
components contributing to the bias. A larger systematic procedures. The inherent uncertainty of the analysis should
difference from the accepted reference value is reflected by be considered when establishing and determining compli-
a larger bias value. ance with specified composition limits. Under the best of
Note: An accepted reference value comes from either a circumstances, two analyses on the same sample will not
certified reference material or results from analysis of the likely produce the same results, even when using the same
product by a method that is accepted as having no bias. instrument. This uncertainty in measuring composition may
• Detection limit, in analysis—The minimum single result cause the following problems when the analysis result is
which, with a stated probability, can be distinguished close to a specification limit:
from a suitable blank value.
Note: The limit defines the point at which the analysis 1. a false negative outcome, (i.e. a measured composition
becomes possible, and this may be different from the that is outside the specification limit when the actual
lower limit of the determinable analytical range. composition meets the specification) or
Note: Detection limit may be estimated by using a fully 2. a false positive outcome (i.e. a measured composition
calibrated method to measure 10 independent sample that meets the specification limit when the actual com-
blanks once each and calculating the mean mass fraction position is outside the specification).
result, xbl , and its standard deviation, s. LoD ¼ jxbl j þ 3s.
• Guard bands—The differences between internal operat-
ing limits and specified composition limits.
• Measurement uncertainty—parameter, associated with the
result of a measurement, which characterizes the disper-
sion of the values that could reasonably be attributed to the
measurand including random and systematic errors.
• Operating range—Compositions within the internal
operating limits, which are inside the specified composi-
tion limits.
• Furnace composition variability—the distribution of
compositions resulting from multiple furnace charges and
furnace alloying practices, which include a variety of
metal sources, uncertainty in melt weight, temperature
variations, and oxidation or volatility considerations.

Introduction

Producers of aluminum or aluminum alloys typically mea-

sure composition on 100% of their cast products by taking
samples from the molten metal, in accordance with ASTM
Fig. 1 False negative outcome
Using Guard Bands to Accommodate Uncertainty in the Spark … 281

results, assumed to be normal or Gaussian shaped, around an

actual (true) value. Figure 1 illustrates the possibility that a
measured result of a sample, having an actual composition
above the specified minimum composition limit, is below the
specified minimum composition limit due to the inherent
uncertainty of the analysis. This illustrates the case of a false
negative outcome. Conversely, Fig. 2 shows the case of a
false positive outcome where a measured result of a sample
is above the specified minimum composition limit, but the
actual composition is below the specified minimum com-
position limit.

Discussion of Guard Bands

An effective way to accommodate measurement uncertainty

Fig. 2 False positive outcome
When the uncertainty interval of a Spark AES measured
result overlaps a specified composition limit, the likelihood
for a false positive or a false negative outcome increases, as
illustrated in Figs. 1 and 2.
The bell shaped curves in Figs. 1 and 2 represent the
expected frequency distribution of measured Spark AES
is through the use of internal operating limits tighter than the
specified composition limits as shown in Fig. 3. Assuming
that the furnace composition variability follows a normal
distribution centered on the nominal composition of a given
alloy specification, the figure shows how the knowledge of
measurement uncertainty can be used to select internal
operating limits that protect against occurrences of false
negative or false positive outcomes. The differences between
internal operating limits and specified composition limits are
sometimes referred to as guard bands. According to Fig. 3,
product having an analysis result between the internal
operating limits would be expected to comply with the
specified limits. However, product having an analysis value

Fig. 3 Illustrates the case where

the specified composition range is
wide enough to accommodate
both the furnace composition
variability and guard bands to
account for Spark–AES test
method uncertainty. This is the
best case scenario for reliably
producing product that meets
specified composition limits
282 T. Belliveau et al.

between the internal limits and the specified composition measurement uncertainty for results close to the operating
limits may or may not meet the specified composition limits limits defined by guard bands may overlap, and the furnace
due to the measurement uncertainty. When establishing composition variability exceeds the specified composition
practices to ensure compliance with specified composition limits. In this case, the use of guard bands and operating
limits, producers should consider the use of guard bands limits to account for Spark AES test method uncertainty is
based on the Spark-AES test method uncertainty. impossible, which increases the probability of shipping
Consider the case illustrated in Fig. 4 where the specified product that is outside the specified composition limits. This
composition range is wide enough to accommodate guard scenario also results in the production of internal scrap and
bands but not wide enough for the operating range to be its attendant impact on cost and delivery.
greater than the furnace composition variability. In this case,
the use of guard bands will ensure the product composition
is within specified composition limits. However, as the
specified composition range becomes tighter, it becomes
more difficult and less practical to produce product that
reliably meets the specified composition limits without
generating excessive internal scrap. Based on the expected
furnace composition variability, some amount of product
with composition between the specified composition limit
and operating limit will be scrapped, which may impact the
cost and on-time delivery of the product.
In the worst case scenario as illustrated in Fig. 5, the
specified composition range becomes so narrow that the

Fig. 5 Illustrates the effect of further restricting the specified compo-

Fig. 4 Illustrates the effect of a narrow specified composition range sition range such that the use of guard bands and operating limits
relative to the operating range and the furnace composition variability becomes impossible
Using Guard Bands to Accommodate Uncertainty in the Spark …
Guard Band Examples
Only a detailed analysis of the various sources of uncertainty
can provide an accurate estimate of their magnitudes. The
magnitude of the uncertainty may vary with concentration
and element as shown by the precision and bias data given in
Table 1 of ASTM E1251. Modern instruments often have a
short term variation (spark to spark) better than 0.5% relative
on good quality certified reference materials (CRM) and 1%
relative on homogeneous production samples. Repeatability
between sparks on reference materials and samples is only
one part of the overall uncertainty of the final composition
result. Sampling, sample preparation, certification uncer-
tainty on CRM, drift correction method, type standardiza-
tion, and instrument drift add to the total uncertainty of the
result. Considering the sources of uncertainty, it is likely that
even the best labs have an overall uncertainty of about ±3%
relative, which is used in the following examples. This
uncertainty may be somewhat higher close to the detection
limit or in certain specific alloys (e.g. hypereutectic alloys).
The uncertainty of 3% chosen for the examples is not
intended to represent the uncertainties for all laboratories. In
some instances it may be possible for individual laboratories
to operate at a lower level of uncertainty.
Example 1—Alloy with specified composition limits
wide enough for effective use of guard bands
Consider an alloy having specified composition limits of
4.0–5.0% with a mid-point composition of 4.5%.
It is expected that the Spark-AES uncertainty from
repeated analysis of the control material and sampling effects
is as much as 3% relative. Calculations based on 3%
uncertainty result in guard bands of 0.135% (i.e. 0.03 *
4.5%) and internal operating limits of 4.135% (i.e.
4.0 + 0.135%) and 4.865% (i.e. 5.0–0.135%). These limits
define the operating range and would protect against false
negative and false positive results, ensuring that the product
complies with the specified composition limits.
The operating range with these internal operating limits
is ±8% relative around the mid-point composition of 4.5%
(i.e. ±(100 * (4.865 − 4.135)/4.5)/2), which is a large
enough window for the combination of furnace composition
variability and analysis uncertainty. In this case, the use of
guard bands is possible.
Example 2—Alloy with specified composition limits
too narrow for effective use of guard bands
Consider an alloy having more narrow specified composition
limits of 4.2–4.8% with a mid-point composition of 4.5%.
Again, calculations based on 3% relative uncertainty
yield guard bands of 0.135% (i.e. 0.03 * 4.5%) and internal
operating limits of 4.335% (i.e. 4.2 + 0.135%) and 4.665%
(i.e. 4.8–0.135%). These limits define the operating range
283
and would protect against false negative and false positive
results ensuring that the product complies with the specified
composition limits. However, because of analysis uncer-
tainty of ±3%, an alloy sample having an actual composi-
tion of 4.5% may yield analysis results between 4.365 and
4.635%, which consumes nearly the entire operating range
of 4.335–4.665%.
The operating range with these internal operating limits
is ±3.7% relative around the target composition 4.5%
(i.e. ±(100 * (4.665 − 4.335)/4.5)/2), which is a very narrow
window for the combination of furnace composition vari-
ability and analysis variability. As a result, the use of guard
bands would not be possible.
This discussion shows the importance of having specified
composition limits that are wide enough to accommodate
producer guard bands based on the expected uncertainty of
measurement process while allowing for an adequate win-
dow for furnace composition variability. Customers should
work with their suppliers to establish practical composition
limits.
The above examples focus on potential risk of a supplier
shipping off-composition product for a single element.
However, the probability of shipping off-composition pro-
duct can significantly increase when analyzing for multiple
elements, if guard bands based on analysis uncertainty are
not used.
Figures 6 and 7 illustrate the probability that out of
specification product will be shipped as a function of the
number of elements with guard bands varying from 0 to 5%
relative difference from specified composition limits. The
y-axis in Fig. 6 has been expanded in Fig. 7 to show the
probability of shipping off-composition product when the
guard bands are between 3 and 5%. The values plotted in
Figs. 6 and 7 have been calculated using two standard
deviations equaling 3% relative uncertainty in analysis.
Figures 6 and 7 highlight the beneficial use of guard
bands by showing that the probability for an alloy to be
off-composition decreases as the magnitudes of the guard
bands increase, especially when multiple elements are con-
sidered. For example, the curve for a guard band of 0%
magnitude (i.e. no guard band) in Fig. 6 shows that there is a
50% probability the alloy will be outside the specified
composition limits when the measured composition of an
individual element is at the specified composition limit. With
the same guard band of 0% magnitude, the probability that
the alloy will be outside the specified composition limits
increases to 75% when the measured compositions of two
individual elements are at the specified composition limits.
As the measured compositions of more elements are at the
specified composition limits, the probability that the alloy
will be outside the specified composition limits increases
exponentially.
284 T. Belliveau et al.

Table 1 Typical sources of uncertainty for spark-AES analysis of aluminum and aluminum alloys
Source of Systematic Random Potential causes
uncertainty error error
Calibration x ∙ Inappropriate calibration model
∙ Too few calibrants
∙ Calibrant(s) with inadequate composition
∙ Calibrant(s) with inaccurate or inhomogeneous composition
∙ Calibration beyond instrument capability range
∙ Extrapolation beyond element calibration range
Spectral x x ∙ Instrument configuration not suitable for analysis requirement
interferences and ∙ Incorrect inter-element correction models
matrix effects ∙ Too few calibrants for setting correction models
∙ Calibrant(s) with inadequate composition
∙ Calibrant(s) with inaccurate or inhomogeneous composition
Standardization x x ∙ Incorrect selection of high (slope) and low (offset) drift correction standard samples
(drift correction) ∙ Only one drift correction standard sample for a particular element
∙ Inhomogeneous drift correction standard sample
∙ Magnitude of the slope and/or offset drift correction factors too high
∙ Insufficient frequency of standardization
∙ Insufficient number of sparks
∙ Extrapolation beyond element calibration range
∙ Calibrant inaccurate composition
∙ Improper replacement procedure for implementing new drift correct standards
∙ Contaminated analytical surface (finger print, coolant, air)
Type x x ∙ Type standard with composition or metallurgical history not similar to production
standardization sample(s)
∙ Extrapolation beyond element calibration range
∙ Type standard with inaccurate composition
∙ Incorrect selection of slope or offset type standardization factor
∙ Inhomogeneous type standard sample
∙ Magnitude of the slope and/or offset correction factors too high
∙ Insufficient frequency of type standardization
∙ Insufficient number of sparks
∙ Contaminated analytical surface (finger print, coolant, air)
Control sample x ∙ Control sample with composition or metallurgical history not similar to production
analysis sample(s)
∙ Inhomogeneous control sample
∙ Insufficient frequency of analysis
∙ Absence of corrective action following an out of control result
∙ Control sample limits too wide or too narrow
∙ Insufficient number of sparks
∙ Contaminated analytical surface (finger print, coolant, air)
Production sample x x ∙ Sample composition outside element calibration range
analysis ∙ Insufficient number of sparks
∙ Air infiltration between instrument stand and sample
∙ Spark overlap
∙ Electrode not properly cleaned
∙ Sparks outside the recommended spark radius as depicted in ASTM E-716
∙ Corrective action not taken when control sample analysis outside control limits
∙ Contaminated analytical surface (finger print, coolant, air)
Instrument x x ∙ Temperature stability of instrument
∙ Optical slit profile adjustment
∙ Cleanliness of sample stand and argon supply line
∙ Argon quality
∙ Electrode positioning adjustment
∙ Lens cleanliness
Laboratory x x ∙ Room temperature fluctuations
environment ∙ Humidity fluctuations
∙ Line voltage fluctuations
Note The list of sources of uncertainty was developed with the understanding that sample and reference material preparation conform to ASTM
E716, and instrument operation and analysis practices conform to ASTM E1251
Using Guard Bands to Accommodate Uncertainty in the Spark … 285

Fig. 6 Probability a cast is

off-composition for product with
guard bands between 0 and 5% of
the nominal concentration for a
sample assuming a 3% relative
uncertainty in analysis

Fig. 7 Expanded scale—

Probability a cast is
off-composition for product with
guard bands between 3 and 5% of
the nominal concentration for a
sample assuming a 3% relative
uncertainty in analysis

Significant Digits
Spark-AES instruments can generate composition results
with many more decimal places than are meaningful based
on the uncertainty of the measurement. As a result, consid-
eration should be given to the numbers of significant digits
both requested and reported. To comply with ASTM E1251
[1], alloy compositions shall not be reported with more
significant digits or higher precision than that of the certified
reference material(s) used to calibrate or type standardize the
spectrometer.
A good guideline regarding the certification of aluminum
alloys is to report composition results using the number of
decimal places specified by The Aluminum Association
286
registration records and ANSI standards [2–5]. The stan-
dards established by the Aluminum Association can gener-
ally be met with commercially available certified reference
materials typically used for the control of spectrometers.
Trace Elements
Most of the discussion above focused on uncertainty in the
analysis of alloying elements that are intentionally added.
Specifications also typically include maximum levels
allowed for some trace elements that may be present natu-
rally in the base metal, in the alloying materials, or unin-
tentionally introduced during the melting and casting
processes. Two factors must be considered before requesting
or accepting a specification for a trace level element: (1) the
ability of the Spark-AES test method to quantify the element
at the mass fraction in the specification, and (2) the avail-
ability of reference materials with values and uncertainties
that are suitable for the maximum level in the specification.
Spark-AES instrument manufacturers typically report
instrument detection limits for most elements in advertising
literature and in documentation supplied with new instru-
mentation. Such estimates of instrument detection limits are
made either under ideal conditions using high-purity alu-
minum or from the calibration model. In either case, the
resulting estimate of the instrument detection limit is nor-
mally much lower than the method detection limit estimated
using a standard test method developed for the analysis of
aluminum alloys. This method detection limit estimation
includes corrections for spectral and inter-element interfer-
ences, background signal shift, metallurgical structure, and
material homogeneity.
Neither the instrument nor the method detection limit
should be used to establish specification limits for trace
elements. The method detection limit determines whether an
element can be reported as present. The quantification limit
determines whether a numerical value can be reported for the
element. The quantification limit typically is 3–5 times the
method detection limit. The maximum specification limit for
a trace element should be set at some factor above quan-
tification limit to accommodate analysis and reference
material uncertainty.
In addition, reference materials of aluminum influence the
lower limit of the calibrated analytical range. Values for
trace elements in reference materials normally have uncer-
tainty estimates up to 100 times greater than the instrument
manufacturer’s estimated detection limit.
Performance data based on actual analysis of trace ele-
ments in aluminum alloys by expert labs in the industry can
T. Belliveau et al.
be found in the inter-lab study included in ASTM E1251
(Standard Test Method for Analysis of Aluminum and
Aluminum Alloys by Spark Atomic Emission Spectrome-
try). ASTM E1251 [1] also recommends against analysis of
mercury (Hg) in Aluminum by Spark-AES.
The Main Sources of Uncertainty of Spark-AES
and Their Potential Causes
Uncertainty in elemental analysis, as in any analytical
method, arises from systematic errors that introduce a bias in
the analysis and random errors arising from small variations
from a number of sources. The following discussion assumes
systematic errors have been minimized by adherence to
appropriate practices as defined in ASTM methods E716 and
E1251, vendor recommended analysis practices, and the use
as calibrants of reference materials composition similar to
the alloys being analyzed.
Random error appears as variability in the measurement
process. The variability may be observed in the short term as
“spark-to-spark” or sample-to-sample variations, or in the
longer term, as observed in a control chart of the average
analysis result on a control sample plotted as a function of
time.
Random errors in elemental analysis can be categorized
according to the underlying cause of the error. A brief dis-
cussion of sample and sampling errors along with a
Table summarizing other common sources of uncertainty
follows.
Sampling and Sample Errors
Sampling and sample related errors tend to dominate the
overall analysis uncertainty. Typically repeatability between
sparks on a sample is 1.5–2 times higher than on a certified
reference material of the same alloy. Poor sampling and/or
sample preparation practices can lead to erroneous analyses
and therefore wrong conclusions and/or decisions about
conformance to specification or process adjustments (furnace
corrections). The uncertainty due to sampling and sample
related errors can be reduced by taking multiple samples
and/or increasing the number of sparks used to determine the
average result.
Sampling errors include factors such as:
• insufficient number of samples
• lack of homogeneity in the metal being sampled
• slow or non-continuous pouring (double pour)
Using Guard Bands to Accommodate Uncertainty in the Spark …
• more than one sample poured out of the same ladle of
metal
• mold not completely filled (sample and/or sprue not
completely formed)
• contaminated metal, sampler or ladle
• improper sampler
• improper care of the sampler or ladle
• segregation related to the sample cooling rate and its
directionality
• taking a sample with a cold mold
• taking sample when metal temperature in the furnace or
trough is too low for a particular alloy
• allowing the metal in the ladle to cool excessively before
pouring the sample
• removing the sample or breaking the sprue before com-
plete solidification
• inclusions, skim or bath in the sample (observed before
or after machining)
• porosity, cracks, voids or pits in the sample (observed
before or after machining)
• rounded corners on the sample.
Sample preparation errors include:
• incorrect or uneven depth of cut
• surface too rough or too smooth relative to an ideal
surface of 63 lin. RMS (1.6 lm) sample and standard
surfaces have different surface roughness
• samples not prepared properly using a milling machine or
a lathe.
Note: sanding or grinding may introduce contamination
on the surface, tend to smear softer aluminum material
over harder intermetallic particles, or eject harder inter-
metallic particles from the sample
• contamination from coolant (if used)
• contamination from cutting tooling
• contamination from sample handling.
287
Other Sources of Uncertainty
Other sources of uncertainty can be attributed to the method,
the instrument or the surrounding environment and are
covered in detail in Table 1.
Conclusions
Uncertainty in measurements is unavoidable. Numerous sour-
ces of errors, including but not limited to sampling, lab prac-
tices, and reference material uncertainty, are inherent in the
analytical process used to certify the compositions of aluminum
and aluminum alloys. When determining specified composi-
tion limits for a new product, or certifying the composition of
an existing product against specified composition limits, it is
recommended that guard bands are used to set internal oper-
ating limits to accommodate analysis uncertainty. Internal
operating limits are an essential practice for producers to ensure
compliance of product within specified composition limits.
References
1. ASTM Standard E716 Standard Practices for Sampling and Sample
Preparation of Aluminum and Aluminum Alloys for Determination
of Chemical Composition by Spectrochemical Analysis (West
Conshohocken, PA; ASTM International, 2016)
2. The Aluminum Association International Designations and Chem-
ical Composition Limits for Unalloyed Aluminum (Arlington, VA:
Aluminum Association, 2007)
3. ISO 3534-1:1993, Statistics—Vocabulary and symbols—Part 1:
Probability and general statistical terms (Geneva, Switzerland;
International Organization for Standardization, 1993)
4. ISO/IEC Guide 99 International Vocabulary of Metrology—Basic
and General Concepts and Associated Terms (VIM) (Geneva,
Switzerland; International Organization for Standardization, 2007)
5. S.L.R. Ellison, A. Williams (ed.), EURACHEM/CITAC Guide: Use
of Uncertainty Information in Compliance Assessment (United
Kingdom; EURACHEM, 2007)
 Laser Marking and 3D Imaging of Aluminum
Products

Alex Fraser, Michael Dallaire, and Xavier P. Godmaire

Abstract
Most industrial products have (challenging) 3D shapes, many of them require traceability
and individual marking. Although some laser marking systems on the market have 3D
capabilities, they require the 3D shape to be loaded in the laser controller and the part to be
precisely located. However, many industrial processes requiring direct part identification
cannot fulfill those precise positioning requirements. To overcome these limitations, a 3D
laser marker with integrated 3D imaging system was developed. This imaging system
obtains the 3D image of the piece, and then the laser controller starts the marking process so
that the focus fits on the part surface. The whole 3D data acquisition and transfer takes less
than 3 s. This solves the problem of part positioning and simplifies the integration, while
also providing 3D data of the surface that can be used for quality control.

Keywords
Aluminum Laser Marking 3D imaging

Introduction use in many industries, with growth being particularly strong

As traceability and process control are becoming more and
more important, not only in a growing number of industries,
but also much wider spread across the value chain, often
starting with the raw material, marking technologies are
increasingly challenged by ever increasing requirements of
customers in the metal production and processing industries.
Many different part marking technologies have been devel-
oped and are being used in the industry, but of all the
available ones the laser marking technology is clearly
evolving now the fastest and is the only one capable of
meeting today’s and tomorrow’s needs in terms of speed,
ability to mark at a (variable) distance, uneven surface which
is sometimes still hot and covered with lubricants or other
contaminants [1].
Galvo-based laser marking systems have been used for
decades to mark identifiers on parts’ surfaces. They are in
A. Fraser
M. Dallaire (&)
X.P. Godmaire
Laserax Inc, 2811 Avenue Watt, Québec, QC G1X 4S8, Canada
e-mail: mdallaire@laserax.com
in the medical, food and beverage industries. The right
choice of laser type, wavelength and pulsed regime allows
the achievement of good marking results on almost any
material. Metals are typically marked with pulsed fiber or
YAG lasers emitting at 1.06 µm. CO2 lasers at 10.6 µm (or
also 10.2 and 9.6 µm) are mainly used for organic materials
such as wood, cardboard, leather and fabric. Plastics can be
marked with both laser types but better contrast is usually
achieved at the 1.06 µm wavelength.
An important parameter of galvo-based laser marking
systems is the lens focal length (FL). The shorter the FL is,
the smaller the focused spot can be, thus increasing the laser
intensity in order to reach the melting or ablation threshold
required to efficiently mark the material. On the other hand, a
shorter FL has a small working field and a small depth of
focus. Working field is the area that the focused beam can
reach, and it must be at least the size of the identifier to be
laser marked, to avoid having to move the laser head. Depth
of focus is the effective distance below and above the focal
plane at which the laser process is still efficient.

© The Minerals, Metals & Materials Society 2017 289

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_38
290
Depth of focus is inherent to any laser marking process
and must be taken into consideration when choosing the
right laser marking system for a specific application. A typ-
ical 160 mm FL lens used to mark a black identifier on an
aluminum surface has a depth of focus around ±1.5 mm.
Using a longer FL of 420 mm allows the beam to reach a
depth of focus of ±3 mm. However, many industrial prod-
ucts cannot achieve this positioning precision using standard
manipulation tools.
In aluminum and iron/steel smelters, the positioning
precisions achieved are far below these values. Typically,
this is overcome by mounting the laser head on a motorized
arm. The arm will position the head in order to maintain the
desired distance from the surface. The distance offset can be
obtained either from a distance sensor or a simple abutment
device. However, these motorized arms can be costly,
require additional floor space and increase the need for
ongoing maintenance. Their movement may also increase
the overall cycle time.
Another method to eliminate these issues may be to use a
3D galvo-based laser head. These heads, in addition to the
two galvo-mounted moving mirrors, also have a
galvo-driven moving lens. With this kind of system, it is
possible to almost instantaneously change the position of the
focal point without moving the head itself. An external
command can be used to have the lens adjust its focal
position through a signal provided by an external distance
sensor. The offset generated could be well sufficient for
applications where the surface to be marked is flat and
always oriented perpendicular to the laser head.
Despite their different limitations and inconveniences,
these existing solutions can be found in many industrial
applications. But it was absolutely important to go one step
further with the developments: An innovative laser marking
system was developed that clearly helps overcome the dif-
ferent limitations and problems of the currently existing
systems. It links a standard three axis galvo-based scan head
with a 3D imaging system. This allows a mark to be applied
to any surface (of any shape, type or temperature) positioned
under the laser head—without the limitation of having to
position it in a very precise way all the time.
Technology Basis
Laserax’s LXQ 3D Vision laser marking technology is based
on the existing Laserax LXQ 3D fiber laser marking system.
This system is combined with a structured light pattern 3D
imaging system. A Digital Light Processing (DLP) system is
used to project structured light patterns on the part to be laser
marked, while a camera, synchronized with the DLP,
acquires the resulting images. The images are then processed
through dedicated 3D reconstruction software which then
A. Fraser et al.
generates a 3D surface model. This 3D surface data provides
the laser marking system with the required information on
the location and the shape of the surface to be marked. This
allows the focus to be placed on the actual part surface. The
automated and rapid data transfer between the 3D vision
system and the laser marking system allows the LXQ 3D
Vision to mark any surface located within its effective focus
range. This eliminates the need to manually download the
3D shape to the laser controller. Also, since the imaging
process is done within the coordinate system of the laser, the
LXQ 3D Vision eliminates the need for the precise posi-
tioning of the piece to be marked with respect to the laser
marking head.
The integrated high resolution camera provides another
very interesting capability to the LXQ 3D Vision: 1D/2D
code reading and validation. The system includes a database
where all the marked codes are stored, along with other
interesting parameters such as the date and time of the
marking, confirmation that the code is read, as well as its
correspondence with the required data. Further to this, other
quality control parameters can also be added to the data set,
such as a rms value of the surface profile and grey level of
the laser marked black identifier.
Another interesting capability of the LXQ 3D Vision is its
ability to detect defects on the surface (or the part in general)
and avoid marking the identifier where these defects are
located. The system has an option to ensure that the surface
beneath the identifier is free of defects, up to a certain user
defined level, to prevent laser marking at this location. If the
default region doesn’t fall within pre-defined criteria, either
the operator is alarmed as the part is scrap, or the marking is
automatically translated to the closest location that meets the
criteria. In the case of castings for example it is possible—if
the marking is placed on the overflow side—to detect
incomplete mold/die fills, which in a fully automated process
might make it to a later stage of the production process
without detection. On parts with still acceptable surface
defects according to the part specification (but such that
could impact the readability of the marking), this can help to
increase the readability percentage to a higher level—which
can overall reduce the scrap rate for this part and avoid
customer complaints related to the part marking. All surface
data are dynamically available to use by OEMs or end users
for quality control purposes.
Performances
The 3D vision system included in the LXQ 3D Vision is
capable of generating high resolution 3D images. The res-
olution provided depends on the optical configuration used.
Three standard configurations are available and are defined
by the focal length of the main focusing lens: 160, 250 and
Laser Marking and 3D Imaging of Aluminum Products 291

420 mm (other focal lengths are also available on request).

The effective focusing range, i.e. the range of distance that
provides an effective marking, is also dependent on the main
focal length. These values are summarized in Table 1.
Most marking applications that use the 3D imaging sys-
tem to compensate for bad or simply inconsistent positioning
or for a curvy or tilted surface have resolution requirements
far below the maximum resolution of the system. In these
cases, the full resolution can be used for surface analysis and
quality control while a lower resolution mapping is trans-
ferred to the laser marking system. This requires a typical
time of three seconds between the beginning of the 3D
imaging process and the beginning of the laser marking
process. This is not only important in the production of sows
or ingots, but especially particularly for parts produced e.g.
by shape casting or forging processes and which are marked
right after the first forming process in order to guarantee
traceability throughout the entire value chain. These parts are
characterized by often complex shapes, not always identical
positioning e.g. on a conveyer belt, and very often short
cycle times that require the marking to be equally fast (as it
should never become the bottleneck in the production
process).
The marking speed is directly proportional to the power
level of the laser used. In order to meet the wide variety of
market requirements, the LXQ 3D Vision marking system is
available in power levels of 20, 50 and 100 W. With the
100 W system, high contrast markings can be obtained at a
marking speed as high as 0.6 cm2/s at 25 °C and over
1.2 cm2/s at 400 °C. With a giving power level the ultimate
marking speed (for a specific given marking) is thus influ-
enced by the temperature of the part to be marked [2].
The LXQ 3D Vision marking system is equipped with a
high definition camera that allows 1D and 2D codes (stan-
dard barcodes, QR code datamatrix) to be read. A large
selection of code subtypes is also supported by the marking
and reading systems.
The Fig. 1a and b show the marking of an ingot piece and
the 3D surface generated showing the position of the iden-
tifier to be laser mark, respectively.
Fig. 1 a View of the laser marked ingot piece. b View of the 3D
Another example of the capabilities of the LXQ3D vision surface generated showing the position of the identifier to be laser
is shown on the Fig. 2. Laser marking has been applied to marked
three aluminum plates located 5 cm apart from one another.
The focus adjustment between each plate was automatically for marking parts “on the fly” without holding them down in
done by the measurement system that transfers the 3D data a fixed position every time. In industrial environments this is
to the laser controller. This is a key enabler of the technology a key feature e.g. for marking parts passing in front of the

Table 1 Summarized Focusing lens focal length

performance of the LXQ 3D
vision 160 mm 254 mm 420 mm
3D image resolution 90 µm 150 µm 250 µm
Effective focusing range 25 mm 70 mm 140 mm
292
Fig. 2 Photograph of laser marking of three aluminum plates, located
5 cm apart from one another
marking system on a conveyer. Laser marking is the only
marking technology capable of this feature (which is simply
impossible to achieve with inkjet, peen marking, etc.) [2].
Discussion
The first goal in coupling a 3D imaging system with our
laser marking system was to offer an automatic focus
adjustment to compensate for the lack of positioning preci-
sion achievable with massive metal pieces. This feature was
at first requested by our customers for aluminum sow and
large ingot laser marking. In the meantime many more
applications in the area of shape casting and forging have
been identified that have identical or very similar require-
ments, often even more extreme. In shape casting often large
parts are cast in automatic cells and they need to be marked
immediately after casting while either on a conveyer (like
sows or ingots) or held by a robot—in both cases repetitive
precision in positioning the parts in front of a marking
system would require significant investment in complex
equipment, would slow down the cycle time, or would give
other challenges very hard to overcome. In addition to
meeting this need for auto focusing on a part in an imprecise
location, the on board camera allows other capabilities in
addition to code reading, which could serve quality control
needs. Such features have already been studied and are in the
process of being developed.
A. Fraser et al.
Conclusion
The LXQ3D Vision system enables direct marking of parts
(including with complex shapes) that are not precisely
located with respect to the laser head. This greatly simplifies
integration of the laser system for such applications by
eliminating the need for motorized positioning of the laser
head or by bringing the parts into the exact same position
every time. The five-inch-wide range for effective marking
of metal surfaces is sufficient to make that solution effective
in e.g. most aluminum smelters marking applications,
including sows, T-ingots and slabs. It is also a very impor-
tant feature for shape casting, forging and other forming
metal technologies with similar requirements. An additional
advantage gained by using the system is that the part surface
is analyzed and imperfections easily detected. If it is still in
specification (and it is acceptable for the customer) the
marking can simply be placed in a different spot that does
not have the imperfection that would impact readability of
the marking. In certain cases this part scanning can even
detect defective parts and therefore identify scrap at the
earliest possible stage of the value chain, which avoids much
higher losses of added value on a scrap part, or worse,
having a scrap part finding its way to the customer! Com-
bined with the high speed laser marking capabilities of the
LXQ-100 laser system, this solution is a very attractive
technology which is now considered by many smelters and
metal processing companies around the globe who want to
improve the reliability of their traceability process and to
decrease their operational costs related to part identification.
References
1. A. Fraser, J. Maltais, M. Hartlieb, C. Frayssinous, R. Vallée, X.
P. Godmaire, Review of technologies for identification of die
casting parts. NADCA Die Casting Congress proceedings 2016
2. A. Fraser, V. Brochu, D. Gingras, X. Godmaire, Important
considerations for laser marking an identifier on aluminum. Light
Metals 2016, Proceedings of TMS 2016, p. 261–264
 Production and Certification of Arconic
Certified Reference Materials

Jeneé L. Jacobs, Michael L. Ruschak, John L. Genna, Keith K. Trischan,

Louis A. Bono, and Samantha L. Stephens

Abstract
Arconic Spectrochemical Reference Materials, formerly Alcoa Spectrochemical Standards,
has been a leading producer of certified reference materials (CRMs) used by the aluminum
industry for more than 70 years. Arconic offers more than 320 catalog alloys as well as
custom specification alloys, all of which are produced by casting techniques that minimize
or substantially eliminate both macro and micro segregations. The alloy compositions are
certified for up to 28 elements using two or more independent analytical methods; most
commonly Spark-AES, ICP-AES, and GD-MS; and rigorous statistical analysis to ensure
the accuracy of the final composition certification, the chemical and physical uniformity,
and the performance of the CRMs in use. The Arconic Spectrochemical Reference
Materials’ process is ISO Guide 34, ISO 17025, and ISO 9001 accredited. This paper
describes the production, analysis, and certification techniques used by Arconic Spectro-
chemical Reference Materials for the production and certification of CRMs.

Keywords

Certified reference materials Spark atomic emission spectrometry Inductively coupled
plasma atomic emission spectrometry Aluminum alloys

Introduction Reference Materials has become widely recognized for the

The Arconic Spectrochemical Reference Materials, formerly
Alcoa Spectrochemical Standards, business naturally
evolved from the pioneering efforts of Alcoa and ARL
(Thermo™) to develop the first optical emission spectrom-
eter instrument. Since that joint effort, Arconic Spectro-
chemical Reference Materials’ certified reference materials
(CRMs) have become a necessary accompaniment to the
spectrochemical methods implemented throughout the alu-
minum industry. With more than 70 years of experience
supplying aluminum alloy CRMs, Arconic Spectrochemical
J.L. Jacobs (&)
M.L. Ruschak
J.L. Genna
K.K. Trischan
L.
A. Bono
S.L. Stephens
Arconic Technology Center, New Kensington, PA 15069, USA
e-mail: jenee.jacobs@arconic.com
production and certification of aluminum alloy CRMs with a
high degree of uniformity and certification accuracy.
Arconic CRMs are produced to provide specific and well
defined reference alloy compositions. CRMs are produced to
either target specific registered alloy compositions or to
bracket those compositions in such a way as to cover a
number of specific alloys within an alloy family [1, 2].
CRMS are also produced to aid in the construction and
maintenance of analytical calibration curves. Special com-
positions are frequently produced that correspond to exper-
imental alloys, specific Arconic modifications to existing
alloys, and customer requested compositions. The special
CRM compositions are confidential and, in general, avail-
able only to the original requestor of the composition.
The following designations are used within Arconic
Spectrochemical Reference Materials to describe the differ-
ent types of CRMs produced:

© The Minerals, Metals & Materials Society 2017 293

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_39
294
Fig. 1 General flow diagram of
the Arconic Spectrochemical
Reference Materials’ production
and certification process
1. “SS”—specific alloy CRMs whose composition is at or
near the midpoint of The Aluminum Association regis-
tered compositions, e.g. SS-3004, SS-7075.
2. “WA, WB, etc.”—range CRMs for wrought alloys
whose composition brackets the composition of the SS
CRMs, e.g. WA-6000 thru WV-6000.
3. “KA, KB, etc.”—range CRMs for casting alloys whose
composition brackets the composition of the SS CRMs,
e.g. KA-380 thru KH-380.
4. Binary CRMs—usually designated by the specific ele-
ment symbol followed by a sequential number, e.g. SI-1,
CU-3. These contain compositions of a single element in
a pure aluminum matrix or in a specific alloy type and are
generally used in preparing initial calibration curves.
5. “SQ”—RMs that correspond to no specific alloy but
contain a range of elements at specific concentration
levels to provide reproducible spectral intensities. Exact
compositions are not certified. SQ RMs are most fre-
quently used to compensate for drift in spark-AES, e.g.
SQ-10, SQ-18.
6. “SAX”—custom made composition CRMs, e.g.
SAX-220.
J.L. Jacobs et al.
Production and Certification of Arconic CRMs
The CRM production and certification procedures used by
Arconic Spectrochemical Reference Materials are designed
to ensure the homogeneity and elemental composition of the
CRM ingot. A general flow diagram of the production and
certification procedure is shown in Fig. 1.
Casting and Machining of CRMs
Arconic CRM ingots are produced using a water cooled
direct chill (DC) casting technique. Ingots are cast one or
two at a time and are approximately 40–50 in. in length and
3 in. in diameter. Each ingot weighs approximately 30–40 lb
prior to machining. Casts are started with a “dry” furnace
into which an accurately weighed amount of aluminum and
component metals are placed. All weights are traceable to
NIST standard weights using calibrated balances.
The cast ingots must have the following attributes to be
moved to the machining and certification processes:
Production and Certification of Arconic Certified Reference … 295

Fig. 2 Machining diagram of an Arconic Spectrochemical Reference Materials’ CRM ingot

1. Minimal radial segregation. Analysis of CRMs

2. Minimal longitudinal segregation with the exception of
volatile elements which may be certified on an individual
section basis.
3. Minimal to no porosity.
4. No dross.
5. Maximum deviation from the nominal composition of
alloying elements of 1–3% (element/alloy dependent)
6. Uniform and small grain structure.
Since some segregation is unavoidable, the ingot is
cropped at both the bottom and top and 0.5″ is machined
from the outside surface. On customer request, a different
outer diameter may be produced. Depending on the product,
the ingot is typically sectioned into 1″ (25.4 mm) or 1.5″
(38.1 mm) thick disks and stenciled from bottom to top—see
diagram (Fig. 2).
The following are the machining and sectioning
requirements for a full ingot as shown in Fig. 2:
1. Turn the ingot from 3 in. to approximately 2.52 in. The
finish on the outside of the ingot should be about 50√.
2. Crop and scrap a minimum of 6 in. (152 mm) of the
bottom of the ingot identified by the position of chamfer.
3. Crop and scrap a minimum of 3 in. (76 mm) off the top
of the ingot.
4. Mark sections consecutively from the bottom to the top
as shown.
5. Lathe the bottom of each section to obtain a smooth
surface and stencil with the Arconic logo and identifying
information.
6. After certification a label with the identification infor-
mation is attached to the outside diameter.
The compositions of Arconic CRMs are determined using
two or more independent analytical methods which may
include spark atomic emission spectrometry (Spark-AES),
inductively coupled plasma atomic emission spectrometry
(ICP-AES), X-ray florescence (XRF), glow discharge mass
spectrometry (GD-MS), inductively couple plasma mass
spectrometry (ICP-MS), or other approaches deemed
appropriate for a specific application. Most commonly,
Arconic Spectrochemical Reference Materials implements
Spark-AES, ICP-AES, and GD-MS for certification. Arconic
CRMs are primarily intended for methods employing
Spark-AES and chill cast sample disks as described in
specific ASTM methods (i.e. B985, E716, and E1251) [3–5].
Due to the homogeneity of the CRMs, they may be appli-
cable to other analytical techniques including, but not lim-
ited to, XRF, AAS, ICP and ICP-MS.
Due to the possibility of radial segregation for some ele-
ments, sampling of the CRMs should be restricted to those
areas shown in Fig. 3. The composition of the CRM is certi-
fied for the 16 mm zone (shaded, Fig. 3). Sampling of the
CRM will depend on the analytical procedures employed:

Where CRMs are particularly susceptible to segregation

or when special CRMs are being cast in limited quantities,
alternate casting methods are available. Machining and
sectioning of these alternatively cast CRM ingots are similar
to the previously discussed procedures; however, ingot
Fig. 3 Diagram of the arconic spectrochemical reference materials’
section thickness and diameter may vary. CRM sampling area (shaded)
296
1. Sampling for Spark-AES—A lathe or milling machine is
used to provide a smooth flat surface that is sparked
within the 16 mm zone. Machining should meet
requirements documented in ASTM Method E716 [4].
2. Sampling for AAS, ICP, and ICP-MS—Use drillings
through the disk within the 16 mm zone or drill a 25 mm
hole through the center of the disk and machine 3–4 mm
from the circumference of the disk. Take lathe turnings
from the remaining 16 mm zone.
3. Sampling for XRF—The circle (Fig. 3) indicates the area
of the disk to be sampled for a 32 mm diameter X-ray
sample. The surface presented to the X-ray must be a
smooth flat surface.
Spark Atomic Emission Spectrometry (Spark-AES)
Analysis
Spark-AES is used during the certification process to
determine both composition and homogeneity. Prior to
undergoing formal certification analysis, a preliminary
analysis is done on a section taken directly from the center of
the new CRM(s) ingot. This analysis provides an initial
estimate of concentration which is compared against the
target compositions. If deviations from specifications that are
outside of internal limits are observed, the ingot is scrapped
prior to proceeding with the certification process.
For certification analysis, a representative number of
sections are chosen from each of the new CRM ingots. The
chosen sections are taken equidistant from the bottom,
middle, and top of the ingot. Along with the new CRM ingot
sections, a series of drift correct, master, range, and QA
CRMs are also analyzed. Drift correct CRMs are imple-
mented to detect and correct spectrometer drift throughout
the analysis. The master and range CRMs are selected so the
composition closely matches that of the CRM to be certified.
The compositions of these CRMs are compared against their
previously certified values to determine if bias is present
throughout the analysis. The QA CRMs are monitored for
quality assurance.
The surface of the samples and CRMs are prepared using
a lathe or milling machine to provide a smooth flat surface
that is sparked within the 16 mm zone (Fig. 3). A total of six
sparks are taken on each of the sections chosen from the new
CRM ingot(s). In order to achieve a total of six sparks per
section, the analysis sequence is repeated six times rather
than sparking six times on a single section and then moving
onto the next section. The analysis sequence consists of drift
correct CRMs, a master CRM, the new CRM ingot, range
CRMs, and a QA CRM. Repetition of the analysis sequence
provides some measure of protection from excessive
instrument drift since all sections have been observed
throughout the entire analytical procedure.
To provide additional assurance of the accuracy of the
Spark-AES analysis, a second Spark-AES analysis is
J.L. Jacobs et al.
conducted on an independent Spark-AES instrument using
different reference CRMs for instrument calibration. This
analysis provides a single, additional reference point for
concentration level.
Inductively Coupled Plasma Atomic Emission
Spectrometry (ICP-AES) Analysis
The use of a single assessment of concentration of new
CRMs via Spark-AES analysis is insufficient in itself in
certifying final composition. Because the Spark-AES pro-
cedure used in the assessment of both homogeneity and
concentration requires the use of a master reference CRM,
which was in turn certified in a similar manner, there is
danger in developing a bias error that will be propagated to
all CRM compositions certified against that master.
ICP-AES is used as an independent analysis technique to
minimize the potential for bias.
The ICP-AES analysis is performed on a section of the
CRM ingot near the center. CRM chips are collected by
lathe from the 16 mm zone shaded in Fig. 3. The chips are
then dissolved in mineral acid or caustic solution and ana-
lyzed via ICP-AES instrumentation. Each ICP-AES analysis
is independently calibrated with matrix matched elemental
CRM solutions made from single element solutions traceable
to the National Institute of Standards and Technology
(NIST).
Glow Discharge Mass Spectrometry (GD-MS)
Analysis
Trace levels of elements present in the CRM ingots cannot
always be detected by ICP-AES, and therefore, glow dis-
charge mass spectrometry (GD-MS) is implemented for trace
element analysis as an alternative [6]. GD-MS analysis is
also performed on a section near the center of the CRM
ingot. The surface of the CRM ingot section is prepared by
electropolishing in nitric acid and methanol. The GD-MS
instrumentation is calibrated with aluminum CRMs and
relative sensitivity factors are determined for each element of
interest. The CRM ingot is then analyzed and the trace
element composition is determined. Similar to ICP-AES,
GD-MS is also independent of the master reference CRM
which helps to minimize any potential bias.
Certification
CRM Homogeneity
The routine statistical analysis performed on the data
developed from the Spark-AES certification procedure is
aimed at providing a measure of homogeneity of the CRM
ingot. The Spark-AES data is analyzed using a two way
analysis of variance (ANOVA). The ANOVA analysis is
necessary to sort out the various components of variability
Production and Certification of Arconic Certified Reference …
Fig. 4 Plot of the estimated
analysis bias (%) as a function of
element concentration (%)
that might otherwise obscure the true nature of the variability
within the ingot, such as Spark-AES instability. This
approach for data analysis of spectrochemical CRM ingots
was first developed from the discussion of such experiments
by Bowker and Lieberman [7].
CRM Composition
The final concentration assignment for each element is
determined using a weighted average of the Spark-AES
analysis results, the alternate Spark-AES value, up to three
repeated analysis from the ICP, GD-MS results, and any
other analysis techniques. Weighting is determined by the
number of independent analyses performed.
Composition Uncertainty
Uncertainty in concentration level due to systematic effects
of calibration and differences between instruments and
methods cannot be easily determined with a high level of
certainty during each ingot evaluation. The uncertainty of
the analysis (uc) is a result of instrument and method bias
(ubias), deviation of concentration within each ingot section
(usection), and deviation of concentration throughout the
entire ingot (ushot).
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uc ¼ u2shot þ u2section þ u2bias
In order to estimate instrument and method bias, a large
number of certifications were examined to determine the
systematic differences between different instrumentation and
different analytical methods. A plot of the estimated bias as a
function of concentration is shown in Fig. 4. From this data
and subsequent regression analysis, estimated bias as a
function of concentration intervals were developed and
assigned for certificate purposes. No significant differences
of bias were observed as a function of element or alloy. The
additional terms in uncertainty, ushot and usection are devel-
oped from the ANOVA analysis of certification Spark-AES
data.
297
In order to define an interval within which the concen-
tration value could be expected to lie with a high level of
confidence, an expanded uncertainty is defined as U and is
given by:
U ¼ kuc ðyÞ ð2Þ
where k is a coverage factor which is chosen on the basis of
the desired level of confidence to be associated with
expanded uncertainty. Typically k is in the range of 2–3.
With the normal distribution assumption applied, k ¼ 2
defines an interval having a level of confidence of approxi-
mately 95%. It would be desirable to choose a specific value
for k that produces a well-defined interval with an
unequivocal level of confidence corresponding to 95 or 99%.
This statistical treatment given does not preclude the use of
subjective judgment to produce or modify the mean levels or
intervals associated with a particular measurement. The basis
for these judgments cannot be predefined but must be based
on clear technical reasoning associated with detailed
knowledge of the measurement systems employed, the
metallurgy of the alloy CRM being produced and, ulti-
mately, the end use of the particular CRM value being
assigned.
ð1Þ
Certificate of Analysis
Upon completion of certification, a certificate of analysis is
produced. No CRM should be issued without an accompa-
nying certificate of analysis. The certificate of analysis
provides the end user the necessary information for the
proper use of the CRM. In addition it provides the user
important information regarding the intended use, produc-
tion and certification. The Arconic Spectrochemical Refer-
ence Materials’ Certificate of Analysis adheres to the
guidelines set forth in ISO Guide 31 [8]. An example the
Arconic Spectrochemical Reference Materials’ Certificate of
Analysis is shown in Fig. 5. The following items will appear
on all Arconic certificates:
298
Fig. 5 Arconic Spectrochemical Reference Materials’ certificate of analysis
1. The Arconic logo along with a certificate title.
2. The CRM identification.
3. The concentration of each CRM constituent along with
an estimated uncertainty when appropriate.
4. The responsible person’s name.
5. The location address.
6. Application notes that will include statements of:
(a) Intended Use
(b) Material Preparation
(c) Explanation of the Material Certification Process
(d) Explanation of the Limits of Uncertainty
(e) Traceability.
Traceability
All Arconic Spectrochemical Reference Materials’ CRMs
are traceable to NIST. During the certification process, NIST
traceable CRMs, both solid and liquid, are used for cali-
bration solution preparation. NIST traceable weights are
used for the calibration and verification of balances in both
CRM production and analysis methods.
Accreditations
Arconic CRMs holds an accreditation to ISO Guide 34: 2009
international standard for “General Requirements for the
Competence of Reference Material Producers”. ISO Guide
34 is the highest level of quality attainable by reference
materials producers. It ensures that the production and cer-
tification of Arconic CRMs and RMs are done in accordance
with a rigorous set of internationally recognized require-
ments. ISO Guide 34 covers the process for making CRMs
from initial customer inquiry through the manufacturing,
J.L. Jacobs et al.
testing, certification and distribution of the Aluminum
Spectrochemical CRMs to our customers.
The testing methods used during the certification process
have also been accredited by the American Association of
Laboratory Accreditation (A2LA) to the ISO 17025:2005
international standard for ‘General Requirements for the
Competence of Testing and Calibration Laboratories’. The
accreditation also meets the requirements for the Interna-
tional Laboratory Accreditation Cooperation (ILAC) for ISO
17025:2005.
The scope of the ISO 9001:2008 quality system at the
Arconic Technology Center (ATC) includes administrative
activities as well as the production and certification of
Arconic Spectrochemical Reference Materials’ CRMs. The
quality system is designed with controls that assure that
product quality meets or exceeds the requirements and
expectations of our customers. It provides for the prevention
of nonconforming product, early detection of discrepancies,
and corrective action to assure consistent delivery of quality
product.
Conclusions
Arconic Spectrochemical Reference Materials has been
producing CRMs with a high degree of uniformity and
certification accuracy for over 70 years. The CRMs are
produced for use as a necessary accompaniment to the
spectrochemical methods implemented throughout the alu-
minum industry to provide specific and well defined refer-
ence alloy compositions. The CRMs are also utilized to aid
in the construction, maintenance, and operation of
Spark-AES instrumentation.
Production and Certification of Arconic Certified Reference …
The production and certification processes for the pro-
duction of Arconic CRMs is a multifaceted procedure
beginning with CRM ingot casting and resulting in a CRM
with a final certificate of analysis. Each component of this
process is designed to determine and ensure the homo-
geneity and elemental composition of the final CRM prod-
uct. All Arconic CRMs are NIST traceable and accredited to
A2LA ISO 17025:2005 and/or ANAB ISO Guide 34:2009.
References
1. The Aluminum Association, International Alloy Designations and
Chemical Composition Limits for Wrought Aluminum and Wrought
Aluminum Alloys (Teal Sheets) (The Aluminum Association,
Arlinghton, VA, 2015)
299
2. The Aluminum Association, Designations and Chemical Compo-
sition Limits for Aluminum Alloys in the Form of Castings and
Ingots (The Aluminum Association, Arlington, VA, 2009)
3. ASTM International, Standard Practice for Sampling Aluminum
Ingots, Billets, Castings and Finished or Semi-Finished Wrought
Aluminum Products for Compositional Analysis (ASTM Interna-
tional, West Conshohocken, PA)
4. ASTM International, Standard Practices for Sampling and Sample
Preparation of Aluminum and Aluminum Alloys for Determination
of Chemical Composition by Spark Atomic Emission Spectrometry
(ASTM International, West Conshohocken, PA)
5. ASTM International, Standard Test Method for Analysis of
Aluminum and Aluminum Alloys by Spark Atomic Emission
Spectrometry (ASTM International, West Conshohocken, PA)
6. Evans Analytical Group, [Interview]. 31 August 2016
7. A.H. Bowker, G.J. Lieberman, Engineering Statistics
(Prentice-Hall, Englewood Cliffs, N.J., 1959)
8. International Organization for Standardization, ISO Guide 30:2015
Reference material—Contents of certificates, labels and accompa-
nying documentation, Geneva (ISO copyright office, Switzerland,
2015)
 Characterization of Large Strain Extrusion
Machining (LSEM) of AA7050

Daniel R. Klenosky, David R. Johnson, Srinivasan Chandrasekar,

and Kevin P. Trumble

Abstract
This work features a characterization of AA7050 strip produced for the first time in a single
deformation step via large strain extrusion machining (LSEM), which has emerged as an
alternative method to produce AA7050 strip. The resultant LSEM plate or sheet
microstructure is promising for applications where SCC and exfoliation cracking resistance
are important. LSEM has been shown to produce grains with a lower aspect ratio than
conventional hot rolling, which has been linked to SCC resistance. In addition, LSEM
grains have a different orientation relative to the strip direction, which may result in an
improvement in exfoliation cracking resistance as compared to hot-rolled strip.

Keywords
Aluminum Deformation Processing Machining LSEM 7050 alloy

Background aluminum alloys. The hot rolling typically involved in the

AA7050 is among the most popular high-strength aerospace
alloys for plate applications. It is typically DC-cast into
slabs, homogenized, hot-rolled in multiple steps, and
heat-treated for strength. AA7050 plate is particularly well
suited for applications that require exfoliation cracking
corrosion or stress corrosion cracking (SCC) resistance.
These two forms of intergranular corrosion occur via dif-
ferent mechanisms, but are both related to the presence of a
galvanic potential between the aluminum and the elevated
concentration of strengthening precipitates located around
the grain boundaries [1].
The rates of SCC and exfoliation corrosion have both
been shown to increase as grain aspect ratio increases for
D.R. Klenosky (&)
D.R. Johnson
S. Chandrasekar
K.P. Trumble
School of Materials Engineering, Purdue University,
701 Northwestern Avenue, Neil Armstrong Hall
of Engineering, West Lafayette, IN 47907, USA
e-mail: dklenosk@purdue.edu
S. Chandrasekar
School of Industrial Engineering, Purdue University, 315 N. Grant
St, West Lafayette, IN 47907, USA
production of these alloys results in a relatively high aspect
ratio—meaning that they are particularly susceptible to these
failure mechanisms. To combat this, the temper designations
T7651 and T7451 have been developed and identified
specifically for AA7050 for their optimizations of corrosion
resistance properties with strength [2].
These tempers have two major characteristics that promote
resistance to failure by corrosion. Tempers designated—T7
are overaged, meaning that they are artificially aged past
their peak strength, so that the strengthening precipitates are
allowed to coarsen slightly. This compromise in strength is
often beneficial, as the same precipitate particles that provide
strength can also act as stress concentrators for failure during
corrosion. In addition, the designation—TXX51 corresponds
to plates that have been stretched to 1.5–3% plastic strain
prior to aging as a way to relieve the residual stresses
inherent to hot working and casting. The relief of these
residual stresses complements the overaging heat treatment
to improve stress tolerance and improve exfoliation cracking
or SCC resistance [3].
These corrosion-resisting tempers are used in the vast
majority of AA7050 plate in aerospace applications—indi-
cating the dominance of SCC and exfoliation cracking as

© The Minerals, Metals & Materials Society 2017 301

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_40
302 D.R. Klenosky et al.

failure mechanisms. Unfortunately, the improvement in processing technique for high-strength aluminum alloys such
corrosion resistance necessarily brings a compromise in as AA7050. This work features a characterization of the
mechanical strength properties. Therefore, it may be desir- resultant microstructure and an analysis of the practicality of
able to develop other methods to produce 7050 plate or sheet the technique as a method to produce AA7050 strip.
that don’t require such strength compromises.
One potential alternative method for producing 7050
plate or sheet is large strain extrusion machining (LSEM). Experimental
LSEM is a modification of the conventional machining
process that employs a constraining tool in addition to the LSEM was performed on AA7050 created via two different
cutting tool into pre-define the cut depth (tc) and the cut processing routes: a 25 mm thick AA7050-T6 plate pur-
thickness (t0) of the resultant chip. This results in a chased from McMaster-Carr, Inc and a 25 mm thick slice of
plane-strain deformation that can be controlled to impose a a DC-cast and homogenized log, donated by Alcoa, inc.
range of strains, strain rates, and adiabatic temperature rises Figures 2 and 3 show the microstructures for the two
on a given material [4–6]. materials, as received. The T6 plate had an elongated
Sheet production via LSEM has a few potential advan- microstructure characteristic of a rolled plate material and a
tages over conventional rolling. The primary advantage is
the potential for a single-step deformation at room temper-
ature, dramatically reducing production time. In addition, the
different deformation path results in a more homogeneous
microstructure with a different microstructure, typically
featuring grains with a lower aspect ratio than those in
conventional rolling. Figure 1 shows a schematic of a typi-
cal rotary LSEM setup.
Cutting speed (V0), tool rake angle (a), and chip thick-
ness ratio (k = tc/to) are all variables that can be pre-defined
to manipulate the shear strain (c), effective strain (e), and
hydrostatic pressure (P). It has been shown previously that
the deformation zone (D) is narrow enough (*50–150 nm
thick) that it can be idealized as a single plane. An
upper-bound model of the LSEM process with a single shear
plane can be solved analytically, yielding the following
solutions for shear strain and von Mises effective strain
during deformation [4]:
Fig. 2 Optical micrograph of a cross-section of as-received
AA7050-T6 plate taken transverse to the rolling direction
k 1
c¼ þ  2 tan a ð1Þ
cos a k cos a
1
e ¼ pffiffiffi c ð2Þ
3
LSEM has emerged as a useful method of producing strip
of other materials, but has not been characterized as a

Fig. 3 Optical micrograph of as-received AA7050 DC-cast and

Fig. 1 Schematic of LSEM in a rotary setup [4] homogenized slice
Characterization of Large Strain Extrusion Machining (LSEM) … 303

Table 1 Grid of machining LSEM

operations. All experiments were
performed at room temperature k = 0.75 k = 0.75 k = 0.75 k = 0.75
(To = 25 °C) without preheating Vo = 0.25 m/s Vo = 2.03 m/s Vo = 4.06 m/s Vo = 5.08 m/s
k=1 k=1 k=1 k=1
Vo = 0.25 m/s Vo = 2.03 m/s Vo = 4.06 m/s Vo = 5.08 m/s
k = 1.5 k = 1.5 k = 1.5 k = 1.5
Vo = 0.25 m/s Vo = 2.03 m/s Vo = 4.06 m/s Vo = 5.08 m/s

measured Vickers hardness of 169 and the DC-cast material microstructures is the alignment of grains with the flow
had an equiaxed microstructure and a measured Vickers direction, which is parallel to the primary shear plane, rather
hardness of 128. than parallel to the length of the strip. Conventional rolled
Both starting materials were machined into 0.3 cm strip typically features grains that are aligned with the rolling
thick, *7.6 cm diameter disks for LSEM experiments. direction.
LSEM was performed on the disks at varying cutting speeds
(Vo) and chip thickness ratios (k), as summarized in
Table 1. All cuts were performed at room temperature,
without preheating the workpieces.
Cutting force measurements were taken during LSEM
using a piezoelectric dynamometer (Kistler Model
No. 9257B) to calculate DT, via the method highlighted in
[5, 6]. The cutting tool was made from hardened M2 steel
cutting tool and had rake angle a = 5°.
Vickers hardness values were obtained using a Leco
LM247AT microhardness tester. A load of 100 g was
applied for 10 indents per sample at a distance at least 2.5d
from each other and the edges of the sample.
The machined strips were sectioned along their centerli-
nes and mounted in epoxy. Samples were then polished with
320 through 2000 grit SiC paper, and 0.05 lm alumina and
0.02 lm colloidal silica on napped cloths. Samples were
etched with Graff and Sargent’s etchant to reveal grain Fig. 4 LSEM of T6 material with Vo = 0.25 m/s, k = 1.5, and
e = 1.15
boundaries, which were observed using optical microscopy eff
[16].

Results and Discussion

LSEM was successfully performed to produce continuous

thin strips of AA7050 with a single deformation step for
both starting materials and all deformation conditions. While
this was to be expected for the soft DC-cast and homoge-
nized material, it is an important result for the hardened
material, as it is not typically possible to produce thin strip
from hardened material via conventional methods such as
cold rolling due to low workability [7]. For comparison,
conventionally rolled AA7050 strip is typically only pro-
duced from the O temper, and always requires several
deformation steps. Figures 4 and 5 show a representative
LSEM microstructure for each starting material.
The LSEM microstructures reveal the material flow path Fig. 5 LSEM of DC-cast and homogenized material with Vo = 2.0
during deformation. A defining characteristic of these m/s, k = 1, and eeff = 1.06
304
For the T6 material, some of the elongated grains that
existed prior to deformation appear to have simply changed
in aspect ratio, with any strength added by cold working
negated by dynamic recovery. The hardness of the LSEM
strip from the T6 material typically stayed around the same
or softened slightly, depending on the cutting speed, with an
average Vickers hardness of 180 at 0.25 m/s, 148 at
2.03 m/s, and 161 at 4.06 m/s (all at k = 1). The slight
increase in hardness at 0.25 m/s is the result of friction
dominating the deformation at such a low speed, resulting in
a lower adiabatic temperature rise, less dynamic recovery,
and an apparent increase in hardness due to cold working. It
remains to be determined whether the increased thickness of
the secondary shear zone at the face of the cutting tool at
slow speeds results in an inhomogeneous (and therefore
undesirable) microstructure.
The microstructure of the DC-cast and homogenized
material also saw the equiaxed grain structure give way to a
grain structure that is aligned with the material flow. This
material also softened slightly, down to a Vickers hardness
of 112 at 2.03 m/s and 108 at 4.06 m/s.
Future Work
Future work on these experiments will feature further
microstructural analysis on the variety of LSEM samples
produced.
Future experiments will focus on strengthening the
LSEM strip via artificial aging to study how the
microstructure and corresponding properties evolve after
deformation under a variety of LSEM deformation condi-
tions. In addition, the secondary shear zones that occur due
to friction near the tooling will be investigated, as they may
result in an inhomogeneous microstructure.
Future work will also focus on the effect of the
misalignment of the grains with the length of the strip as it
relates to corrosion resistance behavior. In particular, the
D.R. Klenosky et al.
exfoliation cracking behavior may be affected by the dif-
ferent orientations of the grains and the length of the strip.
Conclusions
LSEM was used successfully to produce thin strips of
AA7050 from two starting workpieces—DC-cast and
homogenized material and T6 plate. The strips had
microstructures with grains aligned with the primary shear
plane. This is a contrast from the microstructure of
conventionally-produced strip, which has grains aligned
with the rolling direction. This difference may improve
corrosion resistance properties, which will be investigated in
future work.
Acknowledgements Support for this research from Shandong Nan-
shan Aluminum Co., Beijing Nanshan Institute of Aeronautical Mate-
rials and NSF CMMI-MEP-1363524 are gratefully acknowledged.
Andrew Kustas and Xiaolong Bai are also acknowledged for their
advice and help with experiments.
References
1. M.J. Robinson, N.C. Jackson, The influence of grain structure and
intergranular corrosion rate on exfoliation and stress corrosion
cracking of high strength Al-Cu-Mg alloys. Corros. Sci. 41, 1013–
1028 (1999)
2. Alloy 7050 Plate and Sheet—Best Combination of Properties,
ALCOA Mill Products, inc., E22-14752
3. MIL-H-6088, Heat Treatment of Aluminum Alloys (1991)
4. W Moscoso, Severe Plastic Deformation and Nanostructured
Materials by Large Strain Extrusion Machining, Ph.D. Thesis,
Purdue University (2008)
5. M. Efe et al., Acta Mater. 60, 2031 (2012)
6. D. Sagapuram et al., Acta Mater. 61, 6843 (2013)
7. Properties of Wrought Aluminum and Aluminum Alloys, Proper-
ties and Selection: Nonferrous Alloys and Special-Purpose Mate-
rials, vol. 2 (ASM International, ASM Handbook, 1990), pp. 62–
122
 Influence of Trace Element Additions on Fe
Bearing Intermetallic Solidification of a 6063
Al Alloy

S. Kumar, J. Malisano, Y. Ito, and K.A.Q. O’Reilly

Abstract
There is an on-going effort to control Fe bearing intermetallic formation during
solidification in direct chill (DC) casting of dilute Al alloy billets from recycled material
sources, as these insoluble Fe intermetallics control the downstream processing conditions
and final properties of the processed products. This paper investigates the influence of
molybdenum (Mo) and grain refiner combined additions on Fe bearing intermetallic
formation during casting of a 6063 Al alloy. In particular, the grain size and intermetallic
phase content of the samples have been characterised using various microscopies and X-ray
diffractometry. An intermetallic phase extraction technique has been used to facilitate
measurement of the three-dimensional morphology and chemistry of the different Fe
intermetallics present, with changes rationalized in terms of the effect of trace additions.
Both “ac-AlFeSi” and “b-AlFeSi” are observed in all the castings. After the addition of
Al-5Ti-1B grain refiner to the base alloy, b-AlFeSi was predominated in the casting.
Further addition of Mo to the grain refined alloy promoted ac-AlFeSi in the casting. The
possible mechanisms for these effects are discussed.

Keywords
Aluminium alloys Molybdenum Grain refinement Solidification microstructure
Intermetallic phase selection

Introduction ac-AlFeSi (Though ac-AlFeSi have small amount of Mn and

The necessity of making products with recycled aluminium
(Al) for the automotive and building industries increases day
by day [1]. Recycling technologies are being developed to
meet the demands [2]. One of the challenges Al casting
industries faces is to tolerate high level of impurities such as
iron (Fe) into the existing products without affecting much of
the original properties. In the 6xxx Al series alloys, the
presence of Fe and silicon (Si) in the solute level produces
S. Kumar (&)
J. Malisano
Y. Ito
K.A.Q. O’Reilly
Department of Materials, University of Oxford,
Oxford, OX1 3PH, UK
e-mail: kumar.sundaram@materials.ox.ac.uk
Y. Ito
Department of Metallurgy and Ceramics, Tokyo Institute
of Technology, Tokyo, 152-8552, Japan
Mo, for simplicity it was called as ac-AlFeSi though out the
article) and b-AlFeSi intermetallics in the casting [3, 4].
Among those intermetallics, b-AlFeSi was proven to affect
the properties, particularly the hot ductility [5]. Hence it was
common in industries to use a homogenisation heat treat-
ment step to transform the harmful b-AlFeSi to less harmful
ac-AlFeSi before downstream deformation processes
[4, 6, 7]. However, the increase in Fe and Si content to
impurity level means more b-AlFeSi fraction in the casting
[8]. The Al-5Ti-1B grain refiner was commonly added to the
6xxx Al series alloys for the purpose to (a) refine the cast
microstructure, and (b) produce DC cast billet without hot
crack, but had found to increase the b-AlFeSi fraction in the
cast billet [9–11]. Therefore there is a need to control the
formation of b-AlFeSi in DC cast billets of GR added alloys.

© The Minerals, Metals & Materials Society 2017 305

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_41
306
As b-AlFeSi form from the segregated solute rich liquid
film around the primary a-Al grain later in the solidification
process, the presence of other elements in the last liquid
stage will affect its formation. Previous works in literature
suggest, the presence of trace amount of elements such as
vanadium, molybdenum and tungsten promotes the
ac-AlFeSi in Al–Si alloys [12–14]. However, very few
published reports are available in the literature [15–17] on
influence of such elements with the 6xxx Al series alloys,
where b-AlFeSi forms as a “metastable” phase. The
“Metastable” phases are those phase which only form under
non-equilibrium solidification condition [18]. Hence in the
present paper, the effect of combined addition of molybde-
num (Mo) and grain refiner on the b-AlFeSi formation in a
6063 Al alloy has been systematically studied for the first
time. An intermetallic phase extraction technique was used
to reveal the true nature of the intermetallic particles. From
all the studied conditions, it is clear that by adding Mo to a
grain refiner containing 6063 Al alloy promotes ac-AlFeSi in
the casting. The Mo segregation at the inter-dendritic/
inter-granular region is thought to play a significant role in
phase selection response. The various types of IMCs and
their formations are described in detail.
Experimental Details
The chemical composition of the base alloy (BA) AA6063
Al used in this study is given in Table 1. Sample cast with
mushroom mould was used to measure the elemental com-
position using the optical emission spectrometer (OES).
A mini constrained rapid induction-melting furnace (mini-
CRIM) was used to re-melt the base alloy for different
additions. The Mo containing alloys were produced sepa-
rately by adding high pure Mo thin sheets in appropriate
amount to the base alloy melt at *760 °C, and holding it for
30 min with intermediate stirring using boron nitride coated
ceramic rod before casting. For the grain refiner addition
experiments, about 0.2 wt% of Al-5Ti-1B master alloy was
added to the alloy melt at 750 °C, and after holding it for
2 min, the melt was directly cast into the TP1 mould. Each
alloy was cast at 720 °C using the preheated (720 °C) boron
nitride coated TP1 mould and quench tank with water flow
rate fixed at 3.8 l per min. Further details of the TP1 mould
and quench tank setup are given in [19]. Here GR refers to
grain refiner added BA alloy; and GRMo1, GRMo2,
GRMo3 and GRMo4 refer to 0.06, 0.1, 0.3 and 0.5 wt% Mo
added GR samples, respectively.
Table 1 Average chemical Sample Mg Si
composition (in weight percent)
of TP1 samples with different BA 0.38 0.42
additions
S. Kumar et al.
After solidification microstructure, horizontal (38 mm
from bottom) cross-section of the samples was analysed.
Samples for the extraction were also taken from the 38 mm
cross-section. The vertical sectioned samples were grounded
and macro etched using Tucker’s solution. The horizontally
sectioned samples were mounted using non-conductive
bakelite and were mechanically grounded and polished
using colloidal silica. Then the polished samples were ano-
dised using Barker’s reagent ([7 mL HBF4 (48 pct) and
93 mL H2O] for 60 s at 20 V) to reveal primary a-Al grains
using Zeiss Axiophot polarised light microscopy and NIS
elements D 3.0 SP2 software. The grain size was measured
using the mean line intercept method.
Intermetallic extraction apparatus (IEA) was used to
extract the intermetallic particles from the cast samples. IEA
uses anhydrous boiling butan-1-ol (butanol) to dissolve the
Al matrix of the alloy while keeping the intermetallic phases
intact. The intermetallics were then collected on a
poly-tetrafluoroethene (PTFE) filter membrane (47 mm
diameter, pore size of 0.2 µm). The phases were identified
using a benchtop X-ray diffractometer (XRD) Rigaku
MiniFlex600 with Cu-Ka (k = 1.54 Å) source at 40 kV,
15 mA, 1°/min scan speed and 0.002° step size. Both the
mounted and extracted samples were analysed using Zeiss
Merlin field emission gun scanning electron microscopy
(FEG-SEM) equipped with secondary electron (SE) detector,
back scattered electron (BSE) detector, Oxford Instruments
(OI) 150 mm2 XMax energy dispersive X-ray (EDX) detec-
tor and Aztec software. Both the SEM imaging and EDS
analysis were carried out relatively at low voltage (4 kV)
and 500 pA.
Results and Discussion
The primary a-Al grain size reduced significantly with the
(a) addition of Al-5Ti-1B grain refiner, and (b) combined
addition of Mo and Al-5Ti-1B grain refiner, as shown in
Fig. 1. The grain size was almost same in the GR samples
irrespective of Mo content. The fine equiaxed grain structure
in the GR samples were due to the presence of TiB2 particles
(and excess solute Ti) that nucleated large fraction of grains
with less undercooling, whereas in the non-grain refined
sample, the crystals that nucleated on the water cold mould
surface grew in opposite direction to the heat extraction and
resulted in coarse columnar grains. Similar to Ti, the solute
Mo in Al is a peritectic forming element and has high growth
restriction factor, hence expected to contribute to the primary
Fe Mn Ni Ti B Al
0.16 0.07 0.003 0.006 – Balance
Influence of Trace Element Additions on Fe Bearing …
a-Al grain refinement [20]; however there was no further
refinement observed even after the addition of Mo at higher
level to the GR samples.
The XRD patterns of the extracted particles, as shown in
Fig. 2, reveals the presence of cubic ac-AlFeSi, monoclinic
b-AlFeSi and Mg2Si in all the samples. This matches well
with the predicted phases using MTDATA software under
the Scheil assumptions (Fig. 3) for the BA composition.
This simulation predicted the formation of a-Al, Al13Fe4,
a-AlFeSi, b-AlFeSi, a-AlMnSi, Mg2Si and Si in sequence
with decreasing temperature from liquid (Fig. 3). As stated
in the earlier articles [7, 11], the absence of Al13Fe4 in the
XRD analysis was mainly because of the non-equilibrium
solidification condition experienced in the casting which
would kinetically displace Al13Fe4 by promoting later pha-
ses (like a-AlFeSi and b-AlFeSi) to solidify at higher tem-
perature. Though Si could be resolved in the extracted
Fig. 1 Polarised light
microscopy images showing the
a-Al grain structure along the
horizontal cross-section of the
a BA, b GR, c GRMo1,
d GRMo2, e GRMo3 and
f GRMo4 samples; g the average
grain size as the function of
different additions
307
particle SEM analysis [11], the absence of Si in the XRD
spectrum is due to them being less in fraction to detect. The
reflection at 33.01 2Ɵ is from the single crystal Si
(100) substrate on which extracted particles were spread for
the XRD analysis. In the GRMo4 sample, Al5Mo inter-
metallic peak is also additionally observed, suggesting
possible primary peritectic product [21].
The higher ac-AlFeSi and b-AlFeSi peaks in the XRD
traces (Fig. 2) indicate that they are the dominant Fe inter-
metallic phases in all the samples. By comparing the peak
intensity at 44.2 and 44.5 2Ɵ it can be seen that the pro-
portion of ac relative to b: (a) significantly decreased with
the grain refiner addition to the BA sample, and (b) gradually
increased with Mo addition to the GR sample. The result
agrees well with the earlier studies, where a 3 fold increase
in b-AlFeSi was found when Al-5Ti-1B is added to a similar
alloy system [10, 11]. This is because the combined
308
Fig. 2 XRD pattern from the extracted particles formed in the different
addition samples
Fig. 3 Thermodynamic calculations of phase fraction in alloy 6063,
assuming a equilibrium, and b, c Scheil solidification conditions
availability of local solute Si rich liquid and heterogeneous
nucleating TiB2 particles at the inter-dendritic region
favoured the solidification microstructure of b-AlFeSi in the
casting. Similarly the segregation of Mo at the inter-dendritic
liquid could possibly promote the ac-AlFeSi formation in the
casting of Mo added GR samples, as observed. Although the
a-Al grain size is similar in all the grain refined samples
(without and with Mo), the ac-AlFeSi or b-AlFeSi can be
selected depending upon the Mo addition. This again
S. Kumar et al.
confirms that the intermetallic phase selection does not
depend on the grain size as proposed earlier [5, 22, 23], but
purely depends on the solute elements that segregated in the
liquid at the inter-dendritic region.
The metallography and extracted particle analysis
revealed (i) large fraction of small aspect ratio particles
within the grain envelop of the BA sample, as in Figs. 4a
and 5a; and (ii) large fraction of large aspect ratio grain
boundary particles in the Al-5Ti-1B and Mo added samples,
as in Figs. 4b–d and 5b–d. Note: the polarized light micro-
scopy image (not given) was used to locate the Fe inter-
metallic particle position with respect to the primary Al grain
structure. The extracted particle analysis further revealed that
the particles within the grain envelope are discrete, whereas
the particles at the grain boundary are inter-connected. The
particles within the grain envelope mainly have flower-like,
spherical-like, and hexagonal platelet-like morphologies, as
in Fig. 5a, whereas the particles at the grain boundary
mainly have platelet-like b-AlFeSi (Fig. 5b) and dendrite/
petal-like ac-AlFeSi (Fig. 5c) morphologies. The particles
inside the grain envelop were less than 5 lm in size, and
were found to be either ac-AlFeSi, b-AlFeSi, Mg2Si, Si, or
combination of these, similar to that reported in [11]. The
mechanism by which the intermetallics inside the grain
envelop formed and solidified can be found in [7]. The
elemental composition of dendrite/petal-like ac-AlFeSi and
platelet-like b-AlFeSi particles observed in the BA and
GRMo4 samples are tabulated in Tables 2 and 3, respec-
tively. The trace amount of Mo in the ac-AlFeSi solid
solution of the Mo added sample suggests Mo segregation
at the inter-dendritic liquid film before the formation of
ac-AlFeSi. The grain boundary particles in the BA sample
were thin and less curved. The association of TiB2 and
b-AlFeSi were frequently seen in the grain refined samples,
and they were similar to that of [11]. In-addition to the Fe
bearing intermetallics, platelet-like Al5Mo intermetallic
particles with *100 lm size, as in Fig. 5d, and with the
elemental composition, as in Table 4, was also frequently
noticed in the GRMo4 sample. The association of Al5Mo
and ac-AlFeSi were seen frequently (Fig. 6), suggesting
possible heterogeneous nucleation of ac-AlFeSi on Al5Mo
taking place. Al12Mo was also identified in the SEM analysis
of GRMo4 sample, but their absence in the XRD spectrum
suggests them being lower in fraction.
Over all the grain structure dictates the shape, size and
morphology of the Fe bearing intermetallic particles, while
the Al-5Ti-1B and Mo additions dictates the intermetallic
phase selection. The coarser the grain size, the finer the Fe
intermetallic particles. The observed decrease in metastable
b-AlFeSi fraction, and Mo in solid solution of ac-AlFeSi,
suggest a lower homogenisation temperature and shorter
homogenisation time is sufficient to complete b-AlFeSi to
Influence of Trace Element Additions on Fe Bearing … 309

Fig. 4 BSE SEM images of the

IMCs in the a BA, b GR,
c GRMo3 and d GRMo4
metallography samples

Fig. 5 SE SEM images of the

IMCs extracted in the a BA,
b GR, c GRMo3 and d GRMo4
samples

Table 2 SEM-EDS chemical Intermetallic Al K Fe L Si K Mn L

composition (in atomic percent)
of the Fe bearing intermetallics in ac-AlFeSi 74.5 17.2 7.6 0.6
BA sample b-AlFeSi 71.8 16.2 12 –
310
Table 3 SEM-EDS chemical Intermetallic Al K
composition (in atomic percent)
of the Fe bearing intermetallics in ac-AlFeSi 73.7
GRMo4 sample b-AlFeSi 71.1
Table 4 SEM-EDS chemical Intermetallic
composition (in atomic percent)
of the Mo bearing intermetallic in Al5Mo
GRMo4 sample
Fig. 6 BSE SEM image showing the association of Al5Mo with
ac-AlFeSi in the GRMo4 sample
ac-AlFeSi transformation for the Mo containing grain
refined 6xxx series Al alloys. The increase in ac-AlFeSi
proportion by suppressing the detrimental b-AlFeSi also
suggests that Mo could be used to tolerate high level of Fe
impurity in the Al casting.
Conclusions
Both ac-AlFeSi and b-AlFeSi were observed in all the
castings. However the addition of Al-5Ti-1B grain refiner to
the base alloy increased the proportion of b-AlFeSi phase in
the casting, while the addition of Mo to the grain refined
alloy increased the proportion of ac-AlFeSi phase. It was
again shown that the grain size only affect the shape and size
of the Fe intermetallics, and not the intermetallic phase
selection. Overall the results suggest that the type of solute
elements and potent nucleating particles that segregated at
the inter-dendritic liquid dictates the type of intermetallics to
form in the casting.
Acknowledgements The authors acknowledge the financial support of
the UK Engineering and Physical Science Research Council (EPSRC)
Impact Acceleration Account Award, EP/K503769/1.
S. Kumar et al.
Fe L Si K Mn L Mo L
16.5 8.3 0.6 0.9
15.9 13 – –
Al K Mo L
86.6 13.4
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 Part VIII
Aluminum Alloys, Processing and Characterization:
Heat Treatment
 The Optimization of the Homogenization
Treatment of AA7075

Gheorghe Dobra, Ioan Sava, Marin Petre, and Gheorghe Popa

Abstract
The homogenization treatment of 7075 aluminium alloy slabs is required for ensuring the
technological properties for later processing. This usually has two stages. The soaking time
in the second stage has an important influence. In order to evaluate the influence of this
parameter, the homogenization, solution heat treatment, quenching and ageing treatment
were simulated in the laboratory at various homogenization soaking time between 4 and
24 h. The evolution of the eutectic structures in the as-cast and homogenized 7075
aluminium alloy were investigated by scanning electron microscopy (SEM), energy
dispersive spectrometry (EDS), differential scanning calorimetry (DSC) and tensile test.
The results demonstrate that from many standpoints (mechanical properties, microstructure
etc.) the complete dissolution of all soluble phases ends before the limit of 20 h that is
considered as standard all over industry.

Keywords
7075 aluminum alloy Homogenization Microstructural evolution

Introduction it was shown that the three-step homogenization practice

The main purpose of the homogenization treatment after
casting, when the microstructure of the alloy is usually
heterogeneous, is to remove the consequences of dendritic
segregation and dissolution of coarse eutectic intermetallic
phases that cause a decrease of the fracture toughness of the
alloy [1]. Homogenizations is mainly designed to make sure
that all possible soluble elements are in solid solution. The
stress relief takes place concurrent with homogenization to
ensure an even distribution of the internal tensions. The main
parameters of the homogenization heat treatment are the
heating temperature, the holding time and the cooling rate.
The two stage practices are generally used. According to
literature data [2, 3] the microstructure depends on homog-
enization time and only one stage for heat treatment at 460 °
C for 24 h does not ensure complete homogenization. In [4]
G. Dobra
I. Sava (&)
M. Petre
G. Popa
ALRO, 116 Pitesti Street, Slatina, 230104, Romania
e-mail: isava@alro.ro
(200 °C/2 h + 460 °C/6 h + 480 °C/12 h) has a better
effect than single homogenization (465 °C for 6, 16 and
24 h, respectively) as revealed by complete elimination of
the endothermic peak of non-equilibrium phases. In another
study [3] for improving the material ductility, a two-stage
cycle of homogenization (470 °C/18 h + 490 °C/7 h) is
recommended for the AA7075 cast alloy. For 7xxx series
alloys the homogenization is typically performed at 450–
500 °C, but the temperature range is influenced by the alloy
chemical composition [5]. In order to ensure the dissolution
of low melting metastable eutectic phases a short first stage
around 440–470 °C is applied, followed by a long second
stage at higher temperature, usually at 470–490 °C. The long
period for homogenization is required due to the long
solidification range. Usually the optimization of the ho-
mogenization cycle is performed by using a laboratory test
of the thermal cycle in a programmable furnace, with sam-
ples taken from the central part of a cast slab. Scanning
electron microscopy (SEM), differential scanning calorime-
try (DSC) and tensile tests (TT) provides an evaluation of the

© The Minerals, Metals & Materials Society 2017 315

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_42
316
homogenizations degree achieved during the cycle. The
mechanical properties of rolled products are also affected by
the homogenization treatment due to the presence of alloying
elements in solid solution. These elements influence the
material strength, mainly through solid solution or precipi-
tation hardening [6].
This article is intended to provide useful data on opti-
mization for the homogenization treatment of AA7075 from
economical point of view. In that way it was studied how
much the soaking time and temperature can be reduced to
ensure the technological reliable properties for later
processing.
Experimental
The samples for the simulation of the homogenizations
treatment of AA7075 were taken from a cast slab with the
chemical composition according to the Table 1.
Before cutting samples a stress relief treatment of the slab
was performed at 400 °C, for 8 h. Subsequently, a slice of
slab was cut at the dimensions of 25 mm  500 mm
1650 mm and 20 samples were taken from center of the slice
at the dimensions 25 mm  25 mm  250 mm (Fig. 1).
For an easy identification each sample was punched and
numbered. The non-homogenized sample was identified
with the number 100 and the homogenized samples with a
3-digit number: the first digit denotes 1, stands for the slice
number, and the following two digits denotes the soaking
time, in hours, for the second stage of homogenization (e.g.,
124 denotes slice 1, and 24 h of homogenization time).
Table 1 Chemical composition of 7075 aluminium alloy slab used in these experiments (mass fraction, %)
Si Fe Cu Mn Mg Cr
0.16 0.25 1.45 0.04 2.35 0.18
Fig. 2 Diagram for the
simulation of the homogenization
treatment for AA7075 samples
G. Dobra et al.
Fig. 1 The sketch for sampling
The double-stage homogenization treatment was per-
formed in a laboratory furnace (Memmert) at 440 °C for 4 h
and then at 475 °C for 6, 7, 8, …, 23 and 24 h, respectively.
The diagram for the simulation of the homogenizations
treatment for AA7075 samples is presented in the Fig. 2.
After homogenization treatment, the samples were solu-
tion heat treated at 475 °C/2 h in a laboratory furnace
(Memmert). The quenching was done by immersion in cold
water (20 °C). At the end, the artificially ageing treatment
was carried out with the parameters 135 °C/12 h. After heat
treatments, specimens were machined and mechanical tested
on a Zwick tensile test machine.
For thermal analysis a Netzsch DSC 204 F1 Phoenix
apparatus was used in the 50–550 °C range. Experiments
were conducted in synthetic air. The gas flow rate was
20 ml/min, heating rate was 20 °C/min, and aluminium
crucibles were used. Samples were disks of 5 mm diameter,
and 1 mm thickness.
Scanning Electron Microscopy (SEM) images of
heat treated samples were taken with a Zeiss Evo 50
microscope.
Ni Zn Ti Ga V Al
0.006 5.70 0.028 0.009 0.022 REM.
The Optimization of the Homogenization Treatment of AA7075 317

Results and Discussion
Tensile Tests
The results of the tensile tests are presented in the Table 2.
The dependence ultimate tensile strength (Rm)—soaking
time is presented in Fig. 3. The Rm-soaking time variation
show scattered values, but for a soaking time ranging
between 10 and 20 h the values are close to the polynomial
fitting of data. Also the degree of scattering of the measured
properties are due to the other characteristics of the material
induced by the sampling and processing conditions.
As expected, the lowest value for Rm, respectively
465 MPa, was recorded for sample that wasn’t subjected to
the homogenization treatment, while the heat treated samples
show an improvement of Rm with up to *15% (sample 118).

Table 2 The mechanical tensile Sample Soaking time for the second stage (h) Rm Rp02 Elongation
test results number (MPa) (MPa) (%)
100 Non-homogenized 465 – –
106 6 487 460 1.5
107 7 533 500 2
108 8 527 502 1
109 9 487 481 1.5
110 10 499 472 1.5
111 11 529 503 2
112 12 509 494 0.5
113 13 510 469 6
114 14 498 475 1
115 15 503 475 1.5
116 16 514 486 1
117 17 517 479 2.5
118 18 539 506 3
119 19 522 486 3.5
120 20 531 494 4.5
121 21 523 492 2.5
122 22 492 459 2.5
123 23 506 477 2
124 24 505 470 4

Fig. 3 The variation of the

ultimate tensile strength (Rm) on
the soaking time
318
Thermal Analysis
The thermal analysis results are presented in the Fig. 5. For
each sample the transformations at heating and cooling were
recorded.
The sample no. 100 presents an endothermic transfor-
mation at 483 °C, with a pronounced thermal effect, pre-
ceded by another endothermic transformation, wider, but
with lower amplitude (Fig. 4a). This is associated with the
Fig. 4 DSC curves of the
non-homogenized 7075
aluminium alloy sample
G. Dobra et al.
solubilization of AlMgZnCu phase in the solid solution
matrix based on aluminium.
On cooling the transformation associated with precipita-
tion shows an exothermic effect, with a high amplitude,
followed by a wider exothermic transformation of a much
lower amplitude (Fig. 4b).
The samples that were subjected to the homogenization
heat treatment at various intervals of time presents different
thermal evolutions than the untreated sample (Fig. 5).
a. Heating.
b. Cooling.
The Optimization of the Homogenization Treatment of AA7075 319

A consistent behavior is observed on cooling, when all
samples have two exothermic transformations, which are clearly
distinguishable. Instead, when samples are heated, endothermic
transformation at a higher temperature does not always have
the same allure and is preceded by large thermal effects.
The thermal transformation at 483 °C of the untreated
sample (sample 100, Fig. 5) does not occur after samples are
heat treated. Instead, a new transformation occurs in heat
treated samples at *502 °C, attributed to solubilization of
Al2CuMg phase.
The associated endothermic peak does not occur in a
consistent way, until its disappearance (after homogenization
treatment with a duration of 13 h—Fig. 6), and it has dif-
ferent intensities.

Fig. 5 The comparison between

DSC curves of AA7075
homogenized samples and the
non-homogenized sample, during
heating. a 3D representation,
b 2D representation, exo up
320 G. Dobra et al.

EDX Analysis

The chemical composition of the AA7075 according to

Fig. 6 The disappearance of the endothermic transformation (at
*500 °C, exo up), after 13 h of homogenization
ASTM B209 is presented in Table 3.
It is observed that after 12 h of homogenization, the
chemical composition falls into the accepted variation range.
Also, the difference between the calculated average
composition of all the 10 samples analyzed and the sample at
24 h isn’t significant, except for Fe (Table 4, Fig. 7).
Sample no. 100 which wasn’t subjected to homogeniza-
tion heat treatment has grains of Al-based solid solution
(a-Al), with segregation of alloying elements (Mg, Zn, Cu)
to the grain limit (Fig. 8a) in the compounds form, such as
MgZn2 (η), Al2Cu, AlCuMg, Al2Mg3Zn3 (T), Al6CuMg4,
Al2CuMg (S), Al7Cu2Fe and others [7].
The area immediately neighboring of the segregation is
poorer in the precipitation phase. The grains contain fine

Table 3 The chemical AA 7075

composition of the AA7075
according to ASTM B209 Si Fe Cu Mn Mg Cr Zn Ti Other elements Al
Each Total
 0.40  0.50 1.2–2.0  0.30 2.1–2.9 0.18–0.28 5.1–6.1  0.20  0.05  0.15 REM.

Table 4 Chemical composition Sample number Al Zn Mg Cu Fe

determined by EDX for the 10
samples over an area at.% wt% at. wt at. wt at. wt at. wt
corresponding to a magnification % % % % % % % %
of 300 100 93.93 90.88 1.86 4.36 3.39 2.95 0.55 1.24 0.28 0.55
(1024  768 µm2  0.78 mm2)
106 93.78 90.74 1.90 4.46 3.55 3.09 0.57 1.30 0.20 0.41
107 92.01 87.30 3.01 6.92 3.76 3.21 0.59 1.31 0.64 1.27
108 92.14 87.55 3.02 6.95 3.76 3.22 0.56 1.26 0.52 1.02
109 92.24 87.62 2.98 6.87 3.63 3.11 0.60 1.33 0.54 1.06
110 91.33 86.16 3.15 7.21 3.95 3.36 0.81 1.81 0.75 1.46
111 91.92 87.17 3.13 7.19 3.89 3.32 0.82 1.83 0.25 0.48
112 92.99 89.41 2.29 5.33 3.84 3.32 0.66 1.48 0.23 0.46
118 92.00 87.44 2.96 6.83 3.95 3.38 0.78 1.75 0.31 0.60
124 93.06 89.13 2.52 5.85 3.50 3.02 0.67 1.51 0.25 0.49
Average 88.25 6.2 3.2 1.48 0.78
The Optimization of the Homogenization Treatment of AA7075
Fig. 7 EDX analysis report for
sample no. 108
acicular precipitates of MgZn2 or if the Si is present, they
contain Mg2Si, these having spheroidal appearance [7]
(Fig. 8a).
Following the homogenization heat treatment, the segre-
gated elements at the grain boundary diffuses into the a-Al
matrix of crystallites. The grain boundary becoming poorer
in Cu, Mg, Zn, but rich in Fe (Fig. 8b–i). In addition to
narrowing, the precipitate phases are fragmenting along the
grain boundary (Fig. 8e). Also, in crystallites, the fineness of
precipitates of MgZn2 [8] increases with duration of
homogenization.
The segregated phases at the grain boundary are rich in
the following elements: Cu, Zn, Mg and Fe, but poor in Al.
The inside of crystallites is rich in Fe and Mg elements
(Fig. 9).
For the sample homogenized at 10 h an area rich in Fe
and Cu, which can be attributed to the compound Al7Cu2Fe
(Fig. 10) is observed.
321
Industrial Tests
Based on presented experimental results, 5 slabs from two
cast charges were homogenized in industrial facilities at
440 °C for 4 h and then at 475 °C for 13 h. The slabs were
scalped each side, preheated at 430 °C and hot rolled in
plates with thickness in the range 15–90 mm Table 5.
After hot rolling, the plates were solution heat treated and
stress relieved by stretching. At the end, the artificially
ageing treatment was performed and the specimens for
mechanical tests were machined and tested.
The results of the tensile tests are presented in the Table 6.
All values obtained were within the limits imposed by EN
485-2:2013 standard. In order to evaluate the technological
changes brought, we compared for samples of same thickness,
the average values of the industrial tests with the average
values obtained in the current production for one year, from
01-Aug-2015 until 01-Aug-2016. For the current production
322 G. Dobra et al.

Fig. 8 SEM backscattering

images of as-cast and
homogenized at 475 °C samples,
for different times: a as-cast;
b 6 h; c 7 h; d 8 h; e 9 h; f 10 h;
g 11 h; h 12 h; i 18 h; j 24 h
The Optimization of the Homogenization Treatment of AA7075 323

Fig. 9 Multi-element mapping

for as-cast specimen, stress relief
treatment: a Al; b Cu; c Zn;
d Mg; e Fe; f SEM image at
5000 magnification

of AA7075 slabs a two-stage cycle of homogenization is
applied (440 °C/4 h + 475 °C/20 h). The tendency for the
average values and the minimum limits imposed by standard is
represented in Fig. 11. For Rm we established the regression
equations by the least square method [9] and the associated
coefficient of determination, R2.
The obtained values for Rm in the industrial tests presents
a slight decrease compared to the current values from
production.
The difference between the current production and the
industrial tests for Rm easily grows with the increasing of
the plate thickness.
324 G. Dobra et al.

Fig. 10 Multi-element mapping

for homogenized specimen at
475 °C/10 h: a Al; b Cu; c Zn;
d Mg; e Fe; f SEM image at
5000 magnification

Table 5 Chemical composition of AA7075 charges used in these industrial tests (mass fraction, %)
Si Fe Cu Mn Mg Cr Ni Zn Ti Ga V Al
Charge 1 0.10 0.23 1.35 0.04 2.33 0.18 0.006 5.50 0.03 0.009 0.022 REM.
Charge 2 0.15 0.24 1.33 0.04 2.35 0.18 0.006 5.58 0.03 0.009 0.022 REM.
The Optimization of the Homogenization Treatment of AA7075 325

Table 6 The mechanical test No. Charge no. Thickness (mm) Rm (MPa) Rp02 (MPa) Elongation (%)
results
1 1 15 588 523 11.5
2 1 15 576 514 11.5
3 1 15 569 506 12
4 1 15 584 518 11.5
5 1 90 522 443 10.5
6 1 90 515 438 7.5
7 1 90 511 433 7.5
8 1 90 519 443 8
9 1 90 516 435 9.5
10 1 90 523 447 9
11 1 90 523 445 9
12 2 20 578 516 10.5
13 2 20 567 506 10
14 2 41 544 479 10.5
15 2 41 544 477 12.5
16 2 82 522 450 9
17 2 82 531 455 11.5

Fig. 11 The dependence of Rm

on thickness: our industrial tests
versus current production

Table 7 The minimum limits Thick. (mm) Rm (MPa)—minimum acc. EN485-2:2013 Rm (MPa)— Growtha (%)
and the obtained average values average
for Rm
1 year Tests 1 year Tests
15 540 577 579 6.9 7.3
20 540 578 573 7.0 6.0
41 530 559 544 5.4 2.6
82 490 531 527 8.4 7.4
90 490 522 518 6.5 5.8
a
The growth between the mean recorded and the minimum limit imposed
326
As it can be observed from Table 7, the values for Rm
has still enough room till reaching the minimum limits
imposed.
Conclusions
Our study provides useful data regarding the optimization of
AA7075 homogenization treatment from economical point
of view. Thus, it was presented how much the soaking time
can be reduced to ensure the technological reliable properties
for later processing.
If 13 h is considered an optimal homogenization time,
then the total cycle time is reduced with almost 30%. This
also involves a substantial reduction of energy, working time
and other costs.
The experimental results were successfully applied in
ALRO and an important improvement of the productivity
was obtained for homogenization furnaces, without affecting
the products quality.
The technique presented can be used for other alloy slabs
as well, in order to optimize the industrial process.
Depending on the particularities of each producer, the
homogenization time could be adjusted as to save costs
without negative impact over the product quality.
G. Dobra et al.
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(Revere Copper and Brass Inc., New York, 1967), p. 857
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alloy AA7075 using calorimetric and microstructural studies. Metal
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 Precipitation Modeling and Validation
of Al–5%Cu–0.4%Mn Alloy Using Quench
Factor Analysis

Yisen Hu, Gang Wang, Wenguang Wang, Mao Ye, and Yiming Rong

Abstract
Quench factor analysis has been widely used to describe how precipitation in quenching
affects the development of properties of aluminum alloys in subsequent aging treatment. To
minimize the amount of effort and time, Jominy end quench was used to conduct quench
factor analysis. The author applied Jominy end quench test to Al–5%Cu–0.4%Mn alloy,
followed by different artificial aging time, and Rockwell hardness was measured along the
length of the samples. Quench factor analysis was conducted with measured data. Critical
time at different temperatures of Al–5%Cu–0.4%Mn was calculated with the kinetic
parameters and 400 °C was demonstrated to be the sensitive temperature. In addition, the
effect of quenching rate on aging was studied and the strengthening effects of precipitation
during quenching and aging were compared. The results revealed that with decreasing
quenching rate, the peak aging time and the hardness of as-quenched increased, whereas the
peak hardness decreased.

Keywords
Precipitation Quenching rate Al–5%Cu–0.4%Mn alloy Jominy end quench
Peak aging

Introduction quenching rate, the supersaturated solubility of Cu in Al

Al–5%Cu–0.4%Mn alloy is one of light weight and high
strength cast alloys, which is widely applied to large
thin-wall structures in automobile and aerospace industries
[1]. The alloy is heat-treatable and its mechanical properties
depend mostly on quenching rate and aging conditions [2].
There is now a general consensus that with decreasing
Y. Hu (&)
G. Wang
W. Wang
Department of Mechanical Engineering, Tsinghua University,
Beijing, 100084, China
e-mail: hys3225588@126.com
M. Ye
Capital Aerospace Machinery Company, Beijing, 100076, China
Y. Rong
Mechanical and Energy Engineering Department,
South University of Science and Technology of China,
Shenzhen, 518055, China
decreases, causing the loss of the mechanical properties
[3, 4].
To describe the effect of quenching rate on the loss in
ability to develop strength, quench factor analysis (QFA) was
proposed and improved in recent years [5–8]. QFA was a
method based on precipitation theory and kinetic parameters
to determine time-temperature-property (TTP) C-curve of an
aluminum alloy in quenching need to be experimentally
estimated and verified. In general, interrupted quench tech-
nique was used to collect the experimental data to determine
the kinetic parameters [9–11]. However, interrupted quench
technique required tedious experimental work that relatively
limited the use of QFA up to the present time.
The Jominy end quench method was originally developed
to determine the quench sensitivity of steels [12, 13], but
now it has been applied to estimating kinetic parameters of
aluminum alloys for QFA [14–16], as it could provide
multiple sets of cooling curves with only one quench.

© The Minerals, Metals & Materials Society 2017 327

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_43
328
Therefore, amount of experimental work could be saved in
the Jominy end quench test, as compared with interrupted
quench technique.
The kinetics of transformation in QFA followed the
Johnson-Mehl-Avrami-Kolmomogorov equation. In general,
aging kinetics was increased by increasing quenching rates,
for the decomposition kinetics during aging was strongly
influenced by the concentration of quenched-in vacancies
and vacancy-related defects, determined mainly by the
quenching temperature, quenching rate and alloy chemistry
[17]. Thus, the peak aging time to produce peak strength was
affected by quenching rate, causing possible errors in QFA
predictions, which should be considered.
In this paper, the Jominy end quench method was applied
to collect the experimental data of Al–5%Cu–0.4%Mn alloy
for QFA. The kinetic parameters were numerically estimated
by multiple nonlinear regression and a TTP curve was gen-
erated. Furthermore, the hardness of the samples with differ-
ent quenching rates and different aging time were measured
and the effect of quenching rate on aging was studied.
The Mathematical Model
QFA was proposed to predict the loss of strength by cal-
culating the precipitation during quenching based on TTP
C-curves. The nucleation kinetics of equilibrium precipitates
transition show a C-shaped behavior. The critical time Ct ðTÞ
function, which mathematically describes the C-curve, is
defined as the reciprocal of the classic nucleation equation
and is shown in Eq. (1):
k3 k42 k5
CT ¼ k1 k2 exp½ 2
 exp ð1Þ
RTðk4  TÞ RT
where CT is the critical time to precipitate the amount
required to reduce the attainable strength to 0:995rmax (s),
k1 ¼ lnð0:995Þ, k2 is a constant that includes the reciprocal
of the number of potential nucleation sites (s), k3 is a con-
stant that includes the change in free energy associated with
the formation of the nucleus (J K−1 mol−1), k4 is related to
the solvus temperature (K), k5 is the mobility term (J mol−1),
and R is the gas constant (8.3143 J K−1 mol−1).
Cahn [18] studied the precipitation under non-isothermal
conditions and proposed that the precipitation at different
temperatures is additive. For continuous cooling, the fraction
of precipitates can be integrated. To calculate the fraction
transformed, a quench factor is proposed and given by
Eq. (2):
Ztf X
n1
1 Dti
Q¼ dt ¼ ð2Þ
CT 1
CTi
t0
Y. Hu et al.
where Q is the quench factor, t0 is the time at start of quench
(s), and tf is the time at finish of quench (s).
By assuming that the kinetics of transformation follows
the Johnson-Mehl-Avrami-Kolmomogorov equation, the
property of the alloy can be predicted from Eq. (3):
r  rmin
¼ exp½ðk1 QÞn  ð3Þ
rmax  rmin
where r is the yield strength of the alloy (MPa), rmin is the
minimum yield strength of the alloy, which is
temperature-dependent (MPa), rmax is the maximum yield
strength of the alloy after an infinitely fast quench (MPa),
and n is the Avrami exponent.
Experimental Methods
The detailed composition of Al–5%Cu–0.4%Mn alloy used
in this paper was given in Table 1. The experimental sam-
ples for Jominy end quench were divided into two parts and
machined, as was shown in Fig. 1. The thermocouples to
measure the quenching rates were set in the grooves and
distances from the quench end were listed in Table 2.
Finally, the two parts were glued by high temperature
cement.
The samples glued were heated in Muffle furnace at
540 °C for 10 h and quenched in the Jominy end quench
apparatus, whose schematic was shown in Fig. 2. The tem-
perature during quenching were recorded by Graphtec
GL7000 with a 100 Hz sampling rate. And then the samples
were heated in Muffle furnace at 175 °C for different artifi-
cial aging time. The aging time was listed in Table 3.
Finally, the Rockwell hardness of the positions, where the
thermocouples were set, were measured.
Results
Figure 3 gives the cooling curves of the Jominy end quench
test. Because the quenching occurred at one end of a bar, the
cooling along the sample was one-dimensional and the
cooling rate decreased with the increasing distance from the
quench end. The cooling rate curves were obtained by cal-
culating the derivative of the cooling curves, which were
shown in Fig. 4. The maximum cooling rate declined rapidly
from 91 to 39 °C/s when the distance increased from 3.2 to
6.4 mm. And when the distance increased to 63.5 mm, the
maximum cooling rate was only 4 °C/s.
Figure 5 shows the Rockwell hardness along the sam-
ples. The hardness of the as-quenched alloys increased from
10.3 HRB to 28.4 HRB when the distance increased from
3.2 to 63.5 mm. With the increasing aging time, the
Precipitation Modeling and Validation of Al–5%Cu–0.4%Mn Alloy … 329

Table 1 Main element composition of ZL205A

Element Cu Mn Ti Zr Cd B V Al
wt% 4.6–5.3 0.3–0.5 0.15–0.35 0.05–0.20 0.15–0.25 0.005–0.006 0.05–0.3 Bal.

Fig. 1 The experimental samples

Table 2 Distance from the quench end where the thermocouples were set
Number 1 2 3 4 5 6 7 8 9 10
Distance (mm) 3.2 6.4 9.5 12.7 15.8 22.2 31.7 38.1 50.8 63.5

Fig. 2 Schematic of the Jominy end quench apparatus

Table 3 The artificial aging times

Number 1 2 3 4 5 6 7
Aging time (h) 0 1 2 4 8 16 24
330 Y. Hu et al.

600 3.2mm t=0h

6.4mm t=1h
9.5mm 80 t=2h
t=4h
12.7mm t=8h
70
15.8mm t=16h
400 22.2mm 60 t=24h
°C

Hardness (HRB)
31.7mm
50
38.1mm
50.8mm 40
63.5mm
30
200
20

10

0
0 0 10 20 30 40 50 60 70
0 200 400 Distance (mm)
Time(s)
Fig. 5 Hardness along the Jominy end quench sample of Al–5%Cu–
Fig. 3 Cooling curves at different positions of the samples 0.4%Mn with different aging times

Discussion

QFA was conducted with the experimental data and the

strengthening effects of precipitation during quenching and
aging were discussed.
°c

Quench factor analysis of Al–5%Cu–0.4%Mn

In general, the peak aging time for Al–5%Cu–0.4%Mn is

ºC S
Fig. 4 Cooling rate curves at different positions of the samples
hardness increased up to the peak hardness and then
decreased, other than a tiny decrease in the first hour. The
peak aging time was 8 h at the distance between 3.2 and
31.7 mm, whereas it was 16 h at the distance between 31.7
and 63.5 mm. In contrast to the as-quenched hardness, the
peak hardness decreased from 82.6 HRB to 73.6 HRB when
the distance increased from 3.2 to 63.5 mm. Taken together
with the quenching rate, the peak aging time and the peak
hardness, it indicated that the growth rate of the hardness
during aging treatment decreased with the decreasing
quenching rate.
6–8 h. The hardness of the quench end aged for 8 h was
83.8 HRB and it was regarded as the maximum hardness.
The minimum hardness was regarded as 0 and the data of
cooling curves, the hardness of the samples aged for 8 h and
the maximum hardness were utilized in Eqs. (1), (2) and (3).
Using a multiple nonlinear regression analysis, the optimal
value of k1–k5 and n were confirmed and listed in Table 4.
The correlation between the measured and the predicted
hardness was plotted in Fig. 6, which showed that the pre-
dicted data matched well with the measured data.
With the kinetic parameters in Table 4, the critical time at
different temperatures of Al–5%Cu–0.4%Mn were calcu-
lated using Eq. (1) and the TTP curve for 99.5% of 83.8
HRB was shown in Fig. 7. The results revealed that 400 °C
was the sensitive temperature for Al–5%Cu–0.4%Mn and
the critical time at 400 °C for 99.5% of 83.8 HRB was
0.59 s. Therefore, when the temperature approached 400 °C,
short time was required for the precipitates to nucleate and
grow and significant loss of mechanical properties occurred.
Precipitation Modeling and Validation of Al–5%Cu–0.4%Mn Alloy … 331

Table 4 The kinetic parameters of QFA for Al–5%Cu–0.4%Mn

k1 k2 (s) k3 (J/mol) k4 (K) k5 (J/mol) n
−0.00501 1.72e-4 2322 1036 54,093 1.8

Fitted 99.5% of 458MPa

84
Measured 550
82
Predicted
500

80 450
Hardness (HRB)

˚C
78 400

76 350

300
74
250
72
200
70
150
0.1 1 10 100 1000 10000
68
Critical times(s)
0 10 20 30 40 50 60 70
Distance (mm) Fig. 8 TTP curve of Al–5%Cu–0.4%Mn by isothermal quench
technique
Fig. 6 The correlation between the measured and the predicted
hardness
strenghening effects by aging treatment for 8 h
90
as-quenched
80
600
Fitted 99.5% of 83.8RHB
70

500 60
Hardness (HRB)
Critical times (S)

50
400
40

300 30

20

200 10

0
100 3.2 6.4 9.5 12.7 15.8 22.2 31.7 38.1 50.8 63.5
0.1 1 10 100 Distance (mm)
Temperature (˚C)
Fig. 9 Hardness of as quenched alloys and the strengthening effects by
Fig. 7 TTP curve of Al–5%Cu–0.4%Mn by Jominy end quench aging treatment for 8 h

Figure 8 gives the TTP curve obtained by isothermal quench
test, which was conducted by the author before. Although
some differences existed between the shapes of the two TTP
curves, the sensitive temperatures were almost the same.
Thus, this indicated that the TTP curve obtained by Jominy
end quench was valid.
Effects of Quenching Rate on Aging
QFA predicts the loss in ability to develop strength by cal-
culating precipitation in quenching and it assumes that pre-
cipitation in quenching has no strengthening effect on alloys
[19]. However, Fig. 9 shows that the hardness of the
332 Y. Hu et al.

as-quenched alloys increased with the increasing distance Conclusion

from the quench end. It indicated that the alloys were
strengthened by precipitation in quenching, although the (a) The Jominy end quench was applied to construct TTP
effect was lower than precipitation in aging. In alloys of the curve and the Rockwell hardness along the samples for
Al–Cu system, a succession of precipitates is developed Al–5%Cu–0.4%Mn after aging treatment for 8 h were
from a rapidly cooled super-saturated solid solution (SSS). measured and predicted using quench factor analysis.
These precipitates develop sequentially either with increas- (b) Critical time at different temperatures of Al–5%Cu–
ing temperature or with increasing time at temperature 0.4%Mn was calculated with the kinetic parameters. For
between room temperature and the solvus. The several Al–5%Cu–0.4%Mn, 400 °C was the sensitive tempera-
stages are identified by the following notation: ture. Thus, less time was required for the precipitates to
00 0 nucleate and grow at 400 °C.
SSS ! GP zones ! h ! h ! hðAl2 CuÞ
(c) The Rockwell hardness for Al–5%Cu–0.4%Mn after
With the decreasing quenching rate, the time at temper-
quenching and different aging time was measured. The
ature between room temperature and the solvus increased
strengthening effect of precipitation during quenching
and some precipitation occurred during quenching. As a
and aging were compared. The rate of precipitation in
result, the hardness of the as-quenched alloys increased,
aging increased with the increasing quenching rate and
whereas the supersaturated solubility decreased, causing the
the hardness in peak aging state decreased with the
decreasing strengthening effects by aging treatment for 8 h.
decreasing quenching rate.
In Al–Cu alloys, the GP zones are the first to nucleate
because of their small size and coherency with the matrix,
and then generally grow into more stable transition phases
Acknowledgements This work was supported by National Natural
and eventually an equilibrium phase. Each step results in the Science Foundation of China (grant number U1537202) and Beijing
previously precipitated phase being replaced with the new, Natural Science Foundation (grant number 3152013).
more stable phase. Therefore, at the beginning of aging
treatment, the GP zones dissolved and the h′′ precipitates had
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 Young’s Modulus of Al–Si–Mg–Cu Based Alloy
Under Different Heat Treatment Processes

Sajjad Amirkhanlou, Yijie Zhang, Shouxun Ji, and Zhongyun Fan

Abstract
Young’s modulus of metallic materials is one of the most important mechanical properties
in controlling structural design. The increase of Young’s modulus in cast aluminium alloys
is attractive for lightweight structures. In the present investigation, the Young’s modulus of
an Al–Si–Mg–Cu alloy reinforced with TiB2 and Mg2Si phases was investigated under
different heat treatment processes, including T4, T6, T7 and O. The microstructural
evaluation and mechanical properties of the developed Al–Si–Mg–Cu alloys were
examined by X-ray diffractometer (XRD), scanning and high resolution transmission
electron microscopes (SEM and HRTEM), ultrasonic pulse technique and tensile test. The
results revealed that the alloys, in all heat treatment conditions, mainly consist of Si, Mg2Si
and TiB2 phases, which are responsible for the increase of Young’s modulus. HRTEM
micrographs showed the formation of incoherent, clean and smooth interfaces between
aluminium matrix and TiB2 particles. The alloys with over 90 GPa Young’s modulus are
still castable for making shaped castings. In comparison with the conventional aluminium
alloys that have Young’s modulus at a level of 70 GPa, 30% increase of Young’s modulus
can be achieved by the developed alloys.

Keywords
Aluminium alloys Microstructure Mechanical properties Young’s modulus Heat
treatment

Introduction the price of energy is increasing and society requires a

Today, the automotive industry has to respond to the con-
tradictory requirements of obtaining a significant weight
reduction for structures, while guaranteeing passenger
safety. This is of particular interest in today’s context where
S. Amirkhanlou (&)
Y. Zhang
S. Ji
Z. Fan
BCAST, Brunel University London, London, UB8 3PH, UK
e-mail: sajjad.amirkhanlou@brunel.ac.uk
Y. Zhang
e-mail: yijie.zhang@brunel.ac.uk
S. Ji
e-mail: shouxun.ji@brunel.ac.uk
Z. Fan
e-mail: zhongyun.fan@brunel.ac.uk
reduction in CO2 emissions [1–3]. To address this challenge,
a new generation of high modulus aluminium-based alloy
should be developed for automotive applications. Generally,
high modulus phases can be introduced to the aluminium
matrix through alloying elements and/or ceramic particles to
form aluminium matrix composites (AMCs) [4, 5]. Among
the available elements, Si and Cu are the favourite candi-
dates enhancing the modulus of aluminium alloys. Addition
of Si, having Young’s modulus of 150 GPa, into the alu-
minium alloys leads to the direct increases of modulus, while
Cu impact on modulus increment is governed by the for-
mation of stiff Al(Cu) solid solution and Al2Cu (E = 110
GPa) phases. Meanwhile, the aluminium alloys with Si and
Cu are capable of casting complex shapes, but the increases
in Young’s modulus are usually less than 15% [6]. To

© The Minerals, Metals & Materials Society 2017 335

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_44
336
further improvement of Young’s modulus, aluminium alloys
need to be reinforced by adding high modulus phases such
as TiB2 and Mg2Si into aluminium matrix. TiB2 and Mg2Si,
display both high modulus and low density, can lead to a
hybrid alloy exhibiting very different properties from con-
ventional aluminium alloys since their stiffness can be
increased significantly [7, 8]. Up to now, limited attempts
have been performed for Young’s modulus improvement,
which has different emphasis in terms of the phase forma-
tion, reinforcement size and distribution, and particle/matrix
interface. Therefore, the aim of the present work is to
investigate the possibility of fabricating high modulus
aluminium-based alloys. Furthermore, effect of different heat
treatment conditions on mechanical properties was investi-
gated. The microstructures and mechanical properties of the
experimental materials under different heat treatment con-
ditions were studied by optical microscopy, SEM and
TEM/HRTEM.
Experimental
The Al–9Si–1Mg–0.7Cu/TiB2–Mg2Si (thereafter Al–Si–
Mg–Cu hybrid alloy) was produced by adding the mixture of
KBF4 and K2TiF6 into the molten Al–7Si–0.3Mg alloy with
the addition of Si and Cu through the exothermic reaction.
The two types of salts were added to the molten aluminium
alloy in the atomic ratio in accordance with Ti/2B ratio. The
salts were maintained at 850 °C for 30 min to complete the
reactions. Then the melt was degassed by a rotatory machine
at 500 rpm for 3 min, followed by casting tensile samples in
a standard ASTM B108 mould. The alloy was reinforced
with 8.9 vol.% TiB2 and 1.6 vol.% Mg2Si particles. The
chemical compositions of the experimental materials were
analysed using a Perkin-Elmer Optima 5300 dual view
ICP-AES and the results are given in Table 1.
The Al–Si–Mg–Cu hybrid alloy was heat treated under
different heat treatment conditions, as shown in Table 2.
Table 1 Chemical composition of the experimental materials identified by ICP-EDS (wt%)
Elements Si Cu
Al–Si–Mg–Cu hybrid alloy 9 0.7
Table 2 Heat treatment details Code Solutionizing temperature (°C)
of the Al–Si–Mg–Cu hybrid alloy
T4 525
T6 525
T7 525
O 525
S. Amirkhanlou et al.
Desirable times and temperatures for heat treatment pro-
cesses have been selected from data available data in Ref [9].
The microstructures were characterized by high resolu-
tion transmission electron microscopy (HR-TEM, JEOL
2100F, JEOL Ltd. Tokyo, Japan) operated at 200 kV and
field-emission scanning electron microscopy (SEM, SUPRA
35VP, Carl-Zeiss Company, Jena, Germany) operated at
15 kV. Thin foils required for TEM were mechanically
ground and punched into 3 mm discs with an average
thickness of less than 100 lm. The discs were subsequently
ion beam thinned using a Gatan precision ion polishing
system (PIPS) at 5.0 kV and at an incident angle of 4°. The
X-ray patterns of the specimens were recorded by a D8
advanced Bruker X-ray diffractometer (Bruker Corporation,
Billerica, Massachusetts, United States) with CuKa radiation
in the range of 20–90° using a step size of 0.05° and a
counting time of 1 s per step. Consequently, XRD patterns
were analysed by using X’Pert High Score software.
Young’s modulus of the specimens was measured by a
dynamic method namely ultrasonic pulse technique accord-
ing to ASTM E1875-13 standard. Parallel smooth surfaces in
the specimens were shaped by grinding and polishing before
measuring the transversal and longitudinal wave velocities.
The wave velocities of the specimens were measured using a
38DL PLUS Ultrasonic Thickness Gage (Olympus Indus-
trial) and the Poisson’s coefficient (#) and Young’s modulus
(E) were calculated according to the following equations
[10]:
1  2ðVT =VL Þ2
Poisson’s ratio ð#Þ ¼ ð1Þ
2  2ðVT =VL Þ2
VL2 qð1 þ #Þð1  2#Þ
Young’s modulus ðEÞ ¼ ð2Þ
1#
where VT is transverse velocity, VL is longitudinal velocity
and q is density. The tensile test were conducted according
to the ASTM E8/E8 M standard using an Instron 5500
Universal Electromechanical Testing Systems equipped with
Mg Fe Ti B Al
1 0.2 7.7 3.5 Bal.
Solutionizing time (h) Aging temperature (°C) Aging time (h)
6 – –
6 180 24
6 220 24
6 – –
Young’s Modulus of Al–Si–Mg–Cu Based Alloy …
Bluehill software and a 50 kN load cell. The tensile test was
carried out at a nominal strain rate of 1.6  10−1 s−1 and at
ambient temperature (*25 °C). The total elongation of
specimens was measured from the difference in the gauge
length before and after testing via an extensometer.
Results and Discussion
X-ray diffraction patterns of the Al–Si–Mg–Cu hybrid alloys
are shown in Fig. 1. It is clear that the main phases of the
hybrid alloys under all heat treatment conditions are a-Al,
b-Si, Mg2Si and TiB2, phases. The characteristic peaks of
the Al–Si–Mg–Cu hybrid alloys represent high intensities
and are well matched with JCPDS cards (Mg2Si,
No. 00-035-0773 and TiB2, No. 01-075-0967).
Gibbs free energy of TiB2 is more negative than that of
other potential phases such as Al3Ti and AlB2 during
solidification temperature of the hybrid alloy [11], which
thermodynamically resulted in the formation of TiB2 phase.
In order to achieve the maximum potential of particulate
reinforced aluminium matrix composites, it is important to
avoid forming any undesirable phases, which are usually
observed in cast aluminium matrix composites. The phases
such as Al3Ti have been identified to be detrimental on the
mechanical properties of cast Al/TiB2 composites due to
their brittle nature [12]. The XRD pattern of the Al–Si–Mg–
Cu hybrid alloys under different heat treatment conditions
shows no evidence of undesired phases in the
Fig. 1 X-Ray diffraction patterns
of the Al–Si–Mg–Cu hybrid alloy
under different heat treatment
conditions a T4, b T6, c T7 and
dO
337
microstructure, which confirms that the materials manufac-
turing has been properly controlled at the reaction conditions
with appropriate Ti/B ratio. Figure 2 shows the SEM
micrographs of the Al–Si–Mg–Cu hybrid alloys in T4, T6,
T7 and O heat treatments. It is obvious that relatively
homogeneous distribution of the reinforcement, in macro-
scopic scale, has been achieved in all hybrid alloys with
different heat treatment process.
As it can be expected, the distribution of TiB2 particles is
almost similar in all heat treatment conditions. Although
there are many individual particles in the aluminium matrix,
Fig. 3a, TiB2 particles are partially segregated in the eutectic
b-Si regions, Fig. 3b. This phenomenon is attributed to the
particle pushing mechanism during solidification [13]. When
aluminium alloys melt solidifies, the TiB2 and b-Si particles
are pushed away by the solidification front of solid a-Al
dendrites and segregated within the inter-dendritic and
eutectic regions.
High magnification TEM micrographs of the Al–Si–Mg–
Cu hybrid alloy are shown in Fig. 4, representing the TiB2
phase in the morphology of cubic prism. However, the figure
confirms that the TiB2 particle have chamfered edges. This
means that the growth rate of the facets is not capable of
obtaining perfect hexagonal TiB2 particles. The growth rate
of the faces, edges and the corners should maintain a certain
relationship in order to achieve complete shape of the
hexagonal TiB2 particles [14]. Otherwise, higher-index
planes form at the edges and corners of the TiB2 particles.
A typical interface between the aluminium matrix and the
338
Fig. 2 Backscattered SEM micrographs of Al–Si–Mg–Cu hybrid alloy under different heat treatment conditions a T4, b T6, c T7 and d O
TiB2 particle is shown in Fig. 4b, which confirms the clear
and well-bonded interface is formed between the reinforce-
ment phase and the matrix. According to the microstructural
observations in the present study, distribution, size, shape of
TiB2 particles and the interface between aluminium matrix
and TiB2 particles are almost same under different heat
treatment conditions (T4, T6, T7, O). However, high reso-
lution TEM micrographs, Fig. 5, reveal that the size and
density of the precipitates formed at specific heat treatment
processes are different from each other.
Figure 5a, b is TEM images showing the hybrid alloy in
T4 condition where no precipitates were formed in the alu-
minium matrix before applying the aging treatment. Fig-
ure 5c, d illustrates fine precipitates when applying T6 heat
treatment, while Fig. 5e, d shows the coarsening phenom-
ena, which occurs in the precipitates upon applying T7
condition. Desirable selection of time and temperature in T6
condition resulted in the precipitation of fine precipitates
S. Amirkhanlou et al.
distributed densely in the aluminium, as it can be seen in
Fig. 5c. Increasing the aging temperature and time, T7
condition, results in a coarsening of the precipitates and a
reduction of their density in the matrix, as observed in
Fig. 5e. The coarsening of the precipitates together with the
reduction in their density upon extending the aging time or
raising the aging temperature is in conformity with the
Ostwald ripening concept [15]. According to this hypothe-
sizes the large precipitates are favourable to growing at the
expense of atoms from the smaller precipitates, which are
unstable and will ultimately dissolve completely. These
changes are favourable from the thermodynamic point of
view where the system tends to lower its energy through the
formation of coarse stable incoherent precipitates with lower
interfacial energy [16].
Young’s modulus of the hybrid alloy under different heat
treatment conditions measured by ultrasonic pulse technique
is shown in Table 3. It is clear that the Young’s modulus of
Young’s Modulus of Al–Si–Mg–Cu Based Alloy …
Fig. 3 High magnification SEM micrographs of Al–Si–Mg–Cu hybrid
alloy after T4 heat treatment
all Al–Si–Mg–Cu hybrid alloys is about 94 GPa, signifi-
cantly higher than that of conventional aluminium alloys at a
level of 70 GPa. The increase is *30% and the significant
improvement can be attributed to the presence of high
modulus TiB2 and Mg2Si phases in the microstructure.
Young’s modulus is an intrinsic property and governs by
volume fraction and modulus of phases within the Al–Si–
Mg–Cu hybrid alloy. As major phases of the hybrid alloys
are constant, there are no significant changes of Young’s
modulus under different heat treatment conditions.
Table 4 demonstrates the tensile properties of the Al–Si–
Mg–Cu hybrid alloys under different heat treatment condi-
tions (i.e. T4, T6, T7 and O). As seen, a great enhancement
in the yield strength (YS) and the ultimate tensile strength
(UTS) is observed in the alloy under T6 and T7 compared
with T4 and O conditions. This significant improvement of
the strength is attributed to the presence of precipitates.
According to the Orowan mechanism, presence of pre-
cipitates plays a principle role in increasing the overall
339
Fig. 4 High resolution TEM image representing Al/TiB2 interface
being viewed in ½11
20TiB2 projection axis
strength of the alloys as a result of the resistance to dislo-
cation motion by the precipitated phases. The precipitates
obtained at T4 condition are finer in size with a greater
density in the matrix, as shown in Fig. 5c, d. These pre-
cipitates therefore have small interparticle spacing. In this
case, the precipitates provide strong resistance to dislocation
motion and the occurrence of Orowan looping becomes
difficult, leading to a hardening of the hybrid alloy and an
increase in the overall strength of the alloy, as shown in
Table 4.
Figure 6 shows the SEM fractographs after tensile test for
the Al–Si–Mg–Cu hybrid alloy under different heat treat-
ment conditions. The hybrid alloys under all heat treatment
conditions show a quasi-cleavage fracture, characterised by
the cleavage fracture of Si and small and shallow dimples of
aluminium phase. However, it seems that the alloy in O
temper has more dimples compared with other conditions.
Despite of a quasi-cleavage fracture, the materials developed
in the present study can provide reasonable ductility at a
340 S. Amirkhanlou et al.

Fig. 5 TEM micrographs of Al–Si–Mg–Cu alloy under different heat treatment conditions (a and b) T4 being viewed in [110] direction, (c and
d) T6, and (e and f) T7 being viewed in [100] direction

Table 3 Density, velocity Heat Density Longitudinal Shear velocity Poisson’s Young’s
parameters and Young’s modulus treatment (g/cm3) velocity (mm/µs) (mm/µs) ratio modulus (GPa)
of the experimental materials
measured by Archimedes’ T4 2.805 6.80 3.59 0.3 94.72
principle and ultrasonic waves T6 2.805 6.78 3.58 0.3 94.14
T7 2.805 6.78 3.56 0.3 93.12
O 2.805 6.82 3.58 0.3 94.41
Young’s Modulus of Al–Si–Mg–Cu Based Alloy … 341

Table 4 Mechanical properties of the Al–Si–Mg–Cu hybrid alloy under different heat treatment conditions
Heat treatment 0.2% Yield strength (MPa) Ultimate tensile strength (MPa) Elongation (%)
T4 235 305 1.2
T6 363 365 0.59
T7 260 298 0.94
O 218 273 1.35

Fig. 6 SEM micrographs of fractured surface for Al–Si–Mg–Cu hybrid alloy under different heat treatment conditions a T4, b T6, c T7 and d O

level of 1.3% when the Young’s modulus reaches over
94 GPa. This is reasonably good to satisfy the requirement
of automotive industries.
Conclusions
The Al–Si–Mg–Cu hybrid alloy under T4, T6, T7 and O
heat treatment conditions can provide the improved
Young’s modulus over 94 GPa by the formation of Mg2Si
and TiB2 phases in the microstructure. Distribution, size,
shape of TiB2 particles and the interface between alu-
minium matrix and TiB2 particles were almost same under
different heat treatment conditions (i.e. T4, T6, T7, O).
While no precipitates were formed in the aluminium matrix
after T4, nanoscale precipitates were found by applying T6
and T7 heat treatment conditions. Significant enhancement
in the strength was observed in the alloy after T6 and T7
compared with T4 and O heat treatments. The hybrid alloys
showed a quasi-cleavage fracture, characterised by the
cleavage fracture of Si and small shallow dimples of alu-
minium phase.
342
Acknowledgements Financial support from Jaguar Range Rover
(JLR) [grant number R33232] is gratefully acknowledged.
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 Intergranular Corrosion Investigation
on EN-AW 6082 Redraw Rod

Luisa Marzoli, Dominique Cance, Christiane Matthies, Magali Guizard,

Peter Baumgart, and Hubert Koch

Abstract
The request for aluminium with enhanced properties, such as an improved resistance to
intergranular corrosion for the 6XXX alloys has risen in the past years. In the past years
there have been investigations on the IGC behaviour of 6XXX extrusion alloys, but no
studies about the behaviour of rod are known to the authors of this paper. In this article, the
IGC behaviour of 6082 rod will be investigated. The rods were produced by TRIMET in
Castelsarrasin with a continuous casting and rolling process. They were subsequently, in
the labs of TRIMET, homogenised, drawn with final area reduction of 53%, annealed and
heat treated. The samples were than tested according to the VW PV 1113 for ICG of 6XXX
alloys, a test used on extruded profiles, permitting a comparison of the results. Results
indicate that chemical composition and process parameters have a strong influence to the
corrosion sensitivity of this material.

Keywords
Intergranular corrosion IGC EN-AW 6082 Rod

Introduction
Lower CO2 emission targets have caused, among others, the
need for lighter, more efficient vehicles, causing a significant
increase of aluminium usage in the automotive industry.
This, has in turn, generated the need for aluminium alloys
with enhanced properties. The 6XXX alloys family is a very
popular choice for automotive parts, their workability is
excellent, they can be produced in different forms (sheets,
extrusions, redraw rod), and they provide a good compro-
mise between the mechanical characteristics and corrosion
resistance. Within this alloy family, the EN-AW 6082, with
reasonably high mechanical characteristics, and good
formability, is an ideal candidate for medium-high strength
structural parts in the automotive industry. The authors of
this paper decided to investigate the sensitivity of EN-AW
6082 redraw rod to intergranular corrosion (IGC) , which is
used to manufacture screws and rivets for the automotive
industry.
Intergranular Corrosion

The definition of intergranular corrosion given by the Alu-

minium Handbook is selective attack of grain boundaries, or
closely adjacent regions without appreciable attack of the
L. Marzoli (&)
C. Matthies
H. Koch
TRIMET Aluminium SE, Essen, Germany grains themselves. Intergranular corrosion is caused by
e-mail: luisa.marzoli@trimet.de potential differences between the grain boundary region and
D. Cance
M. Guizard the adjacent grain bodies [1]. The 6XXX series is generally
TRIMET, Castelsarrasin, France considered to have a good resistance against this type of
P. Baumgart corrosion.
TRIMET, Saint-Jean-de-Maurienne, France

© The Minerals, Metals & Materials Society 2017 343

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_45
344
However, the increased use of 6XXX alloys in the
automotive industry, and in particular, in Europe of EN-AW
6082, has brought to light the fact that also this alloy series is
not immune to IGC. There are different testing methods for
the IGC such as the ASTM G66, G67, G110, and the
ISO EN 11846:2008, but they are tailored for specific alloy
groups (mainly 5XXX), some automotive companies have
developed their own IGC test, which aim is to foresee the
effect of the IGC on 6XXX structural parts in real life.
For this study, the VW/Audi Group PV 1113 [2] own
standard to test EN-AW 6082 structural parts was chosen, on
the ground that it is well known in Germany and it is per-
formed routinely in the lab of TRIMET in Essen.
Unlike for the 5XXX series, were causes and compen-
sating measures are known, the IGC attack mechanism for
6XXX, although under investigation by many [3–7], is still
unclear [8]. Since IGC attack can cause a reduction of the
life span of structural parts, it is important to find compen-
sating measures also for this alloy series.
It appears however, that, the intergranular sensitivity of
AlSiMg, is influenced by a mix of factors, such the chemical
composition and the thermal history of the material.
Fig. 1 Schematic of a Continuous Casting and Rolling Machine
Fig. 2 Single steps of rolling process
L. Marzoli et al.
Rod Production
The common way to produce rods today is with a continuous
casting and rolling machine (CCR). A comparison of the
traditional and the CCR process is depicted in Fig. 1, a
scheme of a continuous casting and rolling machine in
Fig. 3. The advantages of such a machine are quite obvious;
it combines a casting system with a rolling mill, directly hot
working the solidified bar to a form rod, literally, striking the
aluminium (iron) while is hot (Fig. 2).
Wire Redraw Process
Cold drawing of wire is typically used to generate specific
mechanical properties, uniform and smooth surfaces and
tighter tolerances than achievable in a hot or warm forming
process. These characteristics are the basic requirements for
the use in cold forming processes of fasteners and joining
elements such as screws, bolts and other connecting parts in
the automotive industry. After the transformation in a com-
bined redraw machine, the final product is called redraw rod.
Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod
Fig. 3 Comparison between a traditional process and a Continuous
Casting and Rolling process
The principle of cold forming is illustrated in Fig. 4. The
wire is pulled through tapered die. The forces required for
the drawing operation depend on the wire mechanical
properties, its deformation characteristics, die geometry and
tribological conditions during the drawing process. Thus, the
amount of area reduction of the cross section and the
required pulling forces is limited. In practice, the achievable
area reduction of each single drawing operation is chosen
within a range of 15% u. 35%.
In order to achieve a higher overall area reduction, it is
necessary to carry out several individual drawing steps.
A common, efficient and cheap way to perform the redraw
operation is to combine several drawing operations in one
machine, Fig. 5, instead of single repetitions through a sin-
gle die. The wire is fed in one setup through several draw
dies with declining dimensions and pulled through the dies
by attuned capstan speeds in one run.
345
Fig. 4 Scheme of cold drawing of wire [9]
Experimental
Two different EN-AW 6082 compositions, one with a
standard copper (NCu), one with reduced copper content
(LCu), were used to produce the rods. The chemical com-
position of the two version of the alloy can be seen in
Table 1.
The rods were produced on the TRIMET site of Castel-
sarrasin on an internally modified SECIM CCR machine.
Their original diameter was 15.2 mm, they were not ther-
mally treated and were delivered in “F” condition. They
were then homogenized in the TRIMET labs in Essen
(Status “O”), drawn in 3 steps from a diameter of 15.2–
10.4 mm, with a reduction ratio of 53% (Status “H16”).
They were then solutionized and heat treated to T6 temper.
Between the solution heat treatment and the T6 temper, the
wire underwent 24 h of natural aging. In order to evaluate
the influence of the cold working and the heat treatment, a
corrosion test according to PV 1113 [2] was performed after
each process step (as fabricated, homogenisation, redraw,
thermal treatment).
The surfaces have to be ground with 120 grit iron free
sandpaper, and then they must be cleaned with acetone and
immersed in an ultrasonic bath with alcohol. The sample
must be immersed in a new solution made of 1000 ml H2O,
20 g NaCl, 100 ml HCl (25%), with at least 8 ml solution per
cm2 of the sample. Test duration is 2–2.5 h at room tem-
perature. The sample has to be cleaned with flowing water
346 L. Marzoli et al.

Fig. 5 Scheme of a combined redraw machine [10]

Table 1 Chemical composition of the cast alloys Comparing the influence of the heat treatment on the
different samples, it can also be seen that, among the same
Version 1 Version 2
alloy version, the heat treatment has a beneficial effect on the
Si 0.81 0.86
corrosion resistance, while the cold working due to the
Fe 0.2 0.17 redraw increases the corrosion sensitivity of the material.
Cu 0.08 Confidential In general, the corrosion resistance of the samples is quite
Mn 0.49 0.52 good on the surface, but, on the fresh cut faces there are big
Mg 1.03 0.74 differences. An explanation for this behavior will be shown
Cr 0.001 Confidential in Figs. 22, 23, 24, 25, 26, 27, 28 and 29.
Zn 0.004 Confidential The different corrosion resistance, can be explained by
the microstructural changes in the material. As it can be seen
Ti 0.04 0.03
in Figs. 22, 23, 24, 25, 26, 27, 28 and 29, the untreated rod
has a fiber structure, elongated in the production direction,
only immediately after it is taken out of the solution. After while the heat treated samples are recrystallised. In the fresh
polishing, the depth of the IGC attack can be measured. cut face, the corrosion attack, once initiated, can proceed
along the fibrous structure without encountering any obsta-
cles. On the other hand, in the recrystallised structure, the
Results attack proceeds along the grain boundaries, and every new
grain is a new obstacle on its way. Since on the outer skin of
The maximum corrosion depth was measured as shown in the the rods, due to fabrication, a very thin recrystallised rim is
pictures (Figs. 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, always present, this area is better protected against corrosion
20 and 21), both on the fresh cut face (FCF) and on the rod/ attacks, even in the NCu samples case. Nevertheless, the
wire surface (S) and it is shown in Table 2 for each sample. difference between the corrosion depth of NCu and LCu
There are different effects that can be noted observing the variants is still very visible, also in the recrystallised form.
micrographs, one due to the chemical composition, one due Comparing the influence of the heat treatment on the
to the heat treatment and one due to the redraw work. different samples, it can also be seen that, among the same
The comparison between the two alloys versions shows alloy version, the heat treatment has a beneficial effect on the
that in all cases the LCu samples have lower corrosion depth corrosion resistance, while the cold working due to the
than the co respective NCu specimens. redraw increases the corrosion sensitivity of the material.
Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 347

Fig. 6 Sample 1 ø15,2 NCu F FCF

348 L. Marzoli et al.

Fig. 7 Sample 2 ø15,2 NCu F S

Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 349

Fig. 8 Sample 3 ø15,2 LCu F FCF

350 L. Marzoli et al.

Fig. 9 Sample 4 ø15,2 LCu F S

Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 351

Fig. 10 Sample 5 ø15,2 NCu O FCF

352 L. Marzoli et al.

Fig. 11 Sample 6 ø15,2 NCu O S

Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 353

Fig. 12 Sample 7 ø15,2 LCu O FCF

354 L. Marzoli et al.

Fig. 13 Sample 8 ø15,2 LCu O S

Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 355

Fig. 14 Sample 9 ø10,4 NCu H16 FCF

356 L. Marzoli et al.

Fig. 15 Sample 10 ø10,4 NCu H16 S

Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 357

Fig. 16 Sample 11 ø10,4 LCu H16 FCF

358 L. Marzoli et al.

Fig. 17 Sample 12 ø10,4 LCu H16 S

Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 359

Fig. 18 Sample 13 ø10,4 NCu T6 FCF

360 L. Marzoli et al.

Fig. 19 Sample 14 ø10,4 NCu T6 S

Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 361

Fig. 20 Sample 15 ø10,4 LCu T6 FCF

362 L. Marzoli et al.

Fig. 21 Sample 16 ø10,4 LCu T6 S

Table 2 Maximum Corrosion Sample Diameter Version Heat treatement Corrosion depth Surface
depth of each sample number (mm) condition (µm)
1 15.2 NCu F 344 FCF
2 15.2 NCu F 168 S
3 15.2 LCu F 56 FCF
4 15.2 LCu F 33 S
5 15.2 NCu O 289 FCF
6 15.2 NCu O 58 S
7 15.2 LCu O 29 FCF
8 15.2 LCu O 24 S
9 10.4 NCu H16 133 FCF
10 10.4 NCu H16 102 S
11 10.4 LCu H16 34 FCF
12 10.4 LCu H16 16 S
13 10.4 NCu T6 199 FCF
14 10.4 NCu T6 117 S
15 10.4 LCu T6 27 FCF
16 10.4 LCu T6 12 S
Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 363

Fig. 22 Sample 17 ø10,4 NCu H16 FCF

364 L. Marzoli et al.

Fig. 23 Sample 18 ø10,4 NCu T6 FCF

Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 365

Fig. 24 Sample 19 ø10,4 LCu H16 FCF

366 L. Marzoli et al.

Fig. 25 Sample 20 ø10,4 LCu T6 FCF

Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 367

Fig. 26 Sample 22 ø10,4 NCu H16 S

368 L. Marzoli et al.

Fig. 27 Sample 21 ø10,4 NCu T6 S

Intergranular Corrosion Investigation on EN-AW 6082 Redraw Rod 369

Fig. 28 Sample 23 ø10,4 LCu H16 S

370
Fig. 29 Sample 24 ø10,4 LCu T6 S
Conclusions
The results show that the IGC sensitivity of EN-AW 6082
redraw-rods is influenced not only by the chemical compo-
sition and thermal history of the material, but also by its cold
working history. In order to obtain good results it is therefore
important to control and tune all this parameters.
Acknowledgements The authors would like to thank Mr. Chris
Schaefer, Mr. Mario Lazic and Mr. Marcus Heinen for their support.
References
1. ASM Specialty Handbook 1993
2. Volkswagen AG Konzernnorm PV 1113, 2007-10, Klass.-Nr.
53312
L. Marzoli et al.
3. G. Svenningsen, J.E. Lein, A. Bjorgum, J.H: Nordlien, Y. Yu, K.
Nisancioglu, Effect of low copper content and heat treatment on
intergranular corrosion of model AlMgSi alloys. Corros. Sci. 48,
258–272 (2006)
4. G. Svenningngsen, J.C. Walsmsley, J.H: Nordlien, K. Nisancioglu,
Effect on artificial aging on intergranular corrosion of extruded
ALMgSi alloys with small Cu content. Corros. Sci. 48, 1528–1543
(2006)
5. T. Toßmann, L. Yu, K. Bauer, H. Kaufmann, J. Grimm, Short-time
corrosion test for the evaluation of corrosion sensitivity of
aluminium alloys for the automotive industry. Eurocorr (2012)
6. K. Blommedal, Corrosion development in welded AA 6082 alloys,
NTNU—Trondheim Norwegian University of Science and Tech-
nology, June 2013
7. N. Tyrell, Effect of natural and artificial aging on corrosion of
extruded AA 6082. Trimet internal report, July 2013
8. Friedrich Ostermann, Anwendungstechnologie Aluminium, 3.
Auflage, 2014
9. IBPB Peter Baumgard, 2016
10. Aluminium Taschenbuch, Aluminium Zentrale e.V. Düsseldorf,
Aluminium Verlag Düsseldorf, 1996
 The Influence of Process Parameters
and Themomechanical History on Streaking
Defects in AA6060 Extrusions

Steven Babaniaris, Aiden Beer, and Matthew R. Barnett

Abstract
Streaking is a common surface defect on architectural extrusions. The current study
investigates the effect of processing parameters and thermomechanical history on the
surface finish of a streaked AA6060 extrusion. Streaked profiles were intentionally
produced via extrusion using a die with internal geometry deliberately designed to produce
thermomechanical variation in specific regions of the profile geometry. Extrusions were
conducted at various ram speeds and the profiles were given an anodization pre-treatment
process to reveal streaking in the designated regions. Thermomechanical variation was
analyzed using the “ALE” code HyperXtrude®. The surface profile and roughness of the
treated and mill finish extrudates were analyzed using optical profilometry. The presence of
the streaks were associated with strain rate variability as determined by the die geometry,
independent of the ram speed. The streaked regions of the profile were found to be more
recessed compared to the bulk regions.

Keywords
Aluminium alloy Extrusion Defects Finite element

Introduction color or tone when compared with the surrounding material

Surface quality is an important characteristic of high quality
decorative and architectural extrusions where a consistent
and visually homogeneous surface finish is imperative.
Therefore, the presence of any surface defects, such as
micro-cracks, pickup and streaking can be cause for rejection
of the profile, with considerable economic penalties. Of
these, streaking defects are considered especially problem-
atic as they do not become visible until after anodization,
which is the final step in the production cycle [1]. A streak
defect is characterized as a narrow banded variation in the
material surface appearance stretching along the length of an
extrusion [1–3]. Streaking defects appear as a region of
visible disparity, such as an overly bright or dull band in
S. Babaniaris (&)
A. Beer
M.R. Barnett
Institute for Frontier Materials, Deakin University,
75 Pigdons Road, Waurn Ponds, VIC 3216, Australia
e-mail: snbab@deakin.edu.au
[1–3].
Thermomechanical streaks are those attributed to local-
ized differences in material flow which occurs throughout a
complex extrusion profile [4–6], and as a result often form in
bands above/near geometric features with significant flow or
deformation gradients such as web, screw ports, corners,
welds and changes in the extrusion profile thickness [7]. It is
generally stated that this non-uniformity of metal flow
(producing different thermomechanical deformation histories
of strain, strain rate and temperature) results in regions of
inhomogeneous surface topography or microstructure. These
regions may then experience a different etching response
compared to the rest of the profile and produce a visible
streak defect [1, 3, 6, 8].
It is well established in the extrusion industry that ther-
momechanical streaking can be minimized or eliminated
through controlling the extrusion conditions and the die
design [3, 9, 10], however the underlying mechanisms
responsible for the streak formation remain unclear. A large

© The Minerals, Metals & Materials Society 2017 371

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_46
372
quantity of the available literature on thermomechanical
streaking has come from rejected extrudates from the
industry with questionable thermal history or processing
conditions, dissimilar profile shapes and unknown or unex-
plored internal die geometry [8, 11–13]. As a result, direct
comparisons between studies is not practical as no effort has
been made to recognize and quantify any variations in
thermomechanical history in streak prone regions as the
material is deformed through the die. The current study is
designed to investigate the correlation between extrusion
process parameters and thermomechanical history on the
surface finish of a streaked AA6060 extrusion.
Methodology
An AA6060 alloy was received in the form of a commer-
cially direct chill cast billet. Extrusion billets of 60 mm
diameter and 100 mm length were machined directly from
the billet parallel to the direction the billet was cast. The
material was then solution treated after machining in a
muffle furnace at 540 °C for 40 min and immediately
quenched in water. This solution heat treatment has been
performed to dissolve any MgSi precipitates into a super
saturated solid solution without significantly affecting the
condition of any AlFeSi intermetallic particles [14].
A series of extrusion trials were conducted on a 300 ton
large scale research-dedicated extrusion press. Billets were
heated to 450 °C in an inline induction unit at approximately
2.25 °C/s and extruded at a set ram speeds of 7, 14, 21,
28 mm/s. The Container and Die temperatures were main-
tained at 420 and 450 °C respectively to promote sticking
friction between the billet and container and minimize the
inflow of billet skin [15] Boron nitride lubricant was applied
to the front of the ram to minimize back extrusion onto the
ram. Prior to extrusion the billet underwent a crush/burp
cycle where the billet is compressed to fill the 63 mm con-
tainer, where the pressure is then remove to release any
entrapped gas between the ram and billet. The extrusions
were performed semi-continuously whereby each successive
extrusion was welded onto its predecessor in the die feeder
chamber. After extrusion process was complete, the extru-
dates were left to air cool to room temperature.
The extrusion profile and internal die geometry is shown
in Fig. 1a, b respectively. This profile was designed with
streaking in mind as the region above a screw port is con-
sidered especially streak prone [5, 7, 16]. The primary dif-
ference between the two screw ports is the wall thickness
between the top plate of the profile and beginning of the
screw port. The die design has been optimized to promote
thermomechanical variation between the top plate and the
screw ports. This has been achieved by modifying the dies
bearing length to unsuitably compensate for the increased
S. Babaniaris et al.
Fig. 1 a Geomety of the extrusion profile, b Internal die geometry of
the extrusion die
friction caused by the larger surface area around the screw
ports. Additionally no compensation for friction between the
billet and container walls was made. The internal geometry
of the die consists of a 10 mm deep feeder region as the
initial inlet to the die and a shaped bearing region that varies
between 4.5 and 1.8 mm as shown in Fig. 1b.
The extrudates went a commercial anodization
pre-treatment process consisting of cleaning in a 5% sodium
chloride solution for 20 min at 53 °C, etching in a 10%
sodium hydroxide solution for 20 min at 52 °C and Des-
mutting in a non-chromated liquid desmutter and deoxidiser
for 10 min at room temperature. The extrudate surface were
then assessed visually for any signs of streaking.
The surface of the extrudate extruded at a ram speed of
7 mm/s in both the mill finish and etched state were ana-
lyzed using an Alicona Optical Profilometer. Additionally
profile form measurements were taken across the width of
the screw port with the 3.55 mm wall thickness and streak in
the independent zone (as shown in Fig. 4) at 10 magnifi-
cation with an approximate vertical resolution of 400 nm
and lateral resolution of 2.13 µm. All measurements were
taken at random along the length of the extrudate.
The commercial finite element package, HyperXtrude
was used to simulate the extrusion process. The geometry of
the workpiece was simulated as it is extruded in a pre-filled
die, while the tooling is considered a series of rigid boundary
conditions. The simulation extrusion parameters were pro-
grammed to match those of the experimental extrusions after
the crush/burp cycle (shown in Table 1). A viscoplastic
friction factor of 0.9 was assumed between the billet and
The Influence of Process Parameters and Themomechanical History … 373

Table 1 Process parameters for Container diameter/Billet diameter 63 mm

the Hyperxtrude simulations
Billet length 90.7 mm
Initial billet temperature 450 °C
Initial die temperature 450 °C
Initial container temperature 420 °C
Ram speed 7, 28 mm/s

container, whilst friction between the profile and die was
assumed to be µ = 0.4. A constant heat transfer coefficient of
3000 W/m2 K was assumed between the workpiece and all
tooling.
The high temperature material behavior of the AA6060
aluminum was described using the Sellars–Tegart model
[17]:
extent of local deformation. The regions closest to the die
bearing (Bearing and Profile) will undergo significant shear
deformation, therefore a fine mesh consisting of triangle
prism elements was applied to these regions. As only mild
upsetting occurs in the billet, much coarser tetrahedral ele-
ments were applied.

1 Z 1
r ¼ sinh1 ð Þn ð1Þ Results and Discussion
a A
where r is the material flow stress, a, A and n are material Extrusion
constants and Z is the Zener-Hollomon parameter as defined
by: The extrusion pressure–ram displacement curves after the
crush-burp cycle are shown in Fig. 3. These curves are
Q typical for the direct extrusion process [19]; the pressure
Z ¼ e_ expð Þ ð2Þ
RT initially increases rapidly as the billet is compressed into the
die inlet and then undergoes breakthrough. The peak pres-
where e_ is the strain rate, Q is the material activation energy,
sure then occurs as a result of the development of the
T is the temperature in Kelvin, and R is the universal gas
constant (= 8.314 J/mol K). The values used in this work deformation zone [20]. The extrusion pressure then decrea-
ses as the billet length is reduced. As the extrusion nears
were determined from a series of elevated temperature
completion the short billet length inhibits further flow
compression tests performed at a range of strain rates [18]
resulting in a plateau and slight rise in the load and the end
and are as follows: a ¼ 2:42  108 m2/N, n = 5.78896,
of the extrusion process. Furthermore, the required extrusion
Q = 193.93 kJ/mol and A ¼ 1:00784  1014 s−1.
load throughout the process increases as the ram speed was
In order to facilitate appropriate boundary conditions and
increased.
meshing the simulation was split into four regions, namely
Furthermore the material extrusion force increases
the billet, feeder region, bearing and profile. The model
alongside increases in the set ram speed. This relationship is
mesh consisted of 252,846 elements and 72,231 nodes (as
directly related to the operation of the AA6060 material
shown in Fig. 2). The element size was varied throughout
the primary components of the model in accordance with the
500
450
Profile 400 28mm/s
Extrusion Pressure (MPa)

21mm/s
Bearing 350 14mm/s
300 7mm/s
250
Feeder
200
150
100
50
0
0 10 20 30 40 50 60 70 80 90
Billet
Ram Displacement(mm)

Fig. 3 Extrusion pressure–ram displacement extrusion curves for

AA6060 at a billet temperature of 450 °C. Ram speeds are indicated
Fig. 2 Mesh generation used for numerical analysis beside their respective curve
374
softening mechanisms. Decreasing the set ram speed (and
consequently the resulting strain rate), will decrease the
material flow stress. A reduction in the strain rate allows
more time for dynamic recovery (the primary microstructural
recovery method in 6xxx series aluminum alloys) to coun-
teract the increase in flow stress from work hardening [21,
22], leading to the decrease in the extrusion pressure.
Surface Quality
No signs of streaking were present on the mill finish
extrudate surfaces. However, after the anodization pretreat-
ment process, four dull streaks were visible on the flat sur-
face of the profile under all tested ram speeds (as shown in
Fig. 4):
• A thick dull streak (Fig. 4a) that covers the region above
screw port with the increased wall thickness
• A thin dull streak in an independent zone (Fig. 4b),
slightly offset from profiles center
• Two thin dull streaks (Fig. 4c, d) located above each side
of the screw port with the decreased wall thickness
Fig. 4 Locations of the streaking defects after the anodization
pre-treatment process. Prominent dull streaks can be seen in the region
above the screw ports (a), (c) and (d), and in an independent zone
towards the center of the profile (b)
S. Babaniaris et al.
Under initial assessment the three streaks located above
the screw ports are likely thermomechanical streaks as they
are located directly above the regions of the screw port with
considerable changes in wall thickness, have consistent
thickness and shade and stretch along the entire length of the
profile [9, 23]. Additionally, although there were some dif-
ferences in the mill finish surface quality, all of the profiles
have a similar appearance with no observable differences in
the shade or severity of the streaks for the range of tested
ram speeds.
The profile form data of the streak located in the inde-
pendent zone (b in Fig. 4) towards the center of the extrudate
is shown in Fig. 5. It is apparent that a cluster of four
prominent features are present on the surface of the extrudate
in both the mill finish and treated condition. Previous studies
have shown that streaking defects can form due to physical
damage to the extrudate surface. Non-uniformity of die lines
on the profile surface is an unavoidable product of the
extrusion process, and streaking defects can often be the
product of the visible remains of a prominent die line or
surface abrasions that arise due to a damaged or dirty die [7,
9, 12, 23]. Additionally, like thermomechanical streaks the
visibility of these streaks are altered by etching. Die lines
react more quickly than the surrounding regions due to their
increased surface area and as a result are leveled out or
removed during etching. However, if die lines are not
removed by etching (i.e. insufficient etching time, low
etching temperature or a weak etching solution), localized
profile form variations can remain and produce a visible
streak defect [7, 24, 25].
The profile form data of the streak located above the
increased wall thickness screw port (Fig. 4a) is shown in
Fig. 6. Unlike the streak in located in the independent zone,
this streak shows no sign of damage or increased die line
depth/severity when compared to the surrounding area.
Conversely, the region containing the streak was found to be
more recessed compared to its surroundings in both the
mill-finish and treated state. However, as the streak is only
visible in the treated state it is unlikely that this is the solitary
cause of the streak, though it may be a contributing factor.
More work is required to elucidate the root cause of this
streak defect.
Numerical Analysis
The temperature evolution of the profile during deformation
is shown in Fig. 7. The temperature increases as the material
progresses through the deformation stages of the die, and
remains fairly uniform as the profile exits the die. The
temperature evolution during extrusion is mainly influenced
by heat transfer to the tooling and heat generation due to
friction and plastic deformation, whereby the final
The Influence of Process Parameters and Themomechanical History … 375

Fig. 5 Optical profilometry images and form profiles of the streak located in the independent zone in the mill finish (a) and treated (b) condition

Fig. 6 Optical profilometry images and form profiles of the streak located above the screw port with the 3.55 mm was thickness in the a mill
finish and b treated conditions

temperature is dependent on factors such as the initial billet been suggested that streaking defects may have been a result
temperature, the temperature of the tooling (die and con- of locally high temperature generation in complex regions of
tainer), the ram speed and the complexity of the die. It has the profile such as the screw ports [7, 26, 27]. However,
376
the temperature distribution of the final profile is fairly
uniform, with only a minor drop at the edges of the profile in
the 7 mm/s extrusion and a minor increase at the edges of
the 28 mm/s extrusion. This difference is most likely
attributed to the increased time for heat transfer that is
facilitated by the longer contact time between the edges of
the extrudate and tooling in the 7 mm/s extrusion. As a
result it is unlikely that differences in temperature are the
primary reason for streak formation in this profile.
The FE predicted strain rates for the extrusions are
shown in Fig. 8 and show that the strain rate is highest in
the region inside the die bearing where a majority of the
deformation occurs. Additionally, a cross sectional view of
the profile strain rate at the point located 2.1 mm back from
Fig. 7 Contour plot of the
temperature evolution of the
7 mm (a) and 28 mm/s
(b) extrusion simulation
S. Babaniaris et al.
the feeder region in the die bearing (Fig. 8c). It is apparent
that the regions above the two screw ports where streaking
was found to occur experience locally high strain rates
(approximately 52 s−1 in the region above the screw port
compared to 29 s−1 in the profile center) compared to the
bulk profile. As the temperature was reasonably consistent
throughout the profile the formation of the observed
streaking defects can possibly be attributed to differences in
the local strain rate. It is unknown whether this strain rate
difference is sufficient enough to cause a microstructural or
topographical difference in the profile. Additional simula-
tions and further analysis of the extrusion profile surface
and microstructure will be required to confirm this
hypothesis.
The Influence of Process Parameters and Themomechanical History …
Fig. 8 Contour plot of strain rate
distribution the 7 mm/s extrusion
simulation (a and b). Cross
sectional contour plot of the strain
rate distribution at the point in the
bearing located 2.1 mm from the
back of the feeder (c)
Conclusions
1. Four streaks were produced on all of the extruded pro-
files, three which were located in regions above screw
ports coinciding with a significant change in wall thick-
ness and one in an independent zone towards the profile
center. The severity of these streaks were not affected by
the ram speed.
2. The streak located in the independent zone towards the
center of the profile was associated with four significant
die lines that were not removed during the anodization
pretreatment process.
3. Numerical simulations of the extrusion showed that there
were no significant differences in the local extrudate
temperature. Minor differences in temperature were
observed towards the edges of the profile relating to the
applied ram speed.
4. The regions above the screw ports were found to have an
elevated local strain rate in the bearing region of the die
compared to the bulk area. These regions of increased
strain rate coincided with where the streaks were located
on the experimental extrusions.
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(Deakin University, 2015), p. 75–80
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(2012)
 Effect of Heat-Treatment on Microstructure
and Mechanical Properties of Sonicated
Multicomponent AlMgSiCuZn Alloy

Kwangjun Euh, Jae-Gil Jung, Eun-ji Baek, Jung-Moo Lee,

and Hyoung-Wook Kim

Abstract
In this study, an AlMg8Si9Cu10Zn10 (in wt%) alloy is fabricated with a high volume
fraction of coarse secondary phases, which is higher fraction than in the conventional piston
alloys. Ingots are cast in a permanent mold after an ultrasonic melt treatment for 60 s at the
temperature range of 750–700 °C. Microstructure of AlMgSiCuZn alloy consists of Si, Zn,
Mg2Si, Q-Al5Cu2Mg8Si6, and h-Al2Cu phases. By the heat-treatment at 440 °C, Q-phase at
the vicinity of blocky Mg2Si phase grows and the roundness of the second phases increases
with respect to the heat-treating time. Compared with the as-cast specimen,
room-temperature ultimate compressive strength of the heat-treated specimens increases.
However, maximum compressive stress at 350 °C is slightly decreased by heat treatment.
The formation of fine clusters increases the ultimate compressive strength, while the
spheroidization of bulky secondary phases during heat treatment deteriorates the ultimate
compressive strengths.

Keywords
Heat-treatment Microstructure Ultrasonic melt treatment Multi-component
AlMgSiCuZn alloy

Introduction treatment (UST) is known to reduce the casting defects [7]

Recently, much research has been put forth on the high
entropy alloys (HEAs) due to their extraordinary high
strength and thermal stability at elevated temperatures [1, 2].
Studies on low-density multicomponent alloys have been
already started and Yang et al. reported that
Al80Li5Mg5Zn5Cu5 (at.%) alloy consisted of Al
solid-solution and intermetallic compounds (IMCs) exhibit-
ing excellent room-temperature compressive strength despite
of the low DSconf value (0.78R). [3]. Coarse IMCs act as
main sites of stress concentration and thus deteriorate the
mechanical properties [4–6]. Hence, the IMCs needs to be
refined for further improving the mechanical properties of
low-density multicomponent alloys. Ultrasonic melt
K. Euh (&)
J.-G. Jung
E.-J. Baek
J.-M. Lee
H.-W. Kim
Korea Institute of Materials Science, 797 Changwon-daero,
Changwon, 51508, Republic of Korea
e-mail: keuh@kims.re.kr
with refining the microstructure [5]. The solution treatment
can also affect mechanical properties of low-density multi-
component alloys, since it changes constituent phases and
modifies the morphology of IMCs [8, 9].
In the present study, the effect of heat treatment on the
microstructure and mechanical properties of sonicated mul-
ticomponent Al70Mg10Si10Cu5Zn5 alloy were analyzed.
Furthermore, the mechanical properties of Al70Mg10Si10-
Cu5Zn5 alloy were compared to those of commercial Al
alloys for piston applications.
Experimental
A 1.5 kg of Al70Mg10Si10Cu5Zn5 alloy melt was produced at
800 °C in an induction melting furnace using high-purity
(99.9 wt%) metals (Al, Mg, Zn) and master alloys (Al-25Si,
Al-30Cu). The melt was sonicated for 60 s at the

© The Minerals, Metals & Materials Society 2017 379

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_47
380 K. Euh et al.

energy dispersive X-ray spectroscope. The grain structure

was examined using an electron backscatter diffraction
(EBSD) instrument installed in a field emission scanning
electron microscope. The precipitates were examined using a
field emission transmission electron microscope. Cylindrical
samples (Ø8  12 mm) were prepared for compression
tests. The compression tests were performed at 25 °C using
an Instron 5982 universal testing machine with a strain rate
of 5  10−4 s−1. Compression tests were also conducted at
elevated temperatures ranging from 100 to 350 °C up to
strain of 0.5 using a Thermecmastor-Z testing machine with
a strain rate of 5  10−3 s−1.

Results and Discussions

Several secondary phases are observed in the as-cast alloy

Fig. 1 SEM micrographs of a as-cast alloy and b heat-treated alloy for
10 h
temperature range of 750–700 °C using a Ti sonotrode [10],
and followed by casting in a permanent mold at 700 °C. The
sonicated Al70Mg10Si10Cu5Zn5 alloy was heat-treated at
440 °C for various holding times (1–10 h).
Microstructures were observed using an optical micro-
scope and a scanning electron microscope equipped with an
(Fig. 1a) and are identified as Mg2Si, Q, Si, h and Zn by
analyzing their chemical compositions. Q phases are
observed adjacent to Mg2Si particles and Zn phases are
observed near h particles. This is probably related to the
serial formation of secondary phases; Q and Zn phases are
formed after Mg2Si and h phases, respectively. By the heat
treatment, both area fraction and size of primary Mg2Si
particles are decreased, while area fraction of Q phase
increases (Fig. 1b). The secondary phases are spheroidized
during the heat treatment.
Table 1 shows the size and area fraction of secondary
phases in Al70Mg10Si10Cu5Zn5 alloy with respect to the heat
treatment time at 440 °C. The area fraction of Mg2Si phase
deceases gradually from 10.3 to 6.0% with increasing heat
treatment time. At the same time, the area fraction of Q
increases from 11.5 to 14.3%. This is due to the transfor-
mation from unstable Mg2Si phase to stable Q during heat
treatment. The area fractions of h and Si phases in the as-cast
alloy are 7.1 and 3.3%, and these values are not much
changed during the heat treatment. During the heat treat-
ment, the total area fraction of secondary phases remains to

Table 1 Size and area fraction Phase Heat treatment time (h)
of secondary phases in
Al70Mg10Si10Cu5Zn5 alloy 0 1 4 10
Size (lm) Mg2Si 20.6 18.4 14.5 14.2
h-Al2Cu 11.5 10.5 9.7 9.8
Q-Al5Cu,MgsSi6 6.7 6.4 5.7 5.6
Si 4.2 3.8 3.5 3.6
Fraction (%) Mg2Si 10.3 8.9 7.3 6.0
h-Al2Cu 7.1 7.0 6.3 6.7
Q-Al5Cu,MgsSi6 11.5 11.2 12.3 14.3
Si 3.3 3.9 4.5 4.4
Total 32.2 31.0 30.4 31.4
Effect of Heat-Treatment on Microstructure and Mechanical Properties … 381

similar values (30.4–32.2%). The size of Mg2Si phase
decreases from 20.6 to 14.2 µm due to the dissolution of
Mg2Si during the heat treatment, while the sizes of Q, Si and
h phases are not much changed.
Needle-like precipitates are observed in the Al matrix of
as-cast alloy (Fig. 1a), which are found to be Q and h′ phases
through the EDXS analysis (Fig. 2). Their size is in a wide
range of 10–1000 nm. However, the needle-like Q and h′
phases are not observed in the heat-treated alloys and very
fine precipitates less than 10 nm are present.
Thermal analysis via differential scanning calorimetry
reveals that the as-cast alloy contains both ellipsoidal GP
zones and h′ phase (Fig. 3). On the other hand, the
heat-treated alloy contains both spherical and ellipsoidal GP
zones (Zn clusters). The heat treatment also causes the dis-
solution of h′ and h phases into the Al matrix and then
probably Cu clusters can form at room temperature.
The DSC measurements confirm that the fine precipitates
observed in the heat-treated alloy are spherical and ellip-
soidal GP zones as well as Cu clusters (GP zones). Such a

Fig. 2 TEM micrographs of a, b as-cast alloy and c heat-treated alloy for 4 h [11]
382
Fig. 3 DSC curves of as-cast alloy and solution-treated alloy at
440 °C for 4 h [11]
Table 2 Compressive strength at room temperature and 350 °C
Temperature Compressive Heat treatment time (h)
strength 0 1 4 10
RT r0.2 414 417 417
rmax 681 744 742
350 °C rmax 121 119 118
formation of Zn and Cu clusters during holding at room
temperature (i.e. natural aging) results from the high Zn
(*15 wt%) and Cu (*3 wt%) concentrations of the Al
matrix in the heat-treated alloy enough for them to precipi-
tate even at room temperature [12–14].
The compressive yield strengths (r0.2) of heat-treated
alloys for 1, 4 and 10 h are 417, 417 and 406 MPa,
respectively. It is thought that the yield strength was not
significantly affected by heat treatment, considering as-cast
alloy (414 MPa). The rmax value shows a maximum of
744 MPa at the heat treatment time of 1 h, which is attrib-
uted to the enhanced solid-solution hardening by Zn and Cu
atoms and/or clustering hardening by GP zones. With further
heat treatment time, the rmax value was gradually decreased
to 742 MPa at 4 h and 723 MPa at 10 h.
At the elevated temperature of 350 °C, the rmax value
decreases gradually from 121 to 113 MPa with increasing
heat treatment time. Particularly at high temperatures when
the Al matrix are getting softer, the interconnected network
structure of rigid phases plays a crucial role in mechanical
properties by transporting external load from soft Al matrix
to rigid secondary phases [8, 9]. Therefore, the decreased
rmax value at 350 °C with increasing heat treatment time is
most likely due to the partial break-up of network structures
of rigid phases caused by their spheroidization (Table 2).
K. Euh et al.
Conclusions
In this study, the multicomponent Al70Mg10Si10Cu5Zn5
alloy was successfully fabricated by commercial Al casting
procedure combined with ultrasonic melt treatment. The
effects of heat treatment on the microstructure and
mechanical properties at room and elevated temperatures
were examined. The formation fine clusters such as spherical
or ellipsoidal GP zones increased the ultimate compressive
strength at room temperature. During the heat treatment, the
phase transformation from Mg2Si to Q phase gradually
occurred along with the spheroidization of secondary phases.
The spheroidization of secondary phases occurring during
heat treatment deteriorated the ultimate compressive
strengths.
Acknowledgements This study was supported by a grant of Main
Research Program (PNK4560) and Strategical Materials Program
(No. 10062304) funded by the Korea Institute of Materials Science and
Ministry of Trade, Industry and Energy, respectively.
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 Effect of Interrupted Quenching
on Al–Zn–Mg–Cu Alloys

Gernot K.-H. Kolb, Helmut Antrekowitsch, Daniel Pöschmann,

Peter J. Uggowitzer, and Stefan Pogatscher

Abstract
Al–Zn–Mg–Cu alloys are widely used in aged-hardened condition for aircraft applications
because of their high strength, adequate fracture toughness, stress corrosion cracking
resistance and good machinability. In this study the effect of interrupted quenching (I.Q.)
from solution temperature to 25–225 °C on subsequent artificial ageing was studied.
Hardness measurements, tensile tests and instrumented impact tests were used to
characterize the mechanical properties of Al–Zn–Mg–Cu plates. The results indicate that
a high hardness can be reached directly after I.Q. for medium I.Q. temperatures. Compared
to standard water quenching, the results showed that hardening kinetics and the age
hardening response during artificial ageing can be enhanced for I.Q. at medium artificial
ageing temperatures, but are reduced at high temperatures. I.Q. at high temperatures affects
subsequent artificial ageing via the formation of precipitates, which contribute less to
hardening but consume a significant amount of solute.

Keywords
Aluminum alloys 7xxx alloys Al–Zn–Mg–Cu alloys Ageing Heat treatment

Introduction strength, the fracture toughness as well as the corrosion

Aluminum alloys of the 7xxx series have been widely used
as structural materials in aerospace industries due to their
attractive properties [1–5], such as high strength, ductility,
fracture toughness and corrosion resistance. For new appli-
cations and lighter components, the 7xxx series Al alloys
require enhanced mechanical properties. In addition to the
resistance of the 7xxx series aluminum alloys can be mod-
ified by heat-treatments via the formation of precipitates
[6–10]. Their simplified precipitation sequence upon heating
is generally known as [11, 12]:
SSSS—metastable GP-zones (GPI, GPII)—metastable η′—
stable η

G.K.-H. Kolb
H. Antrekowitsch
S. Pogatscher (&) where SSSS represents the supersaturated solid solution after
Montanuniversitaet Leoben, Franz-Josef-Str. 18, 8700 Leoben, solution treatment and quenching. GP zones are formed
Austria
during natural ageing and in early stages of artificial ageing.
e-mail: stefan.pogatscher@unileoben.ac.at
The metastable phase η′ is commonly responsible for the
G.K.-H. Kolb
main hardening process, whereas the equilibrium phase η is
e-mail: gernot.kolb@unileoben.ac.at
characterized by coarse particles and is typical for overaged
D. Pöschmann
conditions [13–15]. It is generally known that the Al–Zn–
AMAG Rolling GmbH, P. O. Box 32, 5282 Ranshofen, Austria
Mg–Cu alloy series in T6 temper has highest strength
P.J. Uggowitzer
properties, but this condition is rarely used because of their
Laboratory of Metal Physics and Technology, Department of
Materials, ETH Zurich, Vladimir-Prelog-Weg 4, 8093 Zürich, low stress corrosion resistance. To increase the usability of
Switzerland high strength with acceptable corrosion resistance, ageing

© The Minerals, Metals & Materials Society 2017 385

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_48
386 G.K.-H. Kolb et al.

treatments such as T7X have been developed. With of 40 mm thickness with grooves (see Fig. 2a, b), in which
increasing over ageing condition, the strength properties will the samples were inserted immediately after quenching, were
simultaneously decrease. Interrupted quenching (I.Q.) has used to ensure slow free cooling from the I.Q. temperature to
been developed as novel heat treatment procedure for the RT in accordance to industrial conditions. After cooling, the
6xxx series [16, 17]. It was found that the I.Q. treatment not samples were taken out of the plate, pre-strained for
only increase the strength but also reduces the required time approximately 1.5% and naturally aged for seven days.
of ageing. As there are similarities in the effect of other novel Finally, an artificial ageing procedure at 125 °C was
heat treatment strategies for 6xxx and 7xxx series alloys (e.g. examined.
interrupted ageing [18–21]), I.Q. may also be of interest for
optimizing the characteristics of 7xxx wrought aluminum
alloys.
In the present work, the aim was to study the influence of
I.Q. on hardness, strength, elongation at fracture and notch
impact energy of the alloy AA7050. Interrupted quenching
was performed for temperatures between 25 and 225 °C and

300 mm
the evolution of corresponding properties was studied over
the subsequent processing steps, i.e. free plate cooling,
natural and artificial ageing.

Experimental Methods
300 mm
The experimental alloy AA7050 was provided by AMAG
rolling GmbH in form of wrought plates. The sequence of
the heat treatment procedure is schematically shown in
Fig. 1. From plate material, samples were machined with a
geometry of 12  12  125 mm. Solution heat treatment
was performed at 482 °C in a circulating air furnace
(Nabertherm N15/65 SHA) followed by quenching in water
at room temperature, with immediate reheating (see Fig. 1). Milled grooves for the
Laboratory scaled small samples were not directly quenched samples
to the I.Q. temperature as this would be done for industrially
scaled plates because this was found to result in a decreasing
quenching rate with increasing I.Q. temperature, which Fig. 2 a Top view of the plate with grooves into which the samples
overlays the effect of the I.Q. temperature. Preheated plates are inserted; b milled grooves in the test panel to insert the sample

Fig. 1 Scheme of the

experimental procedure of I.Q
Effect of Interrupted Quenching on Al–Zn–Mg–Cu Alloys 387

Brinell hardness measurements (HBW 2.5/62.5) were
carried out on an EMCO TEST M4 unit.
Tensile testing was performed in a Zwick/Roell 100 kN
unit following the procedure given in the standard EN ISO
6892-1:2009-11 with samples according to DIN 50125—
A8  40.
The Charpy V-notch instrumented impact tests were
carried out on a Zwick HIT25P with a 5J pendulum.
Sub-scaled Charpy specimen were used with a geometry
based on the bend SE(B) specimen of ASTM E399—12.
The cross section of the chosen specimen was 6  3 mm
and the length 30 mm. The V-notch was eroded with a
radius of 0.1 mm.
quenched to RT (from 114 HBW to 144 HBW). The hard-
ness increase upon natural ageing for 7 days studied was
small for all I.Q. temperatures. Those samples with plate
temperature >125 °C showed a negligible hardness increase,
but started at a significantly higher level than the RT samples
reaches after natural ageing of 7 days.
Figure 5 compares the effect of I.Q. temperature on
subsequent artificial ageing to the RT reference sample.
At the beginning of the artificial ageing treatment, the
hardness of the RT and 75 °C sample decreases, most
probably by dissolving GP-zones which were formed during
natural ageing [13, 27]. Interestingly also an initial hardness
decrease is observed for I.Q. > 175 °C where no natural
ageing takes place. Once, if the hardness decrease has

Results and Discussion

The effect of I.Q. on hardness directly after slow cooling in

the plate is shown in Fig. 3. It can be seen that the I.Q. and
preheating temperature of the plates, respectively, has a great
influence on the hardness level compared to the as-quenched
reference at RT.
The RT sample has the lowest average hardness after
cooling (114 HBW), while the 175 and 225 °C sample
possess a hardness level of 165 HBW. Note that the typ-
ical peak hardness value for this type of alloy is approxi-
mately 178 HBW in T6. From the directly measured values
after free plate cooling it follows that for the highest I.Q.
temperature almost near peak hardness can be achieved
without requiring a 24 h heat treatment procedure [22].
Hence, a significant amount of hardening precipitates are
assumed to be already present after this thermal impact
[23–26]. Fig. 4 Hardness evaluation during natural ageing
The largest increase in hardness due to subsequent natural
ageing (Fig. 4) takes place at the reference sample water

Fig. 3 Hardness values after I.Q. and slow cooling in the plate Fig. 5 Hardness measurements during artificial ageing at 125 °C
388
Fig. 6 a Yield strength and b elongation at fracture
finished, a renewed continuous hardness increase takes
place, which is attributed to the typical precipitation hard-
ening effect in 7xxx-alloys [13, 28, 29]. The artificial ageing
curves (Fig. 5) showed that the samples treated at I.Q. of 75
and 125 °C exhibit hardness levels slightly above the peak
hardness reached for the RT reference. The artificial ageing
curve for the room temperature sample showed a (peak)
hardness of 182 HBW after 24 h, while I.Q. at 125 °C
generated a hardness of 191 HBW. For artificial ageing after
I.Q. at 175 and 225 °C the peak hardness level is below peak
hardness of the RT reference. The observed trends for the
peak hardness values are nicely reflected in the results of
tensile tests, which are shown in Fig. 6.
The samples for I.Q. at 125 °C showed a higher yield
strength than the standard RT reference sample (both con-
ditions with straining, natural and T6 artificial ageing),
which may be explained by the formation of a denser
G.K.-H. Kolb et al.
Fig. 7 Results of the instrumented notched impact test
distribution of η′ or its precursors. Interestingly, also the
elongation of the 125 °C I.Q. samples was slightly higher.
For I.Q. at 175 °C the yield strength decreases and but the
elongation at fracture shows with 13.6% the highest value
(Fig. 6b). It is apparent that at a temperature of >175 °C the
age hardening mechanism did change. It is supposed that an
overaging situation occurred, which is characterized by
coarse precipitates (also at the grain boundaries). These do
not contribute considerably to yield strength, reduce elon-
gation, and reduce the remaining super saturation for artifi-
cial ageing [30–32].
The notched impact results (Fig. 7) illustrate that all
values for I.Q. are higher than the RT value by trend.
Nevertheless, the standard deviation is large and further
testing is required to prove this trend.
Conclusion
Interrupted quenching was performed for temperatures
between 25 and 225 °C and the evolution of corresponding
properties was studied over the subsequent processing steps.
I.Q. was found to be a potential heat treatment strategy to
optimize 7xxx aluminum alloys.
• Depending on the temperature range, I.Q. can affect
artificial ageing of AA7050 by a reduction of the
remaining super saturation or promote artificial ageing by
the formation of a dense distribution of η′ or its
precursors.
• Increased yield strength in T6 condition can be provided
via I.Q. in the temperature region around 125 °C.
• High I.Q. temperatures (>175 °C) result in an undesired
reduction of the T6 yield strength.
Effect of Interrupted Quenching on Al–Zn–Mg–Cu Alloys
Acknowledgements The authors wish to express their sincere thanks
to the Austrian Research Promotion Agency (FFG) (Grant No. 850427)
and AMAG rolling GmbH for their financial support of this work.
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minum alloy. Mater. Sci. Eng., A 500(1–2), 34–42 (2009)
30. X.M. Li, M.J. Starink, DSC study on phase transitions and their
correlation with properties of overaged Al-Zn-Mg-Cu alloys.
J. Mater. Eng. Perform. 21(6), 977–984 (2012)
31. X.M. Li, M.J. Starink, Identification and analysis of intermetallic
phases in overaged Zr-containing and Cr-containing Al–Zn–Mg–
Cu alloys. J. Alloy. Compd. 509(2), 471–476 (2011)
32. X.-M. Li, M.J. Starink, The effect of compositional variations on
the characteristics of coarse intermetallic particles in overaged
7xxx Al alloys. Mater. Sci. Technol. 17(11), 1324–1328 (2001)
 Part IX
Aluminum Alloys, Processing and Characterization:
Plasticity and Mechanical Behavior
 New Yield Criterion for Description of Plastic
Deformation of Face-Centered Cubic Single
Crystals

Nitin Chandola, Crystal Pasiliao, Oana Cazacu,

and Benoit Revil-Baudard

Abstract
In this paper an analytical yield criterion for description of the plastic behavior of
face-centered cubic single crystals is presented. The new criterion is written in terms of the
generalized invariants of the stress deviator proposed by Cazacu and Barlat (Int J Eng Sci
41:1367–1385, 2003 [1]), specialized to cubic symmetry. The octahedral projections of the
yield surfaces for different crystal orientations according to the new model are presented,
and compared with the yield surfaces according to the regularized Schmid law (Bishop and
Hill, in Lond Edinb Dublin Philos Mag J Sci 42:1298–1307 (1951) [2], Darrieulat and Piot,
in Int J Plas 12:575–612 (1996) [3]).

Keywords
Generalized invariants Yield criterion Single crystal

Introduction {111} crystallographic planes in the <110> crystallographic

Development of general three-dimensional coordinate-free,
invariant formulations for yield criteria for description of the
constitutive behavior of metallic materials has been a prob-
lem of special interest in the field of solid mechanics and
materials sciences. Specifically, when modeling the plastic
behavior of single crystals, it is essential to account for the
symmetry of the yield surface in the five-dimensional space
of the deviatoric stress components. FCC single crystals or
infinitely sharp texture of certain polycrystalline materials
([4]), exhibit three orthogonal mirror planes [100], a
three-fold rotation axis in the <111> direction, and a mirror
plane at 45º with respect to [100] (see [5]). For FCC single
crystals, slip is the primary plastic deformation mechanism.
According to Schmid law, slip involves shearing on the
N. Chandola (&)
O. Cazacu
B. Revil-Baudard
Department of Mechanical and Aerospace Engineering, University
of Florida, REEF, 1350N. Poquito Road, Shalimar, FL 32579,
USA
e-mail: nitinchandola@ufl.edu
C. Pasiliao
Air Force Research Laboratory, Munitions Directorate, Shalimar,
FL 32579, USA
directions. The most widely used yield criterion for FCC
single crystals is a differentiable and convex approximation
of the Schmid law, by a nth order homogenous function of
stresses (see [3]). This yield function is arbitrarily close to
the inner envelope of the Schmid hyperplanes. Another
approach used to develop yield criteria for single-crystals is
to specialize to cubic symmetry orthotropic yield criteria.
For example, specialization of Hill’s [6] orthotropic criterion
to cubic symmetry and its invariant representation was
proposed by Darrieulalt et al. [3]. Based on rigorous theo-
rems of representation of tensor functions (Boehler [7], Liu
[8]), Cazacu and Barlat [9] developed generalizations of the
isotropic invariants of the stress deviator, such as to account
for any type of material symmetry. Using the orthotropic
generalizations of these invariants, these authors proposed a
non-quadratic orthotropic criterion that captures with
increased accuracy the anisotropy in yield stresses and
strain-ratios of textured rolled sheets (see [9]). In this paper,
we specialize this criterion to cubic symmetries, specifically
to the tetratoidal and diploidal classes of face centered cubic
system. Analysis of the shape of the yield surfaces for dif-
ferent crystal orientations is presented and compared to those
obtained using the regularized Schmid law [3].

© The Minerals, Metals & Materials Society 2017 393

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_49
394 N. Chandola et al.

Generalized Schmid Law for FCC Single [001] GS, n=2

Crystals GS, n=inf

According to Schmid law [10], in a FCC single crystal

crystallographic slip takes place on slip systems which are
defined by a plane (unit normal n) and a direction contained
in this plane of unit vector b. Of all potential slip systems, a
system g is active when the resolved shear stress:

s g ¼ j r : M g j ¼ j r0 : M g j ð1Þ [100] [010]

reaches a critical value sgc . In the above equation, “:”

denotes the contracted product between two symmetric
tensors, r is the Cauchy stress tensor, r0 its deviator (i.e.
r0 ¼ r  ðtrr=3ÞI), while M g is the Schmid tensor of the
system g:
Fig. 1 Octahedral plane representation of the generalized Schmid
(GS) yield surface for n = 2 and n ! ∞ for loadings with the principal
directions along the <100> directions. The stresses are normalized by
the uniaxial yield limit in any of the <100> directions

M g ¼ ðb  n þ n  bÞ=2 ð2Þ
the <100> directions) is shown in Fig. 1 for n = 2 and
with b defining the slip direction, n the unit vector of the n = 750 [amounts to n ! ∞ in Eq. (4)].
normal to the slip plane, and “” denoting the dyadic pro-
duct of the two vectors. At room temperature there are 12
slip systems corresponding to the {111} planes and Proposed Criterion for FCC Single Crystal
the <110> directions. If the critical shear stress sgc is the
same for all slip systems, i.e.: sgc ¼ sc , the polyhedron Cazacu and Barlat [9] developed generalizations of the
defined by isotropic invariants of the stress deviator that satisfy the
  !1=n invariance requirements with respect to the symmetry
X r0 : M g n
  ¼1 ð3Þ
transformations of all classes of the cubic systems. In the
 s  Cartesian frame with axes parallel to the <100> directions,
g c

the generalization of the isotropic second-invariant, J2 ¼

is expressed in the Cartesian coordinate frame with axes  
along the <100> directions of the crystal as: tr r0 2 =2 has the following expression:
 n  n
/ðr0 Þ ¼ r022  r033 þ r012  r013  þ r022  r033 þ r012 þ r013  m1 h 0 2  2  2 i
 n  n J2c ¼ r11  r022 þ r022  r033 þ r011  r033
þ r022  r033  r012 þ r013  þ r022  r033  r012  r013  6 
 0    
þ r33  r011 þ r023  r012  þ r033  r011 þ r023 þ r012 
n n
þ m2 r02 02 02
12 þ r13 þ r23 :
 0   
þ r33  r011  r023 þ r012  þ r033  r011  r023  r012  ð6Þ
n n
 0   
þ r11  r022 þ r013  r023  þ r011  r022 þ r013 þ r023 
n n
 n  n Note the cubic second-invariant, J2c , is a homogeneous
þ r0  r0  r0 þ r0  þ r0  r0  r0  r0  ¼ kn :
11 22 13 23 11 22 13 23 function of second-order in stresses, invariant to circular
ð4Þ permutations, and reduces to the classical isotropic J2 when
the anisotropy coefficients m1 and m2 are set to unity. For
In Eq. (4), the exponent n is such that 1  n\1, k is a face centered cubic crystals belonging to the tetratoidal and
material parameter expressible in terms of the critical shear diploidal classes the expression of the generalization of the
stress sc and the exponent n (for more details of the analysis third-invariant of the stress deviator is:
see [3]). In particular, the quadratic form of this criterion
   
(n = 2) is: J3c ¼ n1 r011 r022 r033 þ 2n2 r012 r013 r023
  ð7Þ
2  02   n3 r011 r02 0 02 0 02
23 þ r22 r13 þ r33 r12 :
r02 02 02
11 þ r22 þ r33 þ r23 þ r02 02 2
13 þ r12 ¼ 4sc ð5Þ
3 The cubic third-invariant, J3c , is a homogeneous polyno-
For loadings such that the principal directions of the mial of order three, invariant to circular permutations, and
applied stress are along the <100> directions, the section of involves three independent parameters, n1, n2, n3 which
the generalized yield surface [Eq. (4)] in the octahedral reduce to unity in the case of isotropy. More details on the
plane (i.e. plane of normal equally inclined to derivations of these expressions can be found in [9]. Using
New Yield Criterion for Description of Plastic Deformation …
these cubic invariants, in this paper, we propose the fol-
lowing criterion for FCC single-crystal:
 3  2
f c ðr0 Þ ¼ J2c c J3c ¼ s6 ð8Þ
with c being a material constant and s being the yield limit in
simple shear in any of the planes {100}.
Note that the proposed criterion involves six anisotropy
coefficients: m1, m2, n1, n2, n3, and c. Given that the criterion
is represented by a homogeneous function in stresses with-
out loss of generality the parameter m1 can be set equal to
unity. The remaining five material parameters can be
determined if the yield stresses in uniaxial tension along
different crystallographic directions are available. This cri-
terion is a specialization to cubic symmetry of the ortho-
tropic criterion of Cazacu and Barlat [9]. For isotropy, it
reduces to Drucker [11] criterion.
In the following, we present the yield loci according to
this new criterion for single crystal and the generalized
Schmid criterion [Eq. (4)] for different crystal orientations
and loading scenarios.
Shape of the Yield Surface for Different
Crystal Orientations
We begin by analyzing the section of the yield surface of the
crystal according to the new criterion for loadings such that
principal directions of the applied stress are along
the <100> crystallographic directions. This projection of the
yield surface is obtained by setting to zero the shear stresses
in Eq. (6)–(7), so
1  02 
02 3 0 2
f c ðr0 Þ ¼ r11 þ r02 2 0 0
22 þ r33 cn1 ðr11 r22 r33 Þ ¼ s
6
ð9Þ
8
Therefore, for such loadings only the anisotropy coeffi-
cient n1 appears in the expression of the criterion. In par-
ticular, if Y denotes the yield stress in uniaxial tension along
any of the <100> crystallographic directions, then according
to the criterion the following relation holds:
 s 6
27  4cn21
¼ ð10Þ
ð27Þ2 Y of the anisotropic coefficient m2.
Thus, the coefficient cn21 has a clear physical significance
being directly expressible as a ratio between the respective
yield limits.
According to generalized Schmid (GS) criterion [Eq. (4)]
 s n
¼2 ð11Þ
Y the same is shown in Fig. 4b.
395
[001] GS, n=2
A1 GS, n=inf
Proposed Model
A3 A2
A2 A3
[100] [010]
A1
Fig. 2 Comparison between the sections of the yield surfaces
predicted by the proposed model and generalized Schmid (GS) criterion
[Eq. (4)] for loadings with the principal directions along the <100> di-
rections. The stresses are normalized by the uniaxial yield limit in any
of the <100> directions
It is very interesting to note that for cn21 = 2.25, the yield
surface according to the new criterion approximates well the
generalized Schmid surface (see Fig. 2). In Fig. 2 are also
shown the yield points corresponding to uniaxial loadings
along the crystallographic directions <100> designated by
Ai, A i , i = 1…3. Comparison with the quadratic approxi-
mation is also presented.
The sections of the yield surface of the crystal according
to the new criterion for loadings such that principal direc-
tions of the applied stress are along the [110], [̅110], and
[001] crystallographic directions and the GS model are
shown in Fig. 3. Comparison with the quadratic approxi-
mation is also shown.
Note that for this crystal orientation and loadings the
generalized Schmid criterion writes:
jr1  r3 jn þ jr2  r3 jn ¼ kn =4; ð12Þ
where, r1 , r2 and r3 are the principal values of the applied
stress.
In particular, according to the criterion the ratio between
yield stress in uniaxial tension along the [110] direction and
the yield stress in uniaxial tension along the [100] direction
is 21=n . It is worth noting that according to the new criterion
[Eq. (8)] the ratio between the uniaxial yield stresses along
the [110] and the <100> directions is controlled by the value
It is interesting to represent the yield surface for the [111]
crystal orientation. We analyze the case when the crystal is
subjected to loadings such that the principal directions are
along [111], [1̅21], [͞101] crystallographic directions (see
Fig. 4). The stereographic projection of the family of
directions along which the response of the crystal should be
396 N. Chandola et al.

GS, n=2 GS, n=2

[001] GS, n=inf [101] GS, n=inf
Proposed Model Proposed Model
A1
E1
T3
T1 T1

E1 T3
A1 [̅110]
[110] [121]
[111]

(a)
(a)

[010]
[010]

[-110] [110]

[-111] [111]

[001] [100]
[001] [100]

[-1-11] [1-11]

[-1-10] [1-10]

(b) (b)

Fig. 3 a Comparison of yield surfaces predicted by the proposed
model (Eq. 8) with generalized Schmid (GS) criterion [Eq. (4)] for
loadings with principal directions along the [110], [̅110], [001] crystal
directions; b stereographic projection of the family of directions along
which the response is the same
Fig. 4 a Comparison of yield surfaces predicted by the proposed
model (Eq. 8) with the generalized Schmid (GS) criterion [Eq. (4)] for
loadings with principal directions along the [111], [1̅21], [̅ 
101] crystal
directions; b stereographic projection of the family of directions along
which the response is the same

The GS criterion [Eq. (4)] criterion writes: Yield Surfaces Predicted by the Proposed
 n   Model
2 2  2r1 þ r2  3r3 n
n 
jr2  r3 j þ 2 r1  r2  þ    ¼ kn =2
3 3 3 
In this section, we examine the yield surfaces predicted by
ð13Þ the model for other crystal orientations. We begin the dis-
where, r1 , r2 and r3 are the principal values of the applied cussion with the [112] crystal orientation for the case when
stress. In particular, according to the GS criterion the ratio the applied loading is such that the principal directions of
between yield stress in uniaxial tension along the [111] stress are along the [112], [11̅1], and [1̅10] crystal directions.
direction and the yield stress in uniaxial tension along the According to the GS model, yielding takes place when:
 ð1Þ pffiffiffi  n  
[100] direction is 32 43 n . For n = 2, this ratio is 3, while 2  r1 þ 2r2  3r3 n
n  
jr1  r3 j þ 2 ðr1  r2 Þ þ    ¼ kn =2
for n ! ∞, this ratio is (3/2). It is worth noting that 3 3 
according to the new criterion [Eq. (8)] for the value of the ð14Þ
parameter c fixed, the ratio between the uniaxial yield
stresses along the [111] and the <100> directions is con- where, r1 , r2 and r3 are the principal values of the applied
trolled by the values of the anisotropy coefficients m2 and n2. stress. In particular, according to the GS criterion the ratio
Figure 4 shows the yield surface predicted by the pro- between yield stress in uniaxial tension along the [112]
posed yield criterion [Eq. (8)] and the generalized Schmid direction and the yield stress in uniaxial tension along the
 1n
model [Eq. (1)] for loadings such that principal directions of n
[100] direction is 3n þ42ðn3þÞ 1 þ 1 . For n = 2, this ratio reduces
the applied stress are along [111], [1̅21], [̅ 101]. For the pffiffiffi
proposed criterion the anisotropy coefficients m2 and n2 have to 2 while for n ! ∞, this ratio is 1. On the other hand,
been identified based on the GS yield points T3, and E1 (see according to the new model, the same ratio YY112 100
depends on
Fig. 4). the anisotropy coefficients m2, n1, and n2. Figure 5 shows
New Yield Criterion for Description of Plastic Deformation … 397

GS, n=2 direction and the yield stress in uniaxial tension along the
[1̅10] GS, n=inf
Proposed Model
[100] direction is
E1  1
7n 8 n

þ 1 þ 1 n 3n þ 1
: ð16Þ
3 n þ3 2
n n ð1Þ þ 2 þ 2 n þ5 n

pffiffiffi
For n = 2, this ratio reduces to 2 while for n ! ∞, this
E1 ratio is (7/8).
However, for this orientation of the crystal and loading all
[112] [11̅1] anisotropy coefficients are involved in the expression of the
criterion given by Eq. (8). Figure 6 shows the yield surfaces
predicted by the proposed model and the GS criterion.
Fig. 5 Comparison of yield surfaces predicted by the proposed model
[Eq. (8)] and the GS model [Eq. (4)] for loadings with principal
directions along the [112], [11
1], and [1
10] crystal directions
Conclusions

the yield surfaces predicted by the proposed model and the In this paper, we proposed a general 3-D criterion for
GS criterion for this crystal orientation and loading. yielding of FCC single crystals. The criterion involves five
Next, we examine the response of the single crystal for anisotropy coefficients: m1, m2, n1, n2, n3, and a parameter c.
loadings such that the principal directions of the applied Given that the criterion is represented by a homogeneous
stress are along the [123], [11̅1], [541] crystallographic function in stresses without loss of generality the parameter
directions. The response should be highly anisotropic as m1 can be set equal to unity. The remaining material
evidenced by experimental data (see [12]). According to the parameters can be determined if the yield stresses in uniaxial
GS model, yielding takes place when: tension along different crystallographic directions are avail-
 n   able. This criterion is a specialization to cubic symmetry of
3 þ 5n þ 8n 9r1  14r2 þ 5r3 n
jð r  r Þ j n
þ 2   the orthotropic criterion of Cazacu and Barlat [9]. For iso-
7n
1 3  21 
tropy, it reduces to Drucker [11] criterion. The yield surfaces
 n  n
14r2  18r1 þ 4r3   
þ 2  þ 26r1 þ 14r2  20r3  ¼ kn according to this criterion where presented for different
21   21  crystal orientations and three-dimensional loadings. More-
ð15Þ over, the response according to the regularized Schmid law
was also analyzed. Note that both criteria [Eqs. (4) and (8)]
where, r1 , r2 and r3 are the principal values of the applied satisfy the invariance requirements associated with cubic
stress. In particular, according to the GS criterion the ratio crystal symmetry, namely that the response should be the
between yield stress in uniaxial tension along the [123] same for certain family of planes (see Figs. 3b and 4b which
show the (001) pole figure indicating normal to the planes of
the same families).
It is shown that according to the generalized Schmid law
with n = 2, the yield stress in uniaxial tension along the
[̅54̅1] GS, n=2 pffiffiffi
GS, n=inf [110], [112] and [123] should coincide and be equal to 2
Proposed Model times larger than the uniaxial yield stress in any of
E1 the <100> directions; the uniaxial yield stress in the [111]
pffiffiffi
direction is 3 times larger than the uniaxial yield stress in
any of the <100> directions. For n ! ∞, the yield stress in
the [110] and [112] direction are the same as in <100> di-
E1
rections while the yield stress in the [123] direction is lower
  
than that in [100] Y123 ¼ 78 Y100 and in [111] direction is
[123] [11̅1]   
higher than that in [100] Y111 ¼ 32 Y100 .
On the other hand, according to the proposed criterion the
Fig. 6 Comparison of yield surfaces predicted by the proposed model
uniaxial yield stresses in the <100> directions and [111],
[Eq. (8)] and the GS model [Eq. (4)] for loadings with principal [110], and [123] directions are different, which is what the
directions along the [123], [11̅1], [̅54̅1] crystallographic directions single crystal data on real materials indicate (see [12]).
398
References
1. O. Cazacu, F. Barlat, Application of the theory of representation to
describe yielding of anisotropic aluminum alloys. Int. J. Eng. Sci.
41, 1367–1385 (2003)
2. J.F.W. Bishop, R. Hill, A theoretical derivation of the plastic
properties of a polycrystalline face-centered metal. Lond. Edinb.
Dublin Philos. Mag. J. Sci. 42(334), 1298–1307 (1951)
3. M. Darrieulat, D. Piot, A method of generating analytical yield
surfaces of crystalline materials. Int. J. Plas. 12, 575–612 (1996)
4. G.R. Canova et al., The yield surface of textured polycrystals.
J. Mech. Phys. Solids 33(4), 371–397 (1985)
5. A.E.H. Love, The Mathematical Theory of Elasticity (1927)
6. R. Hill, A theory of the yielding and plastic flow of anisotropic
metals, in Proceedings of the Royal Society of London A:
Mathematical, Physical and Engineering Sciences, vol. 193 (1948),
p. 1033
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7. J.P. Boehler, Lois de comportement anisotrope des milieux
continus. J. de mécanique 17(2), 153–190 (1978)
8. I. Liu, On representations of anisotropic invariants. Int. J. Eng. Sci.
20(10), 1099–1109 (1982)
9. O. Cazacu, B. Frédéric, A criterion for description of anisotropy
and yield differential effects in pressure-insensitive metals. Int.
J. Plast. 20(11), 2027–2045 (2004)
10. E. Schmid, W. Boas, Kristallplastizität: Mit Besonderer Berück-
sichtigung der Metalle (in German), 1st edn. (Springer, Berlin,
1935)
11. D.C. Drucker, Relation of experiments to mathematical theories of
plasticity. J. Appl. Mech. Trans. ASME 16(4), 349–357 (1949)
12. W.F. Hosford, R.L. Fleischer, W.A. Backofen, Tensile deforma-
tion of aluminum single crystals at low temperatures. Acta Metall.
8(3), 187–199 (1960)
 Quantifying As-Cast and Homogenized
AA7050 Mechanical Properties Through
Compression Testing

Yunbo Wang, Matthew John M. Krane, and Kevin P. Trumble

Abstract
Prior studies of cast AA7050 mechanical property are sparse, and only include the as-cast
condition. In order to generate data for simulation of stress development in direct chill
(DC) casting, compression tests were performed on AA7050 specimens in both as-cast and
homogenized conditions in the temperature range of 20–500 °C at strain rates from 10−4 to
10−2 s−1 to a strain of 0.5. Results from test specimens having round and square
cross-sections were compared to each other and to published tensile data. The round
specimens are preferred due to less cornering effect. The flow stress-strain data is fit to the
Ludwik equation to generate constitutive relations for the flow stress as a function of strain,
strain rate and temperature. The microstructural changes from as-cast to homogenized
structures lowers the flow stress of AA7050 with the removal of harder eutectic
microconstituent. This effect is most significant at an intermediate temperature (200 °C)
and decreases with increasing temperature.

Keywords
AA7050 Flow stress High temperature mechanical testing

Introduction formation during or after solidification, and cause hazards in

AA7050 and other 7xxx series aluminum alloys are known
for the unusual combination of high toughness and strength,
and low density. They are used mainly in the structural
applications for aerospace and automotive industries [1, 2].
Direct chill (DC) casting is the most common technology for
production of aluminum alloy ingots. In this process, the
liquid alloy first is cooled while moving through a mold to
form a solid shell, and then exposed to direct contact with
chilling water as it moves out of the mold. Due to the high
and non-uniform heat extraction rate during DC casting,
thermal strains accumulate and give rise to the development
of thermal stress. Tensile stress may result in crack
Y. Wang (&)
M.J.M. Krane
K.P. Trumble
Purdue Center for Metal Casting Research,
School of Materials Engineering, Purdue University,
Neil Armstrong Hall of Engineering,
701 West Stadium Avenue, West Lafayette, IN 47907, USA
e-mail: wang1320@purdue.edu
the subsequent sawing process. This has especially affected
the production of AA7050 due to its relatively wide freezing
range and low ductility in the as-cast state [3]. Homoge-
nization usually follows DC casting. In homogenization, the
cast alloy is heated to a temperature lower than the solidus
point for hours to remove microsegregation and eutectic and
relieve residual stress.
Since the beginning of the 1990s, studying thermal stress
and strain in industrial ingot casting through inexpensive
numerical finite element models has become a
well-established approach. Drezet and Rappaz developed a
three-dimensional model in ABAQUS to predict ingot dis-
tortion [4]. The numerical model and measured results
agreed with each other in terms of the pull-in of ingot rolling
faces, and they showed that increasing casting speed would
introduce more distortion. Afterwards, more finite element
models have been built to calculate the stress level in casting
ingots [5–9]. Advanced experimental techniques such as
neutron diffraction have been applied to validate the

© The Minerals, Metals & Materials Society 2017 399

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_50
400
predicted stress levels [5, 6]. The agreement between the
experimental measurements and numerical simulations
demonstrated that well-defined finite element models are
reliable for stress prediction. To date, various cracking cri-
teria are also embedded into the current models to predict
cracking tendency [10–12].
Despite the great advancement in the finite element
modeling and exploration in cracking criteria during casting,
there is a considerable scarcity of mechanical properties data
of aluminum alloys over relevant temperature and strain rate
ranges, especially in genuine as-cast state for DC casting
models. Wan et al. [2] studied the tensile yield strength and
elongation of cast AA7050 as a function of aging time. Only
two groups have measured temperature-dependent flow
stress data for as-cast AA7050. Lalpoor, Eskin and Katger-
man [13] performed tensile testing on industrial-sized DC
cast AA7050 samples and reported the flow stress as a
function of strain. They also showed that the effect of grain
size over typical variations is not significant, and compared
the yield strength and ductility data to industrial homoge-
nized and stress-relieved specimens [3]. A series of studies
were conducted to continue measuring the flow stress
behavior in semi-solid states [14, 15]. Bai et al. [16] per-
formed compression tests on as-cast AA7050 and claimed
that the flow stress results from tensile and compressive tests
are similar.
In order to continue cast AA7050 mechanical data mea-
surements and also to include the study of the microstruc-
tural influence on cast aluminum alloys properties,
compressive tests are applied in the current study to measure
the flow stress data for AA7050 in both laboratory static cast
and industrial homogenized conditions. The effect of
homogenization on microstructure and the subsequent vari-
ation on flow stress-strain curves will be analyzed. Com-
pression testing is considered to have three advantages:
(1) The test can be easily controlled with a constant true
strain rate as the sample geometry is simple [17]; (2) The
temperature gradient is smaller across the sample with a
smaller size; (3) Test specimen machining is easier and most
of the raw material is utilized.
Experimental Procedures
Industrial AA7050 alloy was used in the current study, and
the chemical composition is within commercial range [18].
The alloy was from cylindrical DC cast ingot sections,
38 cm in radius. The ingot was industrially homogenized
before cutting into plates along the transverse direction.
Two sets of specimens were prepared: one set with
as-received, homogenized condition (cut around the
mid-radius position), and the other being re-melted (from the
Y. Wang et al.
alloy after extrusion) and cast in a steel mold. In order to
produce an equiaxed grain structure with a grain size com-
parable to the industrial homogenized ingot, the 25-mm
thick steel plate mold was preheated to a temperature of
approximately 300 °C, and the pouring temperature was
approximately 660 °C (a superheat of 25 °C).
Specimens for microstructure analysis were polished using
diamond paste and colloidal silica suspension (down to
0.6 µm). The equiaxed grain morphology was confirmed after
macroetching with NaOH. The microstructures were then
examined with an optical microscope to characterize features
such as eutectic microconstituent and precipitates. An SEM
with EBSD detector was used to clearly resolve the grain size
on the polished surfaces. Grain sizes were determined through
line intercept method based on the EBSD images. In order to
perform compression testing, specimens were machined to
cylindrical shapes (10 mm in diameter and 15 mm in length).
A Haas CNC lathe was used for machining and the precision
was within 0.2 mm. Rectangular specimens with a dimension
of 8  8  12 mm were also prepared by milling and the
tolerance was 0.2 mm (same with cylindrical samples). The
height-to-side length ratio was kept as 1.5, following the
compression testing standard [17].
The compression tests are performed on a MTS Insight
material testing system with a clam shell radiation heating
furnace. Compressive loading was applied on the specimens
between 50-mm diameter stainless steel push-rods, con-
nected to a 100-kN load cell. The precision of load mea-
surement was ±15 N, which is relatively small at lower
temperatures (T < 500 °C) compared to the loads measured
(*10 kN) and still acceptable at T = 500 °C when load is in
the order of 1 kN. The entire system was preheated to the
test temperature for 3 h before inserting the sample.
A dummy sample with a thermocouple probe placed in the
center of the surface (shallowly notched) was used to con-
firm the test temperature. Then, the dummy sample was
removed. The test specimen was inserted with a piece of
graphite foil placed between each specimen end and the
push-rods, serving as lubricant. Tests started within 5 min
after specimen was installed to avoid over heat exposure.
Tests were performed at room temperature, 100, 200, 300,
400, and 500 °C. Room temperature was measured to vary
from 22 to 24 °C, and the elevated test temperature ±10 °C.
In order to examine the specimen microstructure right after
preheating and before the deformation, another dummy
sample was placed next to the test sample and taken out right
before the test at selected temperatures.
Compressive stress was applied by moving the top
push-rod downward with fixed displacement rates of 0.008
and 0.8 mm/s, corresponding to average true strain rates
over the strain range of the tests of 5  10−4 and
5  10−2 s−1.
Quantifying As-Cast and Homogenized AA7050 …
Engineering stress and strain were measured, and then the
strain was updated by subtracting the contribution from the
machine stiffness. The data was converted into true stress
and strain using well-known relations for compression test-
ing: et ¼ lnð1  ee Þ; rt ¼ re ð1  ee Þ:
Finally, the very early stage of the curve before yielding
was modified with the temperature-dependent elastic mod-
ulus data from general aluminum alloys [19] to correct for
the deformation of graphite paper in the beginning. How-
ever, this would not have an effect on plastic strain
Fig. 1 Comparison of round and square cross-section cylindrical
compression test specimens (same aspect ratio of 1.5). Round specimen
displays lower flow stress and has a larger fracture strain
Fig. 2 When test temperature is
below incipient melting
temperature, the deformation is
uniform. If the sample is brittle or
the applied compression is too
large, shear failure occurs at an
angle of 45°
401
measurement, as only the curve past the yield point is of
interest for flow stress.
Results and Discussions
Effect of Sample Geometry
Both round (10 mm diameter 15 mm length) and rectan-
gular specimens (8  8  12 mm) were tested at room
temperature, and the results indicate the round specimen
geometry is preferred. As shown in Fig. 1, for the same
sample condition, round sample flows much easier com-
pared to the rectangular one, as no fracture is identified
before the final shear failure. For the rectangular specimen,
it chips off at corners during the test and has several
fractures. Also, the cornering effect that resists deformation
increases the flow stress magnitude in the rectangular
specimens.
Deformation Patterns and Microstructural
Changes
Some of the compression tests were performed to a true
strain greater than 0.8 to study the deformed shapes and
microstructures. Figures 2 and 3 demonstrate the specimen
geometry after compression testing to failure. For test tem-
peratures below and equal to 450 °C, the deformation is
uniform, as shown in Fig. 2, as well as the microstructure in
Fig. 4. If the applied compression is large enough or the
402
Fig. 3 Samples after
compression testing at 500 °C.
a At a strain of 5  10−4 s−1,
the top and bottom surfaces stay
undeformed; b at higher strain
rate (5  10−2 s−1), specimens
shatter immediately after loading
starts
sample is brittle (e.g., homogenized sample at 100 °C fails at
a lower strain than average), shear failure occurs at an angle
of 45°, as along this direction the shear stress is maximum
[20]. At a temperature above the AA7050 incipient melting
temperature (475 °C according to [21]) and a high strain rate
of 5  10−2 s−1, samples shatter within the first 2 s of test
due to liquid embrittlement, as shown in Fig. 3b. Most of the
eutectic microconstituent melts and the interconnected net-
work renders the whole structure brittle. When the strain rate
is low (i.e., 5  10−4 s−1) the deformation inside the sample
is not uniform as shown in Fig. 3a. The top and bottom
surfaces remain undeformed, probably because the structure
collapses inside due to the existence of interior cavities.
The microstructures of as-cast samples before and after
compression at 450 °C are shown in Fig. 4. The mean grain
boundary intercept length decreases uniformly in the direc-
tion of compression across the entire cross-section. Also, the
amount of porosity decreases in the deformed specimen as
pores close under compression.
As-Cast Mechanical Behavior and Effect
of Strain Rate
The as-cast specimens were tested at two strain rates (high:
5  10−2 s−1 and low: 5  10−4 s−1). The measured flow
Y. Wang et al.
stress and strain curves are summarized in Fig. 5. By
increasing the testing temperature, both the flow stress and
the overall stress level decrease, except for the fact that the
samples behave similarly at room temperature and 100 °C.
Strain-rate hardening effect is only significant for tempera-
tures above 300 °C. This agrees well with the results mea-
sured by Lalpoor, Eksin, and Katerman [13] through tensile
tests. Bai et al. [16] heated their samples to 430 °C and
cooled down to the test temperature, and they claimed that
strain-rate hardening effect exists at even low temperatures.
However, the additional heat exposure through the heating
and cooling removes the precipitates that should exist in the
as-cast structure, especially with a long heating duration.
The current study is compared to the previous works on
as-cast AA7050, at low strain rates (in the order of 10−4 s−1)
and small strains (less than 0.1), as these are conditions for
DC casting applications. Figures 6 and 7 illustrate the
comparisons. At temperatures above 300 °C the current
study is very similar to the compressive results by Bai et al.
[16] (Fig. 6). At lower temperatures, the flow stress is higher
in the current work, as the reheating and cooling process in
[16] partially removed the precipitates in the as-cast alloy. In
Fig. 7, the current compression results are compared to
tensile results by Lalpoor, Eksin, and Katerman [3, 13]. At
200 °C and below, the tensile samples failed at very small
strains in the tensile tests, and the stress is slightly higher
Quantifying As-Cast and Homogenized AA7050 …
Fig. 4 Microstructures of as-cast AA7050 samples before and after
testing at 450 °C
than measurement from the current compressive tests. These
differences are possibly caused by difference in grain size
and the existence of porosity, as porosity has strong effect in
tensile tests, but is less significant in compressive tests.
The measured data is also fitted into the modified Ludwik
equation [19] in the form of
rðT; e; e_ Þ ¼ KðTÞðep þ epo ÞnðTÞ ð_ep ÞmðTÞ ð1Þ
Here, r is the true stress, and is dependent on temperature
(T), true strain (e) and strain rate (_e). K is a material constant,
ep is the plastic strain, and epo is chosen as 0.001 by con-
vention. e_ p is the strain rate, n(T) is the strain hardening
coefficient, and m(T) is stain-rate hardening coefficient.
Figure 8 summarizes the fitted parameters (K, n, m) and the
comparison with the previous work on as-cast AA7050 [3,
13, 16]. The trends in the curves for K, m, and n versus
403
Fig. 5 Flow stress versus strain curve for AA7050 in static cast
condition. Strain rate dependence is identified at test temperatures under
300 °C
Fig. 6 Comparison of flow stress versus strain curve of the current
study (WKT) and Bai et al. (BLD) [16]
temperature are consistent among all the three pieces of
work. Especially at temperatures above 200 °C, m(T) and K
(T) almost coincide between three curves. For [3, 13] (the
curve labeled LEK), the uncertainty is from four repeats at
each temperature and strain rate combination. For the current
study, error bars show uncertainty of fitting itself and indi-
cates that the uncertainty in fitting is negligible. The fitted
parameters for the current study are:
KðTÞ ¼ 1:8  105 T 3  1:21  102 T 2
ð2Þ
þ 8:54  101 T þ 553
404 Y. Wang et al.

Fig. 7 Comparison of flow stress versus strain curve of the current

study (WKT) and Lalpoor, Eksin, and Katerman (LEK) [13]

mðTÞ ¼ 1:93  1010 T 3 þ 2:19  106 T 2

ð3Þ
 4:05  104 T þ 1:32  102

nðTÞ ¼ 1:12  108 T 3  7:21  106 T 2

ð4Þ
þ 5:43  104 T þ 2:23  101

Effect of Homogenization

Microstructures of as-cast and industrial homogenized

samples are shown in Fig. 9. As expected, the as-cast
structure is characterized by eutectic microconstituent; and
the homogenization process removes most of eutectic
structure and introduces secondary particles inside the
grains. For the as-cast sample, the width of eutectic con-
stituent is around 10 µm, which is consistent with the
industrial AA7050 as-cast microstructure published in [3].
Also, needle-shaped precipitates are generated as a result of
homogenization, consistent with the results in [22]. The
industrial homogenized AA7050 in the current study is
similar to the laboratory cast samples by Robson after
homogenization at 450 °C and slow cooling [22].
The microstructural differences combining with the test Fig. 8 Parameters fitted to modified Lukwik equation of the current
results of as-cast and homogenized specimens can be used to study (WKT) compared to the previous work [3, 16]. The error bars of
interpret the major strengthening mechanism in a specific LEK shows the uncertainty in four measurements and those of WKT
alloy. The flow stress-strain curves of the as-cast and shows uncertainty in parameter fitting
Quantifying As-Cast and Homogenized AA7050 … 405

Fig. 11 Comparison of AA7050 and AA6201 in homogenized and

as-cast conditions at 300 °C. Data for AA6201 is from [17].
Homogenization has opposite effects on the flow stress of the two
alloys

homogenized AA7050 samples are compared in Fig. 10.

Fig. 9 Optical micrographs of AA7050 alloys a cast in steel mold and
b directly from industrial homogenized ingot. A similar porosity level
is exhibited
The homogenized sample is slightly stronger than the as-cast
counterpart at 500 °C, and they behave the same at 400 °C.
From 400 to 200 °C, homogenization lowers the flow stress
of AA7050, and the effect is the most potent at 200 °C. At
temperatures below 100 °C, the behavior between as-cast
and homogenized samples is similar again. In contrast, for
AA6201, homogenization increases the flow stress as shown
in Fig. 11 according to [17]. This is caused by different
strengthening mechanisms in the specific alloys, whether
solid solution hardening or precipitation hardening is the
dominating factor. Here, it indicates that for AA7050
the precipitate hardening is the dominating mechanism on
the flow behavior; while for the much leaner alloy AA6201,
solid solution hardening is the major factor.

Comparison with AA2024, AA7075, and AA6061

in As-Cast State

Data in the current study is also compared to those of as-cast

aluminum alloys 2024, 7075, and 6061 [17]. The data points
for current study are calculated based on the fitted K(T), m
(T) and n(T) in Eqs. (2)–(4) in order to match the test tem-
peratures and strain rates in [17] (0.1 s−1 = high and
1  10−3 s−1 = low in Figs. 12, 13 and 14), except for the
Fig. 10 Comparison of homogenized and as-cast AA7050 500 °C data. In Fig. 12, AA7050 is compared to AA2024 at
stress-strain curves two temperature ranges. At 500 °C, AA2024 is much
406 Y. Wang et al.

Fig. 13 Comparison of AA7050 and AA6061 in as-cast condition at

300 °C. Data for AA6061 is from [17]

stronger and still has stable plastic flow, as it has a higher

Fig. 12 Comparison of AA7050 and AA2024 in as-cast condition.
Data for AA2024 is from [17]
incipient melting temperature compared to AA7050. At
intermediate temperatures (350 °C), the behavior of
AA2024 is similar to that of AA7050. However, a much
lower strain-rate sensitivity is identified in AA2024 com-
pared to AA7050. Also, it indicates that increasing alloying
element content will not necessarily improve the strength at
higher temperatures where the precipitates are coarsened and
partially dissolved, as shown in Fig. 13. AA7050 and
AA6061 behave similarly at 300 °C, although AA6061 is
much leaner (97 wt%Al) compared to AA7050 (89 wt%Al).
AA7075 is chemically close to AA7050, and they have
demonstrated similar strain-rate dependence of flow stress at
450 °C, as shown in Fig. 14. The flow stress magnitude of
AA7050 is slightly higher at low temperatures (250 °C)
compared to AA7075, and the trend is reversed at higher
temperatures (450 °C).
Quantifying As-Cast and Homogenized AA7050 …
Fig. 14 Comparison of AA7050 and AA7075 in as-cast condition at
250 and 450 °C. Data for AA7075 is from [17]
Conclusions
In this paper, compression tests were used to study the
mechanical behavior of as-cast and homogenized AA7050
alloys. The advantage of applying round specimens over
rectangular ones is less cornering effect that hinders flow.
Uniform deformation is confirmed in the cross-section
microstructures for tests conducted below the incipient
melting point. In as-cast state, AA7050 shows strain-rate
407
hardening at temperatures greater than 300 °C, below which
strain hardening is the major factor influencing flow stress.
The fitted parameters for the constitutive law (modified
Ludwik equation) are consistent with the previous studies.
Moreover, it shows that homogenization lowers the flow
stress of AA7050, as the precipitate hardening is the domi-
nating mechanism on the flow behavior. This trend will
reverse for alloys that have solid solution hardening as the
main strengthening mechanism. This work provides readily
available constitutive relations for AA7050 as input
parameters for DC casting related simulations and also
general data for hot press/work ability. The microstructural
effect on mechanical properties is highlighted and should
continue to be studied in future work.
Acknowledgements The authors would like to thank the Nanshan
Aluminum, Beijing Institute of Aeronautical Materials for their finan-
cial support for this work. Materials for the project donated by Alcoa
Lafayette Operations are also acknowledged.
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 Determining a Stable Texture Condition Under
Complex Strain Path Deformations in Face
Centered Cubic Metals

Usman Ali, Abhijit Brahme, Raja K. Mishra, and Kaan Inal

Abstract
Evolution of texture components during deformation of lightweight aluminum alloy sheet
under different strain paths is studied by analyzing the evolution of element rotation
calculated using a rate-dependent crystal plasticity finite element model. Based on a
stability criteria proposed by Ali et al. (Light Metals 2016. Wiley, London, pp. 159–162,
2016), data from cold rolling, shear and compression simulations is analyzed to determine
stable texture components. The predicted stable texture components, for the same
microstructure, for rolling, shear and compression using the stability criteria are in-line with
experimental observations. Further analysis of simulated data yields a simpler methodology
that stable texture components are those that are aligned with the loading direction. Using
this methodology, stable textures under rolling, shear and plane-strain compression are
analytically identified and the results show an excellent conformity to experimental data.
This new methodology can be included in robust non-texture based phenomenological
modelling to predict texture evolution in engineering design problems.

Keywords
Texture stability Cold rolling FCC Crystal plasticity

Introduction and ignore microstructure effects. Therefore, it is important

The microstructures of polycrystalline materials evolve
during deformation which, in turn, affect their forming
behavior. The forming process typically uses sheet metals,
which themselves are made by a complex strain path viz.
rolling with high thickness reduction [9, 16]. The prediction
of material behavior under complex strain paths using
numerical modelling tools should account for the effect of
microstructure and its evolution during the deformation
process. Current finite element models that can perform large
scale deformation are mostly phenomenological [10, 23, 29]
U. Ali
A. Brahme
K. Inal (&)
University of Waterloo, 200 University Ave W,
Waterloo, ON N2L3G1, Canada
e-mail: kinal@uwaterloo.ca
R.K. Mishra
General Motors Research and Development Center,
30500 Mound Road, Warren, MI 40890-9055, USA
to incorporate the effect of microstructure in phenomeno-
logical models.
Traditionally, numerical simulations using crystal plas-
ticity are a preferred approach to study microstructural
evolution under any strain path [28, 36] both at the micro
and macro-scale. There is considerable work done on ana-
lyzing the texture development during deformation and
incorporating it into texture based models [2, 17, 30, 36].
These range from simple Taylor based approaches [17, 25]
to more advanced numerical methods like Viscoplastic
self-consistent (VPSC) models [24, 26, 31] and crystal
plasticity based finite element approach [7, 32, 33, 36].
However, all these approaches are time consuming, as they
require running computationally expensive material models.
In theory, a simple method that can provide a way to
obtain stable textures would give phenomenological models
the basic ability to predict the texture evolution for any
deformation. In this regard, seminal work by Hirsh et al.

© The Minerals, Metals & Materials Society 2017 409

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_51
410
[11–13] provides in depth research into rolling textures.
Hirsch and Lücke [12] discuss the stable textures during
rolling simulations using Taylor type models. Other studies
presented in literature also predict stable textures under
different strain paths [20, 22, 38]. However, all these
approaches require expensive simulations for every new
loading condition and starting microstructure to determine
texture stability. For example, Knezevic et al. [20] have
recently investigated deformation behaviors and localization
in deformed FCC oxygen-free high conductivity copper by
analyzing the misorientation between initial and final ele-
ment Euler angles (element rotation) and neighborhood
distributions using crystal plasticity simulations and Taylor
factor (M) to predict stable textures. Zhou et al. [38] use
Taylor factor (M) and element rotations to study the stable
textures. Knezevic et al. [21] have also investigated a Taylor
based computationally efficient interpolation method to
speed up the crystal plasticity calculations in FCC metals.
However, this method is difficult to implement and requires
setting up the spectral interpolation database.
Current numerical approaches to predict stable textures
like Taylor [17, 25], VPSC [24, 26, 31], Crystal plasticity [7,
32, 33, 36] etc are computationally expensive. In addition,
existing research, to the best of the authors knowledge, does
not present an analytical method to predict texture evolution
in phenomenological models. Therefore, there is a lack of a
simple method, to predict textures, that can be used in robust
non-texture based phenomenological models in commercial
packages like LS-DYNA [27]. As mentioned earlier, pre-
diction of stable textures can be used to establish a simple
method to predict textures and current methods to predict
stable textures are insufficient to achieve this. Prior work by
the authors [2] present a systematic investigation of the
relationship between the stability of texture components and
element rotation in deformed polycrystalline aluminum
alloys by comparing the experimental data on the evolution
of stable texture components during cold rolling of AA5754
with those predicted by crystal plasticity simulations. The
stability criterion presented in their work was able to predict
stable texture components for FCC alloys during cold roll-
ing. It is important to mention that the stability criteria
proposed by Ali et al. [2], is different from the ones pre-
sented in literature.
In this work, the stability criterion presented by Ali et al.
[2] is validated on simpler strain paths (shear and com-
pression) and is also seen to hold true. In addition, stable
texture results from the stability criterion [2] point to an
elegant and simple method to predict stable textures from the
knowledge of the initial texture and the loading axis without
undertaking experimentation or simulations for any defor-
mation path. This new and simplified approach can be used
for complex strain paths by breaking them into simpler
deformation modes and is expected to enable more accurate
U. Ali et al.
engineering-scale forming simulations of aluminum alloys
by incorporating texture evolution into phenomenological
models without any need for micro-macro coupled
simulations.
The crystal plasticity framework used in this work
incorporates single-crystal constitutive laws based on the
approach by Asaro and Needleman [3], combined with sta-
tistically representative 3D microstructures of AA5754 to
simulate cold rolling, shear and compression (on the same
sample). A more detailed description of the crystal plasticity
framework used in this work can be found in [2, 7, 18, 36]. It
should be noted that the analysis presented in this work can,
in principle, be performed by other methods that can capture
polycrystal texture evolution like the Taylor based models
[17, 25], Viscoplastic self-consistent models (VPSC) [24,
26, 31], Crystal plasticity finite element based models [7, 32,
33, 36], LAMEL and ALAMEL [15, 37] etc.
Problem Formulation and Methodology
Symmetric cold rolling with half symmetry is performed on
a 175  175  1250 µm sample to model an O-temper
2.5 mm gauge AA5754 sheet as described in the work by
Ali et al. [1, 2]. Statistically equivalent microstructure for
AA5754-sheet is created by a procedure similar to the one
developed by Brahme et al. [4]. The 3D microstructure is
created from 2D Electron Backscatter Diffraction (EBSD)
data that matches the orientation distribution function
(ODF) and misorientation distribution function (MDF). The
microstructure is then converted to a finite element mesh
with multiple elements representing each grain (Fig. 2a).
The specimen has *800 grains with an average size of
22 µm. Figure 1a shows the initial <1 1 1> pole figure of the
reconstructed material. The predominant texture components
present in the sheet, in decreasing order of volume fractions,
are Cube, S, Brass, Copper and Goss (Fig. 1b).
Explicit LS-DYNA finite element cold rolling simula-
tions, with a rate-dependent crystal plasticity user defined
material model (UMAT), are performed on the material
described above with 7 µm solid cube elements as shown in
Fig. 2a [2]. The through-thickness of the pre-rolled sheet is
captured by using half symmetry (RD-TD Plane) in the finite
element model. Vertical, parallel to ND ([1 0 0] direction),
and horizontal, parallel to RD ([0 0 1] direction), velocities
are applied on the sample to simulate the roller velocities and
the sample is rolled to 60% thickness reduction (Fig. 2b). In
addition, RD-ND outside surfaces are constrained in the TD
direction. Simulations show different evolution of textures
through the sheet thickness due to different strain paths
(Fig. 2c) experienced by the material at different locations
[1, 8]. For example, the center of the sheet, in the simula-
tions (bottom of the simulated sample) experiences mostly
Determining a Stable Texture Condition Under Complex Strain … 411

Fig. 1 a Initial <1 1 1> pole figure of the pre-rolled sample b Volume fraction of different texture components in the pre-rolled sample

Fig. 2 a Initial finite element mesh b Deformed mesh at 60% thickness reduction c Effective strain distribution at 60% thickness reduction

compressive loading while the top of the sheet experiences
both compressive as well as shear loading.
Crystal plasticity finite element results are analyzed using
an in-house grain analysis code (gCode) that calculates the
misorientation [5] between initial and final orientations of
each element (u1 ; ;; u2 ). Initial and final orientations for
each element are extracted as Euler angles and converted to
quaternions before obtaining the misorientation between
them [5]. Using the orientation, volume fractions of various
texture components for elements belonging to each bin [5]
are also computed.
Results and Discussion
Cold Rolling Results
Euler angles for each element are extracted from the cold
rolling simulations at several rolling reductions (0, 10…
60%). Euler angles for each element are then used to find the
misorientation between the initial and current state (at each
rolling reduction). The misorientation angle indicating the
rotation of the lattice is referred to as element rotation. The
element rotations are then parsed into 6 bins. Each of the six
412
bins contains Euler angles for the elements that rotate 0–10°,
10–20° … 50–60° respectively. This process is repeated for
several rolling reductions (0, 10…60%) to study the evolu-
tion of textures during cold rolling. Initial texture for ele-
ments belonging to each bin at each rolling reduction is
extracted and represented as pole figures shown in Fig. 3.
Figure 3 shows the evolution of element-rotation-
distribution, represented as <1 1 1> pole figures obtained
from initial element orientation data. Only the first four
element-rotation-bins (0–10° … 30–40°) are displayed for
clarity. All pole figures are plotted on the same scale. Each
column of pole figures in Fig. 3 shows element-rotation-
distribution for a given thickness reduction and the rows
show the initial orientation of elements belonging to differ-
ent element-rotation-bins (starting from 0–10°) after 20, 40
and 60% rolling reductions. Results for 40–50° and 50–60°
bins are not shown as they represent a very small fraction of
elements (1.5 and 0.3% respectively) with respect to the
overall sample. Elements that rotate between 0–20° show
typical rolling texture with high volume fractions of Cube.
However, the number of Cube elements that rotate 0–10°
decreases, while those that rotate 10–20° increases, as the
deformation increases i.e. with increasing thickness reduc-
tion. In the elements that rotate between 0–10°, volume
fraction of Brass component increases as deformation
increases and exceeds volume fraction of Cube (7.7%) at
60% rolling reduction (9%). Copper and S are present in
smaller quantities and follow the same trend as Cube.
At 60% rolling reduction, elements that rotate 20–30° and
30–40° have a high Cube content (volume fractions of 10
and 11% respectively) with a small amount of S (1.6 and
0.5% respectively) and Copper (0.6 and 0.5% respectively).
Texture strength in pole figures also decreases with increase
in rolling reduction as shown in Fig. 3g–l.
Stability Criteria
Pole figures (Fig. 3) of elements belonging to various rota-
tion bins provide insight into the evolution of preferential
element rotation during cold rolling. It can be seen that some
components rotate less than others. This leads to the con-
sideration of stable texture components for a given defor-
mation and leads to the stability criteria presented in
previous work by Ali et al. [2].
Stable textures are defined as elements with the least
rotation at a given level of deformation. This is in-line with
the general definition of stable textures that once stable
textures are achieved, they do not evolve after subsequent
deformations [6, 12, 14]. The following definition is pro-
posed by Ali et al. [2] to ensure that the stability criteria
represents stability throughout the deformation and not just
at any specific time during the deformation; let Rs be defined
U. Ali et al.
as the rate of change of volume fraction of a certain texture


component (Vfc) with respect to time Rs ðtÞ ¼ dVfc =dt ; and
let the stability of a texture component during deformation,
be defined as Rs ðtÞ ! 0 8 t.
In other words, the most stable texture is the one with the
least percentage change in Rs throughout the deformation. In
this definition, the most stable texture component is the texture
component that persists throughout the deformation. That is,
the stability criterion looks at the volume fraction of texture
components that are present during deformation and not what
a certain texture component is evolving/transitioning to. For
example, with Rs  0, if Cube, Brass and Goss were found as
the stable textures and the starting texture had 3.5, 1.5 and
0.5% of Cube, Brass and Goss respectively, the final volume
fraction of Cube, Brass and Goss in the deformed sample
would also be *3.5, *1.5 and *0.5% respectively. This
does not automatically imply that the volume fraction of Cube,
Brass and Goss remains same because elements that initially
corresponded to Cube, Brass and Goss do not rotate to other
texture components. Rather, this implies that the volume
fraction of Cube. Brass and Goss remains same because the
number of elements that rotate into and out of these orienta-
tions remain the same. In addition, it is important to mention
that percentage change in Rs gives relative stability of the
texture components for a given deformation and texture. For
example, for Deformation-A, if Cube, Brass and Goss result in
10, 15 and 16% change in Rs respectively, Cube would be the
most stable texture component. On the other hand, for
Deformation-B, if Cube, Brass and Goss result in 5, 4 and 3%
change in Rs respectively, Cube would be the most unstable
texture component.
Stability Criteria Applied to Cold Rolling
Cold rolling results (Fig. 3d–i) show large changes in texture
from 10–20° compared to 20–30° element rotation bins and
thus it is reasonable to consider the elements that rotate less
than 20° during deformation to represent stable orientations
as presented by Ali et al. [2].
Results in Fig. 4 show evolution of volume fraction of
several texture components that rotate between 0–20°. It
should be noted that Fig. 4 does not show the volume
fraction for the whole sample but only for elements that
rotate between 0–20°. Volume fraction of each texture
component is extracted from initial data (Fig. 3) and repre-
sented as percentage of the overall sample. Figure 4 shows
that volume fraction of Goss, Brass and Copper stay rela-
tively constant throughout the deformation at around 0.8, 3.7
and 2.9% respectively. This result is similar to the result
from the work of Zhou et al. [38] that shows Goss, Brass and
Copper to be stable textures. However, volume fractions of S
Determining a Stable Texture Condition Under Complex Strain … 413

Fig. 3 Evolution of element-rotation-distribution represented as pole figures (<1 1 1>) obtained from the initial texture of the elements for various
rolling reductions and misorientation bins
414
Fig. 4 Volume fraction
evolution of texture component
during cold rolling for elements
rotating 0–20°
Table 1 Percentage change of Percentage change of Rs (SR)
Rs for different texture
components under various Cube
deformations Goss
Brass
Copper
S 0.49
and Cube decrease during deformation. Cube is known to be
a soft texture [34, 35, 38] and reduces from 9.5 to 6.3%
while S changes from 10.4 to 8.6% during deformation.
Using the stability criteria [2] on cold rolling simulations
suggests that Copper (0.12%) is the most stable texture
component followed by Brass (0.13%), Goss (0.22%), S
(0.49%) and Cube (1.0%) with the number in the parenthesis
indicating the normalized percentage change of Rs (Table 1).
S [1 2 3] <6 3 4> carries significant importance in rolling
textures [19]. Therefore, volume fractions of variants of S
namely S1, S2, S3, S4 were studied in detail. Results show
S1 and S3 to be relatively stable with normalized percentage
change of 0.14 and 0.37% respectively whereas S2 and S4
were found to be relatively unstable textures. Therefore, it is
concluded that S1 and S3 are relatively stable textures along
with Goss, Brass and Copper.
Stability Criteria Applied to Compression
and Shear
Cold rolling results from [2] show the ability to predict
stable textures. This stability criterion was also applied under
U. Ali et al.
Cold rolling (%) Compression (%) Shear (%)
1.0 0.18 1.0
0.22 0.67 0.95
0.13 0.41 0.07
0.12 1.0 0.97
0.70 0.06
simpler strain paths namely shear and compression to predict
the stable textures. Therefore, simulations for compression
and shear were performed on the AA5754 sheet (used in the
rolling simulation study discussed earlier). Vertical (normal
to sheet surface) and horizontal (parallel to the sheet surface)
velocities were applied to simulate compression and shear
respectively. Results of normalized percentage change in Rs
were calculated and are shown in Table 1. Results show S
(0.06%) and Brass (0.07%), which are close to [1 0 1], as
more stable than Cube (1.0%) under shear loading and Cube
(0.18%) as the most stable texture (close to [0 0 1]) under
compressive loading. These results are also consistent with
the experimental results [6, 14] where the switching of stable
textures under rolling and shear have been reported.
Stable Texture Condition (STC)
Stable texture results from cold rolling, shear and com-
pression [2] give insight into loading dependent texture
evolution. To study this further, initial inverse pole figures
for stable and unstable elements at 20 and 60% thickness
reduction under cold rolling were plotted (Fig. 5a–d). Stable
Determining a Stable Texture Condition Under Complex Strain …
Fig. 5 Inverse Pole figures ([0 0 1]) for initial texture evolution
distribution at a 20% b 60% rolling reduction for stable texture and
c 20% d 60% rolling reduction for unstable texture
textures at 20% (Fig. 5a), show a peak close to the [1 0 0]
direction with a second peak close to the [1 0 1] direction. At
60% (Fig. 5b), the locations of peaks are switched and the
stronger peak is at the [1 0 1] direction and the [1 0 0] peak
is weakened. Unstable textures at 20% (Fig. 5c) show peaks
near [1 0 0] and [1 1 1] direction at 60% (Fig. 5d) the peak at
[1 1 1] has disappeared.
It can be seen that IPF results from cold rolling (Fig. 5a)
show that stable textures are initially closer to [1 0 0]
direction and tend to get closer to the [1 0 1] direction as the
amount of deformation is increased (Fig. 5b). As the overall
rolling reduction increases, more elements undergo both
shear and compressive loading [1] and the stable textures
tend to be closer to [1 0 1] direction, the same direction as
the loading direction. In addition, stable texture predictions
(Table 1) using the stability criteria under shear (along the
RD—close to [1 0 1] direction) and compression (normal to
the sheet surface—close to [0 0 1] direction) also show
stable textures to be aligned with the loading direction ([1 0
1] and [0 0 1] respectively).
Therefore, an important conclusion that can be drawn
from the stable textures obtained from the cold rolling, shear
and compression simulations is that stable texture
415
components are the ones which have the crystallographic
directions aligned with the loading direction (in the material
frame) i.e. the angle between the crystallographic direction
and the loading direction tends to zero. This suggests that a
knowledge of the starting texture and the strain path can be
sufficient to predict texture evolution of aluminum sheet in a
general sense. This conclusion is referred to as the stable
texture condition (STC).
It is noted that in cold rolling and shear simulations if
loading direction is assumed to be identical, then STC would
lead to the same stable textures under cold rolling and shear.
However this is not true as the horizontal and vertical
velocities applied to the rolling and shear model are differ-
ent. While it is appropriate that the loading direction for
shear is [1 0 1], it is not appropriate to say that for rolling as
the velocities applied under rolling in the horizontal and
vertical direction are not same. A more accurate loading
direction for cold rolling would be a combination of [1 0 0]
and [1 0 1]. This would remove the ambiguity between
rolling and shear and predict the correct stable textures under
rolling.
Summary and Conclusions
Prediction of stable textures is thought to be the first step in
incorporating texture prediction in phenomenological mod-
els. In this work, a stability criteria based on the evolution of
element-rotation-distribution, is applied to cold rolling, shear
and compression simulations. Stable texture components are
predicted under cold rolling, shear and compression along
rolling direction on a AA5754 sheet and validated against
published experimental data. On further analysis of stable
texture results, it is concluded that the crystallographic
directions for stable texture components, in each case, are
aligned with the loading direction and this is referred to as
the stable texture condition (STC).
It is believed that the proposed methodology, presented in
this work, can successfully predict the stability of a given
textural component for any strain path deformation in FCC
materials. In the proposed analysis, the initial texture and the
strain path can be used to analytically predict the final stable
textures, based on the STC, without any need for expensive
crystal plasticity based numerical simulations and this could
be of immense help for simulating large strain deformation
of macroscale sheet samples exhibiting texture evolution.
Acknowledgements This work was supported by the Natural Sciences
and Engineering Research Council Automotive Partnership Collabo-
ration (NSERC-APC) Program under grant no. APCPJ 441668-12 and
General Motors of Canada. The authors would also like to acknowledge
the support of the High Performance Computing Center at the
University of Sherbrooke and insightful discussions with Waqas
Muhammad and Jaspreet Singh Nagra.
416
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 Microstructural Transition and Elevated
Temperature Tensile Properties of Modified
Al–Si–Cu–Mg Alloys

Mehdi Rahimian, Shouxun Ji, Paul Blake, Douglas Watson,

and Zhongyun Fan

Abstract
In order to improve the mechanical properties of aluminium alloys used in automotive
powertrain at elevated temperatures, the chemical composition of Al–Si–Cu–Mg alloys is
modified by addition of transition elements. In comparison with the commonly used
EN-AC-42000 alloy, the new aluminium alloy can significantly improve tensile properties
at elevated temperatures. Microstructural investigation revealed that tuning of chemical
composition can refine the strengthening phases and increase their volume fractions in the
aluminium alloy. SEM observation demonstrated the existence of well distributed phases in
the microstructure of the Developed alloy. As a result of microstructural modification, yield
strength of Developed alloy is enhanced versus Base alloy (EN-AC-42000). The multiple
strengthening mechanisms are responsible for the property improvement.

Keywords
Al cast alloys Transition element Heat treatment Phase transition High temperature
tensile

Introduction other high-temperature aerospace alloys such as Ni and Ti

The reduction of fuel consumption and concomitant decrease
of CO2 emission are taken into account as remarkable
necessities for the pioneer aerospace and automotive
industries to keep their users at highly competitive market.
Diesel and direct fuel injection gasoline engines’ perfor-
mance can be promoted by increasing combustion pressures
and temperatures in engine [1]. Intermetallics are potential
materials for elevated temperature applications. However,
their brittle intrinsic limits their application [2]. Finally, Al
alloys are considerably lighter and more affordable than
M. Rahimian (&)
S. Ji
Z. Fan
Brunel Centre for Advanced Solidification Technology (BCAST),
Brunel University London, Uxbridge, Middlesex, London,
UB8 3PH, UK
e-mail: mehdi.rahimian@brunel.ac.uk
P. Blake
D. Watson
Engineering Centre, Jaguar Cars Ltd, Abbey Road, Coventry,
CV34 4LF, UK
based alloys.
Among Al alloys, Al–Si alloys are most versatile mate-
rials, comprising 85–90% of the total aluminum cast parts
produced for the automotive industry [1, 3]. However, since
most of A1–Si alloys suffer from the significant drop in their
performance at elevated temperatures, a wide range of
investments have been driven on the increasing of engine
performance at elevated temperatures [4–6].
Aluminum can be strengthened through various mecha-
nisms including strain-hardening, solid-solution hardening,
grain refining and precipitate hardening among which pre-
cipitation hardening is a more practical method to fortify
castings for high temperature applications. Historically, most
efforts to develop high-strength, thermally-stable Al alloys
have sought alloying elements that exhibit both limited
solid-solubility at ageing temperature and low diffusivity in
Al. This approach was originally promoted by Adam [7]
who argued, based on diffusion-controlled coarsening the-
ory, that dispersed phases formed from such alloying addi-
tions would be resistant to Ostwald ripening [8, 9].

© The Minerals, Metals & Materials Society 2017 419

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_52
420
Nevertheless, development of Al alloy operating at ele-
vated temperature can be inspired from Ni-based superalloys
demonstrating extraordinary creep resistance up to their
0.75 Tm. High solubility of Al and Ti in Ni is substantial
allowing for formation of very large volume fractions of ɣ′
precipitate which, in many commercial alloys, exceeds 70
vol.%. Based on this concept, alloying with transition met-
als, forming thermally stable and coarsening-resistant pre-
cipitates, was found to be very promising method to enhance
Al alloys strength at elevated temperatures. Several studies
have been driven to evaluate the effect of different alloying
elements such as Ni, Fe, Cr, Ti, V, Sc and Zr on high
temperature mechanical properties of cast Al–Si alloys [4,
10].
The Al–Sc system represents a unique combination of a
shallow solvus curve conducive to precipitation strengthen-
ing, an eutectic phase equilibrium favouring conventional
solidification, and thermodynamically stable Al3Sc having
the L12 structure. However, Sc, as expensive trace elements,
is not affordable to be used in automotive engine applica-
tions. Al–Sc system can be superseded with Al–Zr system
that is taken into account as a cost effective system. These
system are characterized by one of the smallest diffusion
rates and lattice parameter mismatch with Al matrix [11].
This study aims to develop an alloy that fulfils the criteria
for automotive powertrain applications based on new
demands for having higher performance Al alloy operating
at elevated temperatures. To achieve this milestone, the
current used alloy was modified by tuning of its own ele-
ments as well as addition of transition elements. Compre-
hensive microstructural investigation from micro to
nano-size phases reveals the formation of thermally stable
phases containing transition elements and withstanding at
elevated temperature. Based on this argument, the alloy
strength is enhanced at room temperature and elevated
temperatures.
Materials and Experimental Procedure
In this study hypoeutectic Al–Si–Cu–Mg alloys were uti-
lized. Two alloys named Base and Developed alloys with
different chemical compositions were produced in this study
to benchmark their characteristic against each other. The
Base alloy in this study was EN-AC-42000 alloy (Al–7Si–
0.5Cu–0.3 Mg) and Developed alloy was obtained by tuning
existed alloying such as Cu and Mg elements in the Base
alloy and addition of Zr. Sr was added into both alloys. The
alloys were melted in the electrical resistance furnace at
740 °C. The melt was subjected to degassing by a com-
mercial rotatory degasser. Thereafter, the melt was poured
into the boron nitride painted steel mould, designed based on
ASTM E8 standard to produce dog-bone shape tensile test
M. Rahimian et al.
specimens. The specimens were subjected to the T6 heat
treatment in air-circulating chamber furnace.
Specimens for microstructural characterization were pre-
pared using standard metallographic technique with a final
polish to the mirror-like surface using colloidal alumina. The
grain structure was revealed via electro-etching method in
which specimens were etched under voltage of 5 V in the
Baker’s etchant solution, containing 200 ml H2O and 10 ml
Fluoroboric acid (35%).
The microstructure of as-cast and heat treated specimens
were investigated by several tools. Grain structure charac-
terisation was done using Zeiss (Jena model) optical
microscope in polarised mode. Quantitative analysis of the
microstructure was performed using AxioVision software.
Phase and micro-constituents evaluation as well as elemental
analysis were conducted by SUPRA 35VP (Carl-Zeiss
Company, Jena, Germany) field emission scanning electron
microscopy (FE-SEM) which was equipped by an energy
dispersive X-ray spectroscopy (EDS).
The room and high temperature tensile tests were per-
formed by means of Instron 5500 Universal Electrome-
chanical Testing Systems equipped with Bluehill software
and a 50 kN load cell. Room temperature tensile test was
carried out based on ASTM E8/E8 M, while high tempera-
ture tensile test was conducted according to the ASTM E 21
in which specimens were exposed to the target temperature
in an electrically heated air-circulating chamber. Dynamic
Strain Gauge Extensometer was utilized for strain mea-
surement. The tensile test results are reported based on
6 tensile tests for each defined condition.
Results and Discussions
Microstructural Features
The wide range of microstructural investigations in this
study enable us to monitor the formation and transition of
various microstructural features formed due to diversity of
alloying elements. The microstructural assessment of as-cast
specimens by optical microscopy represents that dendritic
microstructure of the base alloy is finer than that of devel-
oped alloy, but the difference is negligible (Fig. 1). The
presence of Cu containing phase, supposed to be Al2Cu, is
easily recognized in the developed alloy. The effect of heat
treatment on the microstructure is displayed in (Fig. 1b, d).
It is seen that the heat treated microstructures differ sig-
nificantly from as-cast microstructure, as the eutectic phases
are transformed into separated finer phases. Whereas the
shape of other phases in the heat treated base alloy vary from
round to rod-like shapes, the heat treated developed alloy
contains nearly identical round shape phases. Since both
alloys were subjected to the similar heat treatment, the
Microstructural Transition and Elevated Temperature …
(a)
(c)
Fig. 1 As-cast (a, c) and heat treated (b, d) optical microstructures of the base (a, b) and developed alloys (c, d)
variation of phases shape between two heat treated alloys
should be the consequence of Sr addition and other chemical
composition adjustment.
Grain structure is taken into account as an important
factor which induces remarkable effect on the mechanical
properties of alloys. According to the Fig. 2, grain size of the
base alloy differs from that of the developed alloy in heat
treated conditions. According to the general theory of
heterogeneous nucleation, the grain size is controlled by
nucleation sites along with the undercooling of melt [12].
Heterogeneous nucleation has an effect that is similar to a
catalyst in reactions. Although the undercooling was con-
stant in the fabrication process of both alloys, nucleation
sites in the developed alloywas higher than that in the base
alloy. This means a considerable drop in (DG ) due to the
presence of phase or particles acting as nucleation sites and
encouraging heterogeneous nucleation. As a result, nucle-
ation rate accelerates in the developed alloy, which thereby
421
(b)
(d)
makes grains considerably finer in the developed alloy in
comparison with the based alloy [12, 13].
Although as-cast samples comprises connected and
coarse eutectic phases, eutectic structures transform to finer
and separated eutectic pools after heat treatment (Fig. 3).
Furthermore, eutectic phases are rounder and more distinct
in the developed alloy compared with the base alloy. The
strengthening phases amount in the developed alloy is higher
than that in the base alloy which is related to the higher
concentration of alloying elements in the developed alloy
resulting in phase and precipitate formation especially after
heat treatment (Fig. 3b, d).
The SEM micrograph and EDS map of the as-cast
Developed alloy is shown in Fig. 4a, b. The EDS map of the
as-cast microstructure reveals the presence of the major
elements including Al, Si and Cu in the developed alloy.
According to the Fig. 4c, the analysis of EDS data discloses
that the heat treated alloy consists of Al–Si phases (#1)
422 M. Rahimian et al.

(a) (b)
Fig. 2 Micrographs of heat treated a base and b developed alloys

(a) (b)

(c) (d)
Fig. 3 SEM micrographs of as-cast (a, c) and heat treated (b, d) structures of the base (a, b) and developed alloys (c, d)
Microstructural Transition and Elevated Temperature …
(a)
(c)
Fig. 4 a SEM micrograph of as-cast developed alloy, b EDS map of as-cast developed alloy and c EDS microstructure of heat treated developed
alloy
known as eutectic silicon, and other phases. It is suggested
that those phases containing Al–Cu (#2) elements can be
Al2Cu named h-phase [3]. Surprisingly, other phases such as
Al–Si–Cu–Mg–Fe (#3) and Al–Si–Fe–Cu (#4) represent
partitioning of Si into the Cu and Mg containing phases
(Fig. 4c).
Considering Fig. 4c, heat treated Developed alloy con-
tains very fine phases dispersed uniformly throughout the
microstructure. Phase (#5) having Al–Si–Cu–Mg [14, 15] is
likely related to Al5Cu2Mg8Si6 known as Q-phase. The
presence of Zr containing phases was also identified in EDS
analysis (phases (#6)).
423
(b)
Tensile Properties
According to the Figs. 5 and 6, tuning alloying elements
considerably improves yield strength of the developed alloy
as compared with that of base alloy. The YS of as-cast
Developed alloy is 36% higher than that of as-cast Base
alloy at room temperature. The reason can be found in the
difference of microstructure of the base and developed
alloys. Moreover, the significant improvement of YS due to
heat treatment indicates the undeniable role of heat
treatment on mechanical properties of both alloys
(Figs. 5 and 6).
424
Fig. 5 Improvement of YS compared with the as-cast base alloy at
room temperature
Fig. 6 Improvement of YS compared with the as-cast base alloy at
200 °C
The heat treated developed alloy exhibits 167% YS
improvement against the as-cast Base alloy, but the YS
improvement of the heat treated base alloy versus the as-cast
one is 139%. It should be noticed that the strengthening
effect of those phases seen in the heat treated developed
alloy is confirmed in previous researches [4, 16].
The increment of mechanical properties can be inter-
preted by Orowan and Hall-Petch theories. In fact, increas-
ing volume fraction along with refinement of phases, taken
place in the heat treated developed alloy, lead to the
reduction of distance between two phases and particles.
Thus, the reduction of phase and particle distance leads to
increasing yield strength, since these phases act as an
obstacle against dislocation gliding when the material is
imposed to stress.
In addition to the phases, grain boundary influences
substantially on the yield strength. Figure 2 demonstrates
that the developed alloy consists of finer grains than the base
M. Rahimian et al.
alloy. According to Hall-Petch equation, having lower grain
size, higher fraction of grain boundaries forms which in turn
act as obstacles against the dislocation gliding during plastic
deformation. As a result, more tension for the movement of
dislocations will be required during deformation resulting in
the increasing of alloy strength [17, 18].
Higher improvement of YS is achieved for both as cast
and heat treated developed alloys at high temperature tensile
test in comparison with the base alloy. Presence of thermally
stable phases interpret the YS improvement of the developed
alloy at 200 °C, being 64 and 199% for as-cast and heat
treated specimens, respectively, over the as-cast base alloy.
Conclusions
The microstructure and tensile properties variations of Al–
Si–Cu–Mg alloy due to tuning of alloy composition and
application of T6 heat treatment have been investigated. The
following conclusions may be drawn:
1. New composition leads to the refinement and increasing
of strengthening phases. Moreover, remarkable phase
transition occurs because of heat treatment, as the
eutectic phases modified significantly.
2. The developed alloy exhibits finer grain structure than
the base alloy, as the grain size of the developed alloy is
nearly the half of the base alloy grain size.
3. The EDS analysis using SEM reveals the presence of
various phases in both alloys.
4. Heat treatment increases YS of the Base and developed
alloys at both room and elevated temperatures by
encouraging the formation of morphologically modified
precipitates.
5. The developed alloy comprises the well distribution of
coarsening resistance Zr containing phases, whereas
small amount of Cu and Mg containing phases were
observed in the base alloy microstructure. Hence, the
developed alloy shows higher YS in comparison with the
base alloy at 200 °C.
Acknowledgements This investigation was carried out in frame of the
high temperature Al alloys project. Authors acknowledge gratefully the
Jaguar Land Rover for financial support through the mentioned project.
References
1. J.A. Lee, Cast aluminum alloy for high temperature applications,
in Automotive Alloys, ed. by S.K. Das (TMS, San Diego, 2003)
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in situ intermetallic composites: fabrication and microstructural
characterization. J. Alloys Compd. 453, L4–L7 (2008)
Microstructural Transition and Elevated Temperature …
3. S.K. Shaha, F. Czerwinski, W. Kasprzak, J. Friedman, D.L. Chen,
Monotonic and cyclic deformation behavior of the Al–Si–Cu–Mg
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383–394 (2015)
4. J. Hernandez-Sandoval, G.H. Garza-Elizondo, A.M. Samuel, S.
Valtiierra, F.H. Samuel, The ambient and high temperature
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Ni additions. Mater. Des. 58, 89–101 (2014)
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10. S.K. Shaha, F. Czerwinski, W. Kasprzak, J. Friedman, D.L. Chen,
Improving high-temperature tensile and low-cycle fatigue behavior
of Al-Si-Cu-Mg alloys through micro-additions of Ti, V, and Zr.
Metall. Mater. Trans. A 46, 3063–3078 (2015)
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Strengthened Creep-Resistant Aluminum Alloy Containing Tria-
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Pekguleryuz, Phase formation in as-solidified and heat-treated
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4740–4752 (2012)
17. G.E. Dieter, Mechanical metallurgy, 3rd ed (McGraw-Hill, New
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properties of Al matrix composite made by powder metallurgy.
Mater. Sci. Eng., A 527, 1031–1038 (2010)
 Effect of Alloying Elements
on Anneal-Hardening Behavior of Aluminum
Alloy Foils

Takashi Suzuki, Shigeru Kuramoto, Masaya Endo, and Qi Cui

Abstract
We observed that non-heat treatable Al–Fe–Mn alloy foils exhibit an increase in strength
and a decrease in elongation due to low temperature annealing treatment subsequent to cold
rolling. In this study, we investigate the effects of alloying elements on this
anneal-hardening behavior. The alloys without alloying element of iron were not hardened
by low temperature annealing treatment. On the other hand, the anneal-hardening behavior
was observed only in Al–Fe based alloys containing manganese or chromium. These results
are similar to “hardening by annealing” reported on severe plastic deformation of metal.

Keywords
Aluminum alloy Aluminum foil Ductility Anneal-hardening Grain growth

Introduction deformation (SPD) exhibits the similar phenomenon [2–5].

It is widely recognized that aluminum alloys are grouped into
heat-treatable and non-heat-treatable alloys. Heat-treatable
alloys typified by 6xxx series gain high strength by solution
heat-treating and aging. Aluminum foils gain strength mainly
by cold rolling because almost all these foils are
non-heat-treatable alloys. In non-heat-treatable alloys, it is
generally known that annealing treatment decreases the
strength and increases the elongation. However, we observed
that non-heat-treatable Al–Fe–Mn alloy foils exhibit a sharp
increase in strength and a decrease in elongation due to low
temperature annealing treatment of 200 °C or less subsequent
to cold rolling [1]. This is in contrast to the anneal-softening
behavior by recovery or recrystallization. It has been reported
that nanostructured metal created by severe plastic
This phenomenon is called hardening by annealing or
anneal-hardening in the field of SPD, and has not been still
clarified, although several mechanisms have been suggested.
On the other hand, some recent studies have shown that
the anneal-hardening of aluminum is related to chemical
compositions. It has been reported that Al–Mn alloy
exhibited the anneal-hardening without SPD [6–9]. It has
been presumed in some literatures that very small precipi-
tates containing silicon or manganese lead to the
anneal-hardening, but those small particles or clusters have
not been observed yet. In addition, some reports on the other
aluminum alloys imply the effect of various alloying ele-
ments on the anneal-hardening. In this study, the effect of
alloying elements on anneal-hardening on pure-aluminum
and Al–Fe based alloy foils was investigated.

T. Suzuki (&)
M. Endo
Q. Cui

Products Research and Development, Mitsubishi Aluminum Co.,
Ltd., 85 Hiramatsu, Susono, Shizuoka 411-1127, Japan
e-mail: takashsu@malco.co.jp
S. Kuramoto
Department of Mechanical Engineering, College of Engineering,
Ibaraki University, 4-12-1 Nakanarusawa, Hitachi, Ibaraki
316-8511, Japan
e-mail: shigeru.kuramoto.11@vc.ibaraki.ac.jp
Experimental
In this study, aluminum alloy foils containing various alloying
elements were used as specimens. The chemical compositions
of the alloys are listed in Table 1. The Al–X (X = Cu, Mn,
Mg, Cr) specimens are pure aluminum and iron-free alu-
minum alloys, and the Al–Fe–X specimens are Al-1mass%Fe

© The Minerals, Metals & Materials Society 2017 427

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_53
428 T. Suzuki et al.

based alloys. Table 2 shows the manufacturing process of the
aluminum alloy foils. All of the DC cast slabs with thickness of
50 mm were homogenized at 565 °C for 4 h. After homoge-
nization, the slabs were hot-rolled to 7 mm thickness, and then
cold-rolled to 0.7 mm thick sheets with a rolling speed of
3 m/min. These cold-rolled sheets were subjected to inter-
mediate annealing, furthermore cold-rolled to 40 lm thick
foils. The rolling speed of final cold rolling was 1 m/min. The
final cold-rolling reduction of the foils is 94.7% (equivalent
strain of 3.3). The cold-rolled foils were annealed for 10 h at
temperature from 75 to 200 °C to investigate the
anneal-hardening behavior. The mechanical properties of the
as-rolled and annealed foils were measured by tensile tests.
Tensile test specimens with a gauge length of 50 mm and a
width of 25 mm were punched with the tensile axis parallel to
the rolling direction (RD) of the foils. Tensile tests were car-
ried out at room temperature with constant crosshead speed of
2 mm/min, which corresponding to an initial strain rate of
6.7  10−4 s−1. Microstructure of the as-rolled and annealed
foils was characterized by electron backscattered diffraction
(EBSD). EBSD scans were performed in the RD-ND plane
(ND: normal direction).
Results and Discussion
Figure 1 shows the changes in 0.2% proof stress and elongation
for Al–X alloy foils with annealing temperature. All iron-free
alloys did not clearly exhibit the anneal-hardening behavior.
Pure aluminum, Al–Cu and Al–Mg alloys exhibited a decrease
in strength with increasing annealing temperature due to the
recovery of dislocations. On the other hand, Al–Mn and Al–Cr
alloys were not softened by annealing at 200 °C, and 0.2%
proof stress increased only slightly. In general, Mn, Cr and Zr
prevent grain growth and recrystallization in aluminum alloys
during annealing [10, 11]. Therefore, it is believed that the
strength of Al–Mn and Al–Cr alloys did not decrease by
annealing because recovery or other softening process was
suppressed by manganese or chromium addition. As for the
elongation of Al–X alloys, these changes with annealing tem-
perature were not clear. Al–Cu and Al–Mg alloys exhibited a
slightly increase in elongation with increasing annealing tem-
perature. In contrast, the elongations of pure aluminum, Al–Mn
and Al–Cr alloys remained almost the same with annealing.
Concerning this elongation behavior, it can be explained based
on the mechanism of recovery except for pure aluminum.
Figure 2 shows the changes in 0.2% proof stress and
elongation for Al–Fe–X alloy foils with annealing temper-
ature. The anneal-hardening behavior was observed only in
Al–Fe–Mn and Al–Fe–Cr alloy foils. In the both alloy foils,
0.2% proof stress increased with increasing annealing tem-
perature up to 175 °C, and decreased at higher annealing
temperature of 200 °C. The other Al–Fe–X alloy foils
exhibited a decrease in strength with increasing annealing
temperature, which is a same tendency observed in iron-free
Al–X alloy foils (Fig. 1). The elongation of all Al–Fe–X
alloy foils decreased with increasing temperature below
150 °C. After annealing at 200 °C, all Al–Fe based alloys
except of Al–Fe–Cr alloy exhibited the elongation higher
than that of as-rolled.

Table 1 Chemical composition of aluminum alloys

Alloy Si Fe Cu Mn Mg Cr
Al–X Al 0.02 0.05 – – – –
Al–Cu 0.02 0.05 0.21 – – –
Al–Mn 0.02 0.05 – 0.18 – –
Al–Mg 0.01 0.04 – – 0.21 –
Al–Cr 0.02 0.05 – – – 0.18
Al–Fe–X Al–Fe 0.02 0.95 – – – –
Al–Fe–Si 0.30 0.92 – – – –
Al–Fe–Cu 0.02 1.03 0.23 – – –
Al–Fe–Mn 0.02 0.97 – 0.18 – –
Al–Fe–Mg 0.02 1.05 – – 0.21 –
Al–Fe–Cr 0.02 1.03 – – – 0.18

Table 2 Manufacturing process of aluminum foils

Homogenization Hot rolling (mm) Prior cold rolling (mm) Intermediate annealing Final cold rolling (lm) Reduction in final
cold rolling (%)
565 °C-4 h 7.0 0.7 500 °C  30 s 40 94.3
(salt bath)
Effect of Alloying Elements … 429

200 5
Al Al-Cu Al Al-Cu
Al-Mn Al-Mg Al-Mn Al-Mg
180 Al-Cr 4 Al-Cr
0.2% Proof stress (MPa)

Elongation (%)
160 3

140 2

120 1

100 0

≈
≈

As
0 rolled 50 100 150 200 250 As
0 rolled 50 100 150 200 250
Annealing temperature for 10h, T (ºC) Annealing temperature for 10h, T (ºC)

Fig. 1 Effect of annealing temperature on the change in 0.2% proof stress and elongation in Al–X alloy foils

220 20
Al-Fe Al-Fe-Si Al-Fe Al-Fe-Si
Al-Fe-Cu Al-Fe-Mn Al-Fe-Cu Al-Fe-Mn
Al-Fe-Mg Al-Fe-Cr Al-Fe-Mg Al-Fe-Cr
200 16
0.2% Proof stress (MPa)

Elongation (%)

180 12

160 8

140 4

120 0
≈

As
0 rolled 50 100 150 200 250 As
0 rolled 50 100 150 200 250
Annealing temperature for 10h, T (ºC) Annealing temperature for 10h, T ( )

Fig. 2 Effect of annealing temperature on the change in 0.2% proof stress and elongation in Al–Fe–X alloy foils

Figure 3 shows the EBSD grain boundary image maps of
the as-rolled aluminum foils, which have been observed in
ND-RD plane. The black lines and the red lines delineated
the high-angle boundaries (HAGBs) and low-angle bound-
aries (LAGBs), respectively. The grain size of the Al–Fe–X
alloy foils is much smaller than the iron-free Al–X alloy
foils. Clearly, the anneal-hardening behavior needs the
fine-grain structure, because all of the Al–X alloy foils with
coarse-grain structure did not clearly exhibit increasing the
strength and decreasing the elongation by annealing treat-
ment. Alternatively, the important element for the
anneal-hardening might be not grain size but the fraction of
HAGBs.
Although all of Al–Fe–X alloy foils have fine-grain
structure, the anneal-hardening behavior appeared only in
Al–Fe–Mn and Al–Fe–Cr alloy foils. Figure 4 shows the
430
Fig. 3 EBSD grain boundary
image maps of Al–X and Al–Fe–
X alloy foils. The black and red
lines are related to high-angle
grain boundaries, low-angle grain
boundaries, respectively
(Color figure online)
EBSD grain boundary image maps of Al–Fe–Cu and Al–Fe–
Mn alloy foils before and after annealing at 150 °C for 10 h.
As shown in Fig. 2, Al–Fe–Cu alloy foil was not hardened
by annealing. Both alloy foils with fine-grain structures
exhibited obvious grain growth during annealing, while the
grain size of annealed Al–Fe–Mn alloy foil is smaller than
Al–Fe–Cu alloy foil. It is well-known that manganese and
chromium inhibit grain growth and recrystallization in alu-
minum alloys. For this reason, it is likely that manganese
prevented grain growth in Al–Fe–Mn alloy during
annealing.
The experimental results imply that the strengths of the
Al–Fe–X alloy foils with fine-grain structure are influenced
by the hardening due to the anneal-hardening and the soft-
ening due to grain growth. As for the mechanism of the
T. Suzuki et al.
anneal-hardening in the fine-grained structure materials,
Huang et al. have proposed the dislocation source-limited
strengthening [2–4]. Although this mechanism has still not
been proven, our experimental results are similar to their
reports. According to this mechanism, we presume that the
anneal-hardening behavior occurs both Al–Fe–Mn and
Al–Fe–Cu alloys, because both as-rolled alloys have the
fine-grain structure. However, Al–Fe–Cu alloy is easily
softened by low temperature annealing due to recovery and
grain growth. From this point of view, in Al–Fe–Mn and
Al–Fe–Cr alloy foils, it is likely that the effect of the
anneal-hardening behavior exceeded that of the softening
due to grain growth. However, the mechanism for the
anneal-hardening behavior is still unclear, so further research
will be required for critical discussions.
Effect of Alloying Elements … 431

Fig. 4 EBSD grain boundary

image maps of Al–Fe–Cu and
Al–Fe–Mn alloy foils before and
annealed at 150 °C for 10 h. The
black and red lines are related to
high-angle grain boundaries,
low-angle grain boundaries,
respectively (Color figure online)

Conclusions 2. In the Al–Fe–X alloy foils, only Al–Fe–Mn and Al–Fe–

In this study, we investigated the effect of alloying elements
and microstructures on the anneal-hardening behavior of
aluminum alloy foils using iron-free Al–X binary alloys and
iron-containing Al–Fe–X ternary alloys. The following
conclusions were drawn:
1. The Al–X alloy foils exhibited decreasing in strength and
increasing in elongation by annealing. However, Al–Mn
and Al–Cr alloy foils showed very small changes in
strength and elongation below 200 °C.
Cr alloys exhibited the anneal-hardening behavior by
annealing at less than 200 °C. The elongation of all the
Al–Fe–X foils decreased with increasing temperature.
3. The grain size of as-rolled Al–Fe–X alloy foils was much
smaller than the iron-free Al–X alloy foils.
4. In the Al–Fe–X alloy foils with fine-grain structure, the
grain growth occurred by annealing subsequent to
cold-rolling. However, the grain growth of Al–Fe–Mn
alloy foil was suppressed much in comparison with
Al–Fe–Cu alloy foil.
432
In summary, it was found that the anneal-hardening
behavior of aluminum foils is closely related with grain
structure, and that aluminum foils with fine-grain structure
exhibited an increase in strength by annealing. The addition
of manganese or chromium in aluminum alloy increases the
magnitude of the anneal-hardening because it is probable
that these elements prevent the decrease in strength due to
the softening process like recovery or grain growth during
annealing.
References
1. T. Suzuki, S. Nakanishi, Q. Cui, Effects of low-temperature heat
treatment on hardening for Al-Fe-Mn alloy foil. J. Jpn. Inst. Light
Met. 65, 131–136 (2015)
2. X. Huang, N. Hansen, N. Tsuji, Hardening by annealing and
10. D.B. Goel, P. Furrer, H. Warlimont, Recrystallization and
softening by deformation in nanostructured metals. Science 312,
249–251 (2006)
11. D.B. Goel, Recrystallization in Al-Mn-Cr alloys. Def. Sci. J. 30,
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ing in nanostructured steel produced by severe plastic deformation.
Mater. Sci. Forum 638–642, 1959–1964 (2010)
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4. N. Kamikawa, X. Huang, N. Tsuji, N. Hansen, Strengthening
mechanisms in nanostructured high-purity aluminum deformed to
high strain and annealed. Acta Mater. 57, 4198–4208 (2009)
5. J.R. Bowen, P.B. Prangnell, D. Juul Jensen, N. Hansen,
Microstructural parameters and flow stress in Al-0.13%Mg
deformed by ECAE processing. Mater. Sci. Eng. A 387–389,
235–239 (2004)
6. C.Y. Yu, P.W. Kao, C.P. Chang, Transition of tensile deformation
behaviors in ultrafine-grained aluminum. Acta Mater. 53,
4019–4028 (2005)
7. Ø. Ryen, O. Nijs, E. Sjölander, B. Holmendal, H.E. Ekström,
Strengthening mechanisms in solid solution aluminum alloys.
Metall. Mater. Trans. A 37A, 1999–2006 (2006)
8. N.H. Lee, P.W. Kao, T.Y. Tseng, J.R. Su, Effect of manganese
addition on the tensile properties of cold-rolled and
recovery-annealed aluminum alloy sheets. Mater. Sci. Eng.
A 537, 297–305 (2012)
9. N.V. Govindaraj, R. Bjørge, B. Holmedal, Characterizing harden-
ing on annealing of cold-rolled aluminum AA3103 Strips. Metall.
Mater. Trans. A 45A, 1597–1608 (2014)
precipitation in Al-Mn alloys. Aluminum 50, 641–646 (1974)
121–124 (1980)
 Increasing Strength and Corrosion Resistance
of AlMgSi Alloys by Tailor-Made
Thermomechanical Processing

A. Wimmer

Abstract
The impact extrusion process of aluminum is an important manufacturing method for
production of semi-finished products. Actually AlMgSi (EN AW 6xxx) alloys are impact
extruded in a soft state (0 condition), however a heat treatment on the final products is
needed to generate a high ductility and strength (T6 condition). Through this heat treatment
distortions on the final product could occur and new process routes have to be developed.
The purpose of this study is to compare mechanical properties and corrosion resistance of
different process routes to be able to optimize industrial processes. In this work the
deformation resistance, heat generation during deformation, strength and corrosion
resistance as a function of thermomechanical processing and microstructure were analyzed.

Keywords
Aluminum Age hardening Impact extrusion Carbon footprint Thermomechanical
processing

Introduction 6. Water quench

In the past months the brisance of light weight design
decreases due to comparable low fuel prices, however cli-
mate change is still continuing and there is an increasing
demand for aluminum parts for mobile applications. There is
a strong rivalry between well-known materials such as alu-
minum, steel and plastic, however technical progress fea-
tures new materials such as carbon fiber laminate (CFK).
The traditional process route for impact extrusion (cold
forging) of hardenable aluminum alloys is:
1. Casting
2. Homogenization anneal (*550 °C [1, 2])
3. Soft-anneal (350–400 °C [3])
4. Cold deformation
5. Solution heat treatment (SHT, *550 °C [3])
A. Wimmer (&)
Neuman Aluminium Industries, Werkstraße 1,
3182 Marktl, Austria
e-mail: alexander.wimmer@neuman.at
7. Artificial aging (150–250 °C [4])
This process route indicates that the material suffers 4
heat treatments after casting, resulting in a high energy
demand. Furthermore, the high temperature of SHT gener-
ates distortion in the cold deformed parts. If the material
could be cold deformed in the solutionized (T8 process) or
hardened state (T9 process), at least the soft anneal could be
eliminated. Furthermore, the homogenization and SHT could
be combined.
Recent studies on AlMgSiCu (EN AW 6061) by Li [5]
indicated, that under-aging before deformation and subse-
quent peak aging (pre-aged T8) after deformation could
improve mechanical and corrosion properties. However, up
to now the mechanical and corrosion properties of EN AW
6082 (AlMgSi1) and EN AW 6162 (AlMgSiCu) for different
cold deformation processes have not been analyzed and
compared.
Consequently, the deformation behavior, mechanical
properties and corrosion resistance of the well-known T6
process route (with and without natural aging) and 3 new

© The Minerals, Metals & Materials Society 2017 433

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_54
434 A. Wimmer

process routes applied to AlMgSi and AlMgSiCu should be
compared:
1. Pressing in the soft state, 10 min natural aging before
artificial aging (T6)
2. Pressing in the soft state, 1 week aging before artificial
aging (T6)
3. Pressing in the solutionized state with artificial aging
after deformation (T8)
4. Pressing in the solutionized, pre-aged state with an
additional anneal after deformation (pre-aged T8)
5. Pressing in the hardened state (T9)
1. Under-aged (T6, SHT and 9 h artificial aging after
deformation)
2. Peak-aged (T8, SHT before and 9 h artificial aging after
deformation)
3. Over-aged (T9, SHT and 14 h artificial aging before
deformation)
The sample surface was grinded, cleaned and 2 h ± 5
min exposed to the etchant, consisting of deionized water
with 2.3% HCl and 1.8% NaCl. In the areas, where the
strongest intercrystalline corrosion was visible with the
microscope, metallographic specimens were prepared and
depth of the corrosion cracks was measured.

Experimental Details Results and Discussion

AlMgSi and AlMgSiCu alloys (Table 1) were casted with a
horizontal direct chilled (hdc) bolt casting line to a bolt with
203 mm diameter. Homogenization was performed at
550 ± 10 °C for 4 h (2 h heating, 2 h holding time).
Afterward bolts were extruded to a bar with 60 mm diameter
and cutted to slugs with a length of 30 mm. Soft anneal was
done at 370 ± 10 °C for 4 h, solution heat treatment at
540 ± 10 °C for 1 h and artificial aging (AA) at 160 °C
between 2 and 48 h.
Pre-aging was performed for 4 h at 160 °C for the
pre-aged T8 samples. Natural aging (NA) was done at room
temperature (23 ± 3 °C). The error bars in the figures are
indicating the measured standard deviation.
Slugs were extruded to a cup with 60 mm outer diameter,
54 mm inner diameter and a length of approx. 140 mm.
Deformation simulations to determine strain and temperature
during deformation were performed with DEFORM™ V11.
For simulations only the two extreme cases (T6 and T9)
were simulated, as it can be assumed, that the other cases
(T8 and pre-aged T8) could be interpolated, as T6 is the
softest state with lowest deformation resistance and T9 is the
hardest state with highest deformation resistance.
For corrosion testing the following conditions were
tested:
Deformation Simulation and Experimental
Results
In the case of cold deformation of the soft material (T6
process), the maximum deformation force Fmax is *1.5MN,
in the case of the hard material (T9 process) *3.7MN
(Fig. 1a). A 2.5 times higher force for T9 compared to T6
was also found in impact extrusion experiments of the cup
(Fig. 1b and Table 2).
However, the curves for T6 and T9 show a different
shape. For T6, the force increases slowly to the maximum
and decreases slowly afterwards to *1.2MN (DF approx.
0.3MN), for T9 the force increases fast to 3.7MN, however
then it decreases fast to finally 2.5MN (DF approx. 1.2MN).
This can be explained by the temperature profile: Due to
the higher force for the T9 process more deformation energy
is generated, consequently the temperature goes up to 350 °C
(Fig. 1c), for the T6 process only to 200 °C (Fig. 1d).
Through this high temperature the deformation resistance is
significantly lowered, resulting in a strong decrease of the
deformation force. The temperature of the samples was
measured 30 s after deformation. For T9 the average sample
temperature was 250 °C for low alloyed material (Mg +
Si#), and 280 °C for high alloyed material (Mg + Si""), for

Table 1 Chemistry of the used Alloy Si Fe Cu Mn Mg Cr Mg + Si

alloys [wt%]
Mg + Si# 0.63 0.20 0.03 0.16 0.61 0.01 1.23
Mg + Si + Cu 0.61 0.31 0.24 0.83 0.80 0.01 1.41
Mg + Si 0.92 0.23 0.03 0.77 0.62 0.02 1.54
Mg + Si" 1.20 0.23 0.08 0.54 0.81 0.18 2.01
Mg + Si"" 1.24 0.25 0.09 0.58 0.99 0.17 2.23
Signs (#, ", ) are indicating the combined magnesium and silicon content (Mg + Si), which is shown in the
last row
Increasing Strength and Corrosion Resistance … 435

Fig. 1 Simulation results for

impact extrusion of a cup. a Force
evolution during extrusion of a
soft annealed slug (T6 process,
blue crosses) and of a artificial
aged slug (T9 process, red
circles). b Extruded
cup. c Temperature field in the
deformed cup (T9 process).
d Temperature field in the
deformed cup (T6 process).
e Cumulative strain in the
deformed cup (Color figure
online)

Table 2 Overview about T6 T8 Pre-aged T8 T9

measured temperature T and
deformation force F T [°C] F [%] T [°C] F [%] T [°C] F [%] T [°C] F [%]
Mg + Si# 120 29 200 66 240 77 255 82
Mg + Si + Cu 120 29 200 66 250 82 270 89
Mg + Si 120 38 210 66 250 86 250 89
Mg + Si" 120 40 230 74 250 90 280 100
Mg + Si"" 120 41 230 75 270 97 280 96

T6 120–150 °C, in good accordance with the simulation
results. For both samples the maximum strain is 4, the
average strain in the wall of the extruded cup is 2 (Fig. 1e).
Mechanical Properties
As it can be seen from simulations, the fast deformation of
solutionized or even hardened AlMgSi (T8 and T9) gener-
ates high temperatures of >200 °C, annihilating the positive
effect of cold deformation.
Figure 2 shows the achievable strength of the different
process routes.
For the well-known T6 process (Fig. 2a) the alloy with
the highest content of magnesium and silicon shows as
expected the highest hardness, with decreasing magnesium
and silicon content the hardness decreases. Through one
week natural aging between solutionizing and artificial aging
(Fig. 2b) the achievable hardness decreases by 5–10 HB,
however this effect is smaller for the Cu containing alloy as
Cu is inhibiting particle precipitation at room temperature.
The hardness plateau (peak-hardness) starts roughly after
436 A. Wimmer

Fig. 2 Hardness evolution during artificial aging for alloys with varying alloy composition. a T6 process with 10 min natural aging before
artificial aging. b T6 process with 1 week natural aging before artificial aging. c T8 process. d Pre-aged T8 process. e T9 process

12 h, however even after 48 h no hardness decrease due to
overaging has been observed.
For T8 (Fig. 2c), pre-aged T8 (Fig. 2d) and T9 (Fig. 2e)
the AlMgSiCu shows despite the comparatively low mag-
nesium and silicon content the highest hardness. For T8, all
AlMgSi alloys show roughly the same hardness, for
pre-aged T8 and T9 the high alloyed AlMgSi show the
lowest hardness, the low alloyed AlMgSi shows the highest
hardness. This can be explained by the deformation resis-
tance and consequently increase in temperature during (so
called) cold deformation: For the low alloyed material, the
maximum temperature during pre-aged T8 and T9 defor-
mation is approx. 30 °C lower than for the high alloyed
material (Table 2). Through this, in the high alloyed T9
material the material overages through the deformation heat,
whereas the low alloyed material reaches the peak hardness
through *250 °C for approx. 5–10 min (cooling without
forced convection). However, for T9 deformation all alloys
showed overaging through the deformation heat of up to
280 °C and an additional artificial aging resulted in a hard-
ness decrease.
For comparison slow isothermal T9 deformation experi-
ments on high alloyed material (Mg + Si"") were con-
ducted, leading to a Brinell hardness of 150HB, showing the
potentials of isothermal cold deformation with combined
particle and dislocation hardening.
Increasing Strength and Corrosion Resistance …
Fig. 3 Corrosion attack on EN AW 6xxx alloys, material flow
direction during cold deformation parallel to the attacked surface. The
first line shows a Cu containing alloy, the middle line a Cu-free,
Corrosion Resistance
The under-aged samples (Figs. 3a, d, g and 4a, d, g) show
intercrystalline corrosion, the Cu alloyed sample (Table 2,
Figs. 3a and 4a) shows corrosion cracks up 300 µm depth,
the high alloyed sample (Mg + Si", Figs. 3d and 4d)
shows cracks up to 250 µm, the medium alloyed sample
(Mg + Si, Figs. 3g and 4g) shows cracks up to 200 µm.
The peak-aged samples (Figs. 3b, e, h and 4b, e, h) show
pitting corrosion with a depth up to 400 µm for the Cu
alloyed sample (Figs. 3b and 4b), the Cu free alloys show
pitting corrosion up to 200 µm. Finally the over-aged
samples (Figs. 3c, f, i and 4c, f, i) show combined uniform
and pitting corrosion, however to a much smaller extend
than the peak aged samples, independently of the alloy
composition the corrosion depth was approx. 200 µm. In
summary, with increasing content of alloy elements
437
high-alloyed AlMgSi and the last line a Cu-free, medium-alloyed
AlMgSi. The left row shows the under-aged, the middle row the
peak-aged and the right row the over-aged condition
corrosion sensibility increases, however copper has a much
stronger influence than magnesium and silicon. This indi-
cates, that EN AW 6xxx alloys with Cu < 0.1% show a
lower susceptibility for intergranular corrosion (IGC) and
pitting corrosion (PC), however the alloy with 0.24% Cu is
susceptible to IGC and pitting corrosion, depending on the
thermomechanical process route, which is in accordance
with Svenningsen [6]. Furthermore, these results are in line
with studies of Oberhauser [7], where over-aging showed a
positive effect on alloys with high silicon or copper con-
tent. In contrast, previous studies on EN AW 6061 [5] and
on EN AW 6056 [8], found the best stability for AlMg-
SiCu with pre-aging and subsequent peak aging after
deformation, however there was also found a change from
IGC to pitting corrosion with increasing aging time. This
indicates a strong influence of the alloy composition to the
corrosion properties.
438
Fig. 4 Corrosion attack on EN AW 6xxx alloys, material flow
direction during cold deformation orthogonal to the attacked surface.
The first line shows a Cu containing alloy, the middle line a Cu-free,
Conclusion
It has been shown, that during so-called cold deformation of
AlMgSi, especially for T8 and T9, temperatures of up to
350 °C could be reached (semi-hot deformation). This
results in unwanted artificial overaging processes, recovery
of dislocations and subsequently deterioration of mechanical
and corrosion properties. However, as studies about super-
fast aging at 250 °C have been published recently [4],
deformation heat could be used to replace a heat treatment
step if the alloy composition and process parameters are
tuned. On the other hand, if work hardening (dislocation
hardening) potential should be used, slow isothermal
deformation methods (e.g. hydraulic presses) have to be
used.
T8, pre-aged T8 and T9 have disadvantages in the
deformation resistance and mechanical properties, however
the corrosion resistance is significantly better. Consequently
this three process routes should be considered for industrial
A. Wimmer
high-alloyed AlMgSi and the last line a Cu-free, medium-alloyed
AlMgSi. The left row shows the under-aged, the middle row the
peak-aged and the right row the over-aged condition
processes where low distortions and a high corrosion resis-
tance is needed.
Acknowledgements The author thanks B. Schwarz for the fruitful
discussion and simulation results. We are also grateful to the Austrian
Research Promotion Agency FFG for their financial support (FFG
project number 853869).
References
1. Y. Birol, Mater. Charact. 80, 69–75 (2013)
2. Q. Zhao, J. Alloy. Compd. 666, 50–57 (2016)
3. B. Milkereit, Mater. Des. 76, 117–129 (2015)
4. M. Werinos et al., Scripta Mater. 112, 148–151 (2016)
5. H. Li, Mat. Sci. Eng. A 617, 165–174 (2014)
6. G. Svenningsen, Corros. Sci. 48, 3969–3987 (2006)
7. P. Oberhauser, Korrosionsverhalten von aushärtbaren Aluminium-
legierungen für den Karosseriebau, Conference proceedings of
3LKT (2014)
8. Z. Wang et al., Mat. Sci. Eng. A 590, 267–273 (2014)
 Microstructural Optimization of a High
Mechanical Properties Aluminum Alloy By
Using CobaPress Process

Mamadou Balde, Christophe Desrayaud, Véronique Bouvier,

and Frédéric Perrier

Abstract
CobaPress™ process is a hybrid process of casting and forging leading to the
manufacturing of high integrity/critical safety components and sub-assemblies for the
automotive industry. Throughout this process, the main objective consists of the elaboration
of an aluminum alloy with yield strength of 300 MPa and at least 8% of elongation. The
use of Thermocalc© simulations allowed us to set up with annealing temperatures and
chemical composition. Channel die experiments have been carried out to study
sub-structure evolution for a fixed temperature and different strain rates. Observations on
EBSD have been made in order to characterize recovery and/or recrystallization. Apart
from the fact that sub-structuration improves yield strength and ultimate tensile strength,
fatigue life is much greater than AS7G03 usually used through the CobaPress™ process.

Keywords
Casting Forging EBSD Channel die Recrystallization Fatigue

Introduction of a wide range of aluminum alloys. This innovative process

In the continuing quest for car weight reduction, aluminum
alloys such as AU5GT (block engine, clutch housing,
cylinder head covers), or AS7G03 (suspension arm, damper
arm…) have been widely used due to their high
strength-to-weight ratio, good formability and resistance to
corrosion.
Several processes of elaboration of aluminum alloys exist
(die casting, stamping, forging…) but there is one which
combines both casting and forging process: the CobaPressTM
[1]. The characteristics of this process allow the elaboration
M. Balde (&)
C. Desrayaud
Centre SMS/LGF UMR 5146, Ecole Nationale Supérieure des
Mines de Saint-Etienne, CS 62362, 42023 Saint-Etienne Cedex 2,
France
e-mail: mamadou.balde@emse.fr
V. Bouvier
F. Perrier
Saint Jean Industries SAS, 180 rue des Frères Lumière, 69220
Saint-Jean d’Ardières, France
consists first of the filling of a mold by an aluminum alloy
using gravity casting or by low pressure casting in order to
create a preform. Once the preform created, it is pre-heated
at a high temperature to give it a viscous-plastic behavior.
The preform is then forged at this temperature and air
cooled. The last step consists of a Heat-Treatment T6 type in
order to induce precipitation hardening of the alloy. In this
study, we are focusing on the microstructural evolution of a
high mechanical properties alloy (HMP alloy) through the
different steps of the CobaPressTM. In this study, the HMP
alloy is used for the elaboration of damper arms which will
allow extracting the specimens to investigate. The cast pre-
forms are then machined into specimens that will be inves-
tigated. Only a very specific zone of the damper arm is
selected so that no metallurgical defects (pores, inclu-
sions…) disturb the channel die experiments. In this study,
first a state of the art on casting and wrought alloys is done
to characterize chemically the HMP alloy. This study is a
necessary step for the interpretation of the results of the
channel die experiments. On a second hand, we are carrying
out channel die experiments in order to study the

© The Minerals, Metals & Materials Society 2017 439

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_55
440 M. Balde et al.

microstructural behavior of the HMP alloy after hot working Experimental Procedure
and different strain and strain rates. On a last part, we are
focusing on life cycle fatigue of the HMP alloy and note the The first step is to define the chemical composition of the
gain between the HMP and AS7G03, which is the coba- HMP alloy. To do so, the use of the database TCAL2 of
pressed alloy, used at the company Saint-Jean industries. Thermocalc allows representing the phase diagram of the
HMP alloy (Fig. 1). Thus, the identification of a range of
temperature allowing the ideal solid dissolution of the Mg2Si
State of the Art precipitates can be made. According to bibliographical
researches, none of these precipitates or phases has their
The HMP alloy can be considered as a cast/wrought alu- melting points above the chosen solution heat temperature.
minum alloy derived from the 6XXX, 3XXX and 2XXX After the quenching step, the HMP is submitted to
series, with good casting properties. The Al-2XXX and artificial-ageing.
Al-6XXX series are structural hardening alloys, whereas Figure 2 shows the chemical compositions of both HMP
Al-3XXX series are solid solution hardening alloys. and AS7G03 alloys.
The fact that the HMP alloy derives from the 3XXX
series is due to the presence of Manganese element. The Mn
is combining with Al, Fe and Si to form the a-phase Al (Mn, Optical Micrography Confirmation
Fe)Si [2]. This phase substitutes to b-AlFeSi which is very
damaging for the elongation properties of the alloy, but also The Optical Micrography observations allow confirming the
a zone for the crack initiation during fatigue tests. presence of all the desired phases and confirmed by the
Despite considerable increasing of mechanical [3] prop- Thermocalc simulations (Fig. 3).
erties the Al-2XXX series is very sensitive to corrosion The chemical aspect resolved the channel die experiments
[4, 5]. can be carried out.
The Al-6XXX series does not increase significantly the
mechanical properties but they have good hot working
abilities [6].
The chemical composition of the HMP alloy has been
determined by taking into account all the mentioned effects.
To reach this goal, we are mainly focusing on the conse-
quences of the addition of chemical elements, which allows
also avoiding not desired metallurgical phenomena in this
study such as: hot tearing [7–9], cooling rate [10], and
recrystallization [11].
A lot of researchers like Yıldırım and Özyürek [12], but
also Massion et al. [13] have investigated benefit effects of
solution hardening of the Mg2Si precipitates, which is
responsible for the increasing of yield strength. A good
dissolution of macro precipitates and a precipitation at nano
scale allows an enhancing of the mechanical properties [14]
(yield stress, fatigue life cycle…).
The influence of the chemical elements is also important
during the thermomechanical step, because of the dynamic
of dislocations induced. The sub-grain boundaries migration
is modulated by the concentration of solute and their dis-
persion [15] (Mn [16], Mg [17] and Si [17]) within the Al Fig. 1 Phase diagram of the HMP alloy. 1 Liquid; 2 Liquid + Al; 3
matrix. For instance, De la Chapelle et al. [18] have studied Liquid + Al + a-Al(Mn,Fe)Si; 4 Liquid + Al + a-Al(Mn,Fe)Si + Si; 5
the effect of the Zener Pining on the microstructure during an Al + a-Al(Mn,Fe)Si + Si; 6 Al + a-Al(Mn,Fe)Si; 7 Mg2Si + a-Al
(Mn,Fe)Si + Si + Al; 8 Mg2Si + a-Al(Mn,Fe)Si + Al; 9 Mg2Si +
annealing step. Inasmuch as the HMP alloy results from the
a-Al(Mn,Fe)Si + Si + Al + b-AlFeSi; 10 Q_AlMgSiCu + Mg2Si +
combination of multiple properties of aluminum alloys, this a-Al(Mn,Fe)Si + Si + Al + b-AlFeSi; 11 Q_AlMgSiCu + Mg2Si +
theoretical study allowed us to understand better its ther- a-Al(Mn,Fe)Si + Al + b-AlFeSi; 12 Mg2Si + a-Al(Mn,Fe)Si + Al +
mochemical behavior. b-AlFeSi; 13 a-Al
Microstructural Optimization of a High Mechanical Properties … 441

Si Mg Cu Mn Ti Fe Zn
HMP 1.5 - 2.5 0.5 - 1 0.1 – 0.3 0.1 – 0.25 0.1 – 0.2 0.08 – 0.15 -
AS7G03 6.5 – 7.5 0.25 – 0.45 0.2 0.1 0.2 0.2 0.1

Fig. 2 Chemical composition of HMP and AS7G03 (in %weight)

Fig. 3 Optical Micrography of

the HMP alloy of a casted damper (a) (b)
arm. a General microstructure.
b and c Main phases of the HMP
alloy

Al(Mn,Fe)Si

(c)

Channel Die Experiment
To lead channel die experiments, first it was important to
take a look at the homogeneity of the mechanical properties
at various zones of the damper arm (Fig. 4). A series of 20
damper arms have been submitted to the whole CobaPress
process. Cylindrical specimens with a standard geometry
used at the company Saint-Jean industries have been
extracted from the damper arms, and submitted to tensile
test.
According to Figs. 4 and 5, the zone 2 corresponds to the
best balance between elongation and yield stress. Indeed, the
zone 1 located to the head of the damper arm presents a
mean yield stress of 310 MPa, but a mean elongation of 6%.
The zone 3 on the contrary, shows a good elongation, but a
lower yield stress. The zone 2 has then been machined to
obtain cuboid samples (Fig. 6); whose exact dimensions
have been determined in function of the aimed strain rate.
The channel die device (Fig. 7) is composed of dies, but
also a stamp under which we introduce the sample to deform
after having lubricated it. Firstly the whole system is heated

Fig. 4 Damper arm Fig. 5 Yield stress and elongation at different zones of the damper arm
442
ho: initial size of the sample
hf: final size of the sample
Fig. 6 Geometry of a channel die specimen
at 520 °C. Secondly, the sample is introduced just below the
stamp and locked by the dies so that when stress is applied,
there is only one flow direction. After waiting for about
2 min to get a homogenous temperature, the plane strain
compression occurs at the strain rate and the strain desired.
Once the samples deformed, they are heat treated in
ovens for a T6 heat-treatment type. Thus, the samples are
machined into small flat mechanical tensile specimens
(Fig. 8) in order to perform tensile tests.
The device used is an Instron tensile test at a velocity of
5  10−3 mm/s. An important carefulness has been
Strength applied
Stamp
Die Die
Sample
Fig. 7 Representation of the channel die experiment
Fig. 8 Tensile test specimen (scale in mm)
M. Balde et al.
undertaken to manipulate the specimens because of their
small size.
EBSD Analysis
Once the samples damaged after the tensile test, a zone
between the jaws and the effective length is cut with a wire
saw. Thus one face has been isolated and submitted to
electro polishing and analyzed thanks to a Scanning Electron
Microscope JEOL 6500 with HKL “Channel” software for
the orientation indexation and mapping.
Fatigue Test
To lead fatigue tests, a damper arm with the composition of
the HMP alloy has been mounted on a fatigue bench at
Saint-Jean Industries company. The fixation points are
located at the two end of the piece (Fig. 9) as we can see on
the following scheme.
The arm has been cobapressed and then submitted to
uniaxial mechanical stress 29.55/−38.55 KN at 2 Hz. The
aim is to compare the fatigue life of the HMP alloy with the
cobapressed alloy AS7G03 used at Saint-Jean Industries in
production during a tensile-compression test.
Fig. 9 Damper arm and the fixation points for fatigue test
Fig. 10 Channel die stress-strain curves at different strain rates,
different strains and at 520 °C
Microstructural Optimization of a High Mechanical Properties … 443

Fig. 11 EBSD pictures of the hot compressed specimens HMP alloy after a T6 heat treatment. a Microstructure no hot compressed (V0).
b Corresponds to the microstructure at strain rate V1. c Corresponds microstructure at strain rate V2 and picture, d to strain rate V3

Experimental Result
Channel Die Results
According to the theory of Zener-Hollomon [19, 20], during
a thermomechanical working, the higher the strain rate is, the
more the mean sub-grain size decreases. This phenomenon is
related to the dynamic recovery occurring within the
microstructure. Figure 10 shows the flow stress of speci-
mens for various strain rates (V1 < V2 < V3) at 520 °C.
According to the curves, no dynamic recrystallization was
observed, because of the absence of softening effect during
the deformation of the HMP alloy. We can also notice that
all the flow stress curves are increasing with strain rate.
Furthermore, for strain rate between 2 and 3 s−1 (V1), strain
hardening is a bit more important compared with stress at
higher strain rates (V2 and V3).
EBSD Results
The EBSD (Fig. 11) analysis allows confirming an impor-
tant sub-structuration in picture (b), representing the HMP
alloy at strain rate V1 and after a T6-heat treatment. In fact,
444 M. Balde et al.

Fig. 12 Mechanical properties

of hot compressed specimens
after a T6 heat treatment

Fig. 13 Elongation before crack

of T6-treated specimens

picture (b) illustrates recovery phenomenon if we compare
this microstructure with no hot compression (V0), corre-
sponding to picture (a). This evolution is beneficial for the
mechanical properties like Yield Strength and Ultimate
Tensile Strength. By increasing strain and strain rate,
recrystallization starts to take place and some grains are
growing as we can see in picture (c). The picture (d) shows a
recrystallized microstructure with new grains and conse-
quently mechanical properties that are affected. We shall
also take into account the Zener pinning and the solute drag
effect on the growth of the sub-grains, which may explain a
recrystallization occurring at V2. Without those effects, we
could have this phenomenon occurring for strain levels
below 0.4.
Static Results
The mechanical tensile test results are in accordance with the
EBSD results. We can see the beneficial effect of the
sub-structuration at V1, leading to an increasing of Yield
Strength and Ultimate Tensile Strength (Fig. 12).
The increasing of strain rate and strain generate an
increasing of elongation and a reduction of Yield Strength
Microstructural Optimization of a High Mechanical Properties …
Fig. 14 Fatigue life results after submitting damper arms to
traction-compression test
and Ultimate Tensile Strength at V2 and V3, which is in
accordance with the recrystallization phenomenon observed
previously. (Fig. 13).
A compromise can be noted between loss of Yield
Strength and gain of Elongation for intermediate strains.
Cyclic Results
The fatigue result tests show that fatigue life of the HMP
alloy is at least twice higher than the AS7G03 alloy for the
same load cycles (Fig. 14).
According to Lados et al. [21], such a result gap can be
interpreted by a difference in the microstructure. With lower
silicon content, the brittle particles are less numerous and the
crack initiation and propagation is reduced.
Conclusion and Discussions
In this study, we have investigated the microstructural
behavior of a High Mechanical Properties aluminum alloy
through the different steps of the CobaPress process. Several
parameters have their importance such as chemical compo-
sition, strain rate, working temperature…
Thermocalc simulations have allowed finding out a
chemical composition necessary to avoid undesired phases
for the HMP alloy. Once experimental tests confirmed the
validity of the theoretical composition, thermomechanical
tests have been carried out. Important information concern-
ing microstructural behavior during thermomechanical
transformation has been spotlighted. Recovery leading to a
sub-structuration occurs progressively at low strain rates.
The sub-grains appeared due to this phenomenon allows
increasing of mechanical properties (Yield Strength, Ulti-
mate Tensile Strength and fatigue life cycle), which is in
445
accordance with the Hall-Petch law. Meanwhile, the
sub-grains can evolve into new grains during the annealing
for samples submitted to higher strain rate. The static re-
crystallization occurred leads to a decreasing of these
mechanical properties but increases ductility of the material.
In a last part, the HMP alloy has been submitted to fatigue
tests on a damper arm. Fatigue life cycles of HMP alloy is
much higher than cobapressed AS7G03 alloy. Despite all the
apparent advantages of the HMP alloy, metallurgical prob-
lems are to be studied such as the formation and reclosing of
pores within the preforms. Simulation is under investigation
with ABAQUS software, considering the
elasto-viscoplasticity of the material. In parallel, tests on
fatigue specimens are to be made in order to study precisely
the zones of cracks initiation and propagation.
Acknowledgements We want to thank all the engineers and techni-
cians from Saint Jean Industries and the Ecole Nationale Supérieure des
Mines de Saint-Etienne for their support in samples development and
manufacturing. Their help was also necessary for the microstructure
observations and mechanical testing.
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 Cyclic Stress-Strain Behavior and Low Cycle
Fatigue Life of AA6061 Aluminum Alloy

F.A. Mirza, K. Liu, and X.-G. Chen

Abstract
AA6061 alloy is one of the most widely used aluminum alloy in modern aerospace and
automotive industries due to low cost, good formability and high specific strength. Most of
aluminum structural components experience dynamic loading, which leads to fatigue
failure. Since studies on the strain-controlled fatigue behavior of these alloys are very
limited, this study was aimed to evaluate the strain-controlled cyclic deformation behavior
of an extruded 6061 aluminum alloy and determine the fatigue life under varying higher
strain amplitudes. The stress-strain responses exhibited essentially symmetric responses
with slight Bauschinger effect. A slight cyclic hardening occurred at high strain amplitudes
(0.8–1.2%) within the first ten cycles, and then cyclic stabilization follows until failure. It
had longer fatigue life which can also be described by the Coffin–Manson law and
Basquin’s equation. Crack initiated from the specimen surface and crack propagation was
characterized by fatigue striation-like features at lower strain amplitudes.

Keywords

AA6061 aluminum alloys Cyclic deformation Low cycle fatigue Fracture
morphology Fatigue life

Introduction applications. The structural application of the 6061 alloys

Due to the mounting environmental concern to improve fuel
efficiency and reduce emissions of harmful CO2, the devel-
opment of lightweight vehicles has turned into a crucial
approach in the automotive and aerospace industries [1–3].
For this purpose, aluminum alloys have become the primary
choice of materials in aerospace, construction, transporta-
tion, and many other industries due to their high
strength-to-weight ratio, good machinability, good castabil-
ity, high corrosion resistance, low coefficient of thermal
expansion and good abrasion resistance [4–6]. In this regard,
the most commonly used extruded aluminum alloys is the
6061 alloy, which already have a great promise for structural
F.A. Mirza (&)
K. Liu
X.-G. Chen
Department of Applied Sciences, University of Québec at
Chicoutimi, 555, Boulevard de l’Université, Chicoutimi, QC G7H
2B1, Canada
e-mail: mirza-foisal.ahmed1@uqac.ca
involves unavoidably fatigue and cyclic deformation char-
acteristics due to the fact that structural components in the
vehicles experience dynamic loading, which results in the
occurrence of fatigue failure [6]. Hence, an understanding of
fatigue and cyclic deformation behavior of 6061 alloys is
critical for the design and durability evaluation of
engineering components.
Although studies on strain-controlled low-cycle fatigue
(LCF) provide important input into the design of engineering
components [7], most of the literature data are focused on
tensile properties and high-cycle fatigue (HCF) behavior of
aluminum alloys. To the authors’ knowledge, studies on the
LCF fatigue of 6061 alloys are very limited [6, 8, 9].
Brammer et al. [6] conducted strain-controlled fatigue tests
of an extruded 6061-T6 aluminum alloy at a fixed 5 Hz
frequency under different strain amplitudes. The tests were
performed up to highest 0.006 amplitude. Studies related to

© The Minerals, Metals & Materials Society 2017 447

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_56
448 F.A. Mirza et al.

higher strain amplitudes such as up to 1.0, 1.2% and
different frequency for different strain amplitudes is not
reported yet. Furthermore, there is practically no systematic
work on cyclic stress-strain behavior specially the
tension-compression asymmetry, cyclic stress and strain
response, and fatigue life of 6061-T6 alloys in the open
literature. The objective of this study was, therefore, to
illuminate the strain-controlled cyclic deformation behavior
of an extruded 6061 aluminum alloy and determine the
fatigue life under varying higher strain amplitudes, i.e.,
0.4–1.2%.
Material and Experimental
The material used in the present study was an extruded
aluminum alloy AA 6061. The material was received in T6
condition as cylindrical rods with a parallel gauge sec-
tion 20 mm long and 6.5 mm in diameter. The T6 temper
designation indicates that this material has been solution heat
treated and then artificially aged to the peak condition. The
nominal composition of the alloy as certified by the supplier
is given in Table 1. Tensile tests were performed in accor-
dance with the ASTM: E8 standard by means of a com-
puterized Instron 8801 servo-hydraulic testing system with a
gauge length of 25 mm at a strain rate of 1 × 10−3 s−1 at
room temperature. Prior to testing, all specimens were hand
ground in the loading direction with 800-grit silicon carbide
paper to remove residual stresses and any machining marks.
The strain-controlled, pull-push-type fatigue tests were
conducted in accordance with the ASTM: E606 standard at
examined via scanning electron microscope (SEM) to
identify fatigue crack initiation sites and propagation
characteristics.
Results and Discussion
Tensile Properties
Typical tensile stress–strain curves of the extruded 6061-T6
aluminum alloy tested at a strain rate of 1 × 10−3 s−1 is
shown in Fig. 1 and the tensile properties obtained are listed
in Table 2. As seen from Table 2, the present 6061-T6 alloy
exhibited similar yield strength (YS) and ultimate tensile
strength (UTS) as the extruded 6061-T6 alloys reported in
the literature [6] with a significant increase in elongation
(*21.5%). However, there is a significant difference in the
obtained monotonic strength coefficient, K (470 vs.
*178 MPa [6]) and strain-hardening exponent, n (0.12 vs.
*0.36 [6]), which indicates strain softening after yielding.
Hysteresis Loops
Typical stress-strain hysteresis loops of the first, second, and
mid-life cycles at a total strain amplitude of 1.2% and strain
ratio of Rε = −1 for the 6061-T6 alloy is shown in Fig. 2.
400
Engineering stress, MPa

room temperature with a 25 mm extensometer using a fully 300

computerized Instron 8801 servo-hydraulic testing system
operated by Bulehill LCF2 software. The cyclic deformation
test conditions consisted of a zero mean strain (i.e., a strain 200
ratio of Rε = −1, completely reversed strain cycle) and a
constant strain rate of 1×10−2 s−1 with triangular loading
waveform. The cyclic frequency was varied depending on 100
the strain amplitude to maintain a fixed strain rate.
Low-cycle fatigue tests were performed at total strain
0
amplitudes of 0.4, 0.6, 0.8, 1.0, and 1.2 pct. If the sample 0 5 10 15 20 25
survived 10,000 cycles, then the strain-controlled tests were Engineering strain, %
transferred to load control at a frequency of 50 Hz using a
sinusoidal waveform. The fatigue life was considered as the Fig. 1 Typical tensile stress–strain curve of the extruded 6061-T6
number of cycles to completely separate apart the samples. alloy tested at a strain rate of 1 × 10−3 s−1
The fracture surfaces of the fatigue specimens were
Table 2 Monotonic material properties for the as-received extruded
6061-T6 aluminum alloy
Table 1 Chemical composition of the AA6061 alloy Elastic Yield Ultimate Monotonic Strain-hardening
Chemical composition (wt%) Modulus, strength, tensile strength exponent, n
GPa MPa strength, coefficient K,
Alloy Si Mg Cu Mn Fe Cr Al MPa MPa
AA6061 0.63 0.85 0.26 0.045 0.25 0.05 Balance 66.9 297 319 470 0.12
Cyclic Stress-Strain Behavior and Low Cycle Fatigue Life … 449

400 400
Total strain amplitude 1.2%
300 1.0%
350

Stress amplitude, MPa

0.8%
200
0.6%
300
Stress, MPa

100 0.4%
0 250
-100
200
-200

-300 1st cycle 150

2nd cycle
Mid-life cycle
-400 100
-1.4 -1 -0.6 -0.2 0.2 0.6 1 1.4 1.E+0 1.E+1 1.E+2 1.E+3 1.E+4 1.E+5
Total strain, % Number of cycles, N

Fig. 2 Typical stress-strain hysteresis loops of different cycles of the Fig. 3 Stress amplitude versus the number of cycles of the extruded
extruded 6061-T6 alloy tested at a given total strain amplitude of 1.2% 6061-T6 alloy tested at different total strain amplitudes at a strain ratio
and strain ratio of Rε = −1 of Rε = −1

The current 6061-T6 alloy was observed to exhibit nearly 0.9

Total strain amplitude 1.2%
symmetrical hysteresis loops with only a slight downward 0.8 1.0%
Plastic strain amplitude, %
shift in compression, which were similar to most of the
0.7 0.8%
face-centered cubic (fcc) metals as a consequence of the
0.6%
dislocation slip-dominated deformation in most materials 0.6
0.4%
[10]. In addition, it is clearly noticed that slight unsym- 0.5
metrical tensile and compressive yielding phenomenon was
0.4
presents in the alloy which is distinguished as the
Bauschinger-like effect [11, 12]. This Bauschinger effect was 0.3
also found to be a function of damage to particles/inclusions, 0.2
dislocation/particle interaction, and the work hardening rate 0.1
[13]. Furthermore, the pseudoelastic or nonlinear elastic
0
behavior in both descending and ascending phases in the
1.E+0 1.E+1 1.E+2 1.E+3 1.E+4
current 6061-T6 alloy was also exists, as it originated from Number of cycles, N
reversible movement of dislocations, twinning, and stress
induced phase transformation [14]. Fig. 4 Plastic strain amplitude versus the number of cycles of the
extruded 6061-T6 alloy tested at different total strain amplitudes at a
strain ratio of Rε = −1
Cyclic Stress and Strain Responses
The cyclic hardening behavior depends on the yield
The evolution of stress amplitudes and plastic amplitudes strength of the material. If the total stress amplitude of the
with respect to the number of cycles at different strain alloy is much lower than the yield strength, it will not
amplitudes from 0.4 to 1.2% is shown in Figs. 3 and 4, undergo cyclic hardening and plastic deformation. At higher
respectively, under a semi-logarithmic scale along the X- total strain amplitudes (0.8–1.2%), the maximum total stress
axis. It is observed that both stress amplitudes and plastic amplitude was much closer (*280 to *296 MPa) to the
strain amplitudes augmented, whereas fatigue life of the yield strength (297 MPa) of the alloy as showed in Table 2,
extruded 6061-T6 alloy decreased with increasing total thus at higher strain amplitudes the alloy underwent hard-
strain amplitudes. At strain amplitudes of 0.8–1.2%, only ening for first ten cycles. At lower total strain amplitudes
slight change, i.e., an initial slight cyclic hardening within (0.4 and 0.6%) the cyclic stress amplitude remained essen-
the first ten cycles and then minor cyclic softening up to tially constant throughout the entire fatigue life. The ten-
failure, could be seen from Fig. 3, which is in contrast to the dency towards cyclic hardening became stronger with
result reported for the extruded 6061-T6 alloy in Ref. [6]. increasing strain amplitudes from 0.8 to 1.2%, as indicated
The extent of initial hardening also decreased with by the increasing slope in the semi-log scale diagram
decreasing strain amplitudes. (Fig. 3). In the low cycle fatigue tests, plastic strain
450 F.A. Mirza et al.

amplitude has been considered as a physical quantity that
results in several damaging processes and influences the
internal microstructure which is closely related to the strain
resistance and eventually the fatigue life [15]. The variation
of the plastic strain amplitude during cyclic deformation is
shown in Fig. 4, which corresponded well to the change of
the stress amplitude during cyclic deformation as shown in
Fig. 3 at different total strain amplitudes. It is seen from
Fig. 4 that as the total strain amplitudes increased the plastic
strain amplitudes also increased however fatigue life
decreased. Cyclic stabilization only occurred at the strain
amplitude of 0.4%. For the rest of the strain amplitudes, it
showed a trend of decreasing with the number of cycles up
to first ten cycles, which is another indication of cyclic
hardening that occurred in all the tested samples except the
one under strain amplitude of 0.4%.
where Δσ/2 is the mid-life stress amplitude, Δεp/2 is the
mid-life plastic strain amplitude, n′ is the cyclic
strain-hardening exponent and K′ is the cyclic strength
coefficient. Figure 6 illustrates the elastic, plastic, and total
strain amplitudes as a function of the number of reversals to
failure (2Nf). In order to make sure that cyclic stabilization,
also called cyclic saturation, has already occurred, the stress
and strain values of the mid-life cycles were used. Hence, the
fatigue life parameters obtained by means of Eqs. (1) and (2)
were presented in Table 3, in comparison with the data
reported in the literature for various extruded 6061-T6 alloys
[6, 8]. It is seen that the obtained fatigue parameters were
well within the range. The obtained cyclic strain hardening
exponent (n′) of the present 6061-T6 alloy was lower than
the corresponding monotonic strain hardening exponent, as
seen from Tables 2 and 3. This could be the reason why this

Fatigue Life and Fatigue Parameters

1.4
Figure 5 displays the total strain amplitude Δεt/2 as a function 1.2
of the number of cycles to failure (Nf, i.e., fatigue life) for the
extruded 6061-T6 alloy. The run-out data points were spec- 1.0
ified by arrows pointing horizontally. The present extruded
0.8
Δεt/2, %

6061-T6 alloy showed a trend of increasing fatigue life with

decreasing strain amplitude and overall the alloy basically 0.6
showed an improved fatigue life than the extruded 6061-T6
alloys reported in the literature [6]. This phenomenon is 0.4
closely related with material strength and ductility. The 0.2
present 6061-T6 alloys showed a higher ductility and lower
strength (Fig. 1 and Table 2) which might lead in better 0.0
fatigue resistance at larger stain amplitudes. The total strain 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05
Number of cycles to failure, Nf
amplitude could be expressed as two parts of elastic strain
amplitude and plastic strain amplitude according to the Fig. 5 Total strain amplitude versus the number of cycles to failure for
Basquin equation and Coffin-Manson relation [16, 17], i.e., the extruded 6061-T6 alloy

Det Dee Dep r0f ð2Nf Þ

b
¼ þ ¼ þ e0f ð2Nf Þc ð1Þ -1
2 2 2 E
where E is the Young’s modulus (for the present alloy the -1.5 YT = -0.3732XT - 1.01
average value obtained during fatigue testing was *68 R² = 0.9964
-2
Log (Δε/2)

GPa), Nf is the fatigue life or the number of cycles to failure, YE = -0.0821XE - 2.1023
σ′f MPa is the fatigue strength coefficient, b is the fatigue R² = 0.8993
-2.5
strength exponent, ε′f is the fatigue ductility coefficient, and
c is the fatigue ductility exponent. In addition, cyclic -3 Total
deformation behavior is normally considered to be related to
YP = -1.1018XP + 0.6522 Plastic
the portion of the plastic strain amplitude and is independent -3.5
R² = 0.9144
of the elastic strain amplitude, which could be expressed by Elastic
the following equation [18], -4
1 2 3 4 5 6
 n0
Dr Dep Log(2Νf)
¼ K0 ð2Þ
2 2
Fig. 6 Cyclic total, plastic, and elastic strain amplitude-fatigue life
response of the extruded 6061-T6 alloy
Cyclic Stress-Strain Behavior and Low Cycle Fatigue Life … 451

Table 3 Low cycle fatigue Low cycle fatigue Extruded 6061-T6 Al Extruded 6061-T6 Al Extruded 6061-T6 Al
parameters obtained for the parameters alloy (present study) alloy (Ref. [6]) alloy (Ref. [8])
extruded 6061-T6 alloy, in
comparison with those reported in Cyclic strain 0.039 0.078 0.24
the literature [6, 8] hardening exponent, n′
Cyclic strength 369 268 372
coefficient, K′, MPa
Fatigue strength 534 705 593
coefficient, σ′f, MPa
Fatigue strength −0.082 −0.11 −0.093
exponent, b
Fatigue ductility 4.49 2.40 5.39
coefficient, ε′f
Fatigue ductility −1.10 −0.98 −1.10
exponent, c

alloy exhibited a certain extent of cyclic softening even at (a) (b)

higher strain amplitude of 1.2%.

Fractography

Figure 7 showed the overall view of the fracture surfaces of

the extruded samples at a total strain amplitude of (a) 0.4%
and (b) 1.0%, respectively, containing fatigue crack initia-
tion (as indicated by dashed yellow-box), propagation, final
fast fracture regions. It is seen from this low magnification
images that fatigue crack initiated basically from the speci-
men surface. It was observed clearly that fatigue crack
propagation area was larger at a lower strain amplitude of
0.4% than at a higher strain amplitude of 1.0% (Fig. 7a, b).
Fatigue crack propagation was basically characterized by
fatigue striations observed at higher magnifications as shown
in Fig. 8a, in conjunction with some secondary cracks. It is
known that the occurrence of fatigue striations was due to a
repeated plastic blunting-sharpening process in face-centered
cubic (fcc) materials arising from the slip of dislocations in
the plastic zone in front of the fatigue crack tip [19].
While no sign of fatigue striations could be identified,
rather a mix of cleavage-like features and tearing ridges
can be observed at higher strain amplitude of 1.0%
(a) (b)
Fig. 7 SEM images of overall fracture surfaces of the extrded 6061-T6
specimens fatigued at a total strain amplitude of a 0.4% and b 1.0%
Fig. 8 SEM micrographs of the fatigue crack propagation region of
the extruded 6061-T6 specimens fatigued at a total strain amplitude of
a 0.4% and b 1.0%
(Fig. 8b). In addition, the fatigue striations were perpen-
dicular to the crack propagation direction. These charac-
teristics were more obvious at lower strain amplitudes, as
seen in Fig. 8a.
Conclusions
Strain-controlled low cycle fatigue tests were conducted on
an extruded 6061 aluminum alloy under varying strain
amplitudes. The stress-strain responses exhibited essentially
symmetric responses as a consequence of the dislocation
slip-dominated deformation with slight Bauschinger effect.
At higher strain amplitudes of 0.8–1.2%, only slight change,
i.e., an initial slight cyclic hardening within the first ten
cycles and then cyclic stabilization follows until failure,
could be seen. The extent of initial hardening also decreased
with decreasing strain amplitudes. The fatigue life of the
present alloy was observed to be longer than other extruded
6061 alloys, which can be well described by the Coffin–
Manson law and Basquin’s equation. SEM examinations
revealed that fatigue cracks initiated from the specimen
surface or near-surface defects. Crack propagation was
characterized mainly by the typical fatigue striations at lower
strain amplitudes.
452
Acknowledgements The authors would like to thank the Natural
Sciences and Engineering Research Council of Canada (NSERC) and
Rio Tinto Aluminum, through the NSERC Industrial Research Chair in
Metallurgy of Aluminum Transformation at the University of Québec at
Chicoutimi (UQAC) for providing financial support.
References
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of extruded 6061-T6 aluminum alloy. JMEPEG 22, 1348–1350
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7. K.L. Fan et al., Tensile and fatigue properties of gravity casting
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10. S. Suresh, Fatigue of Materials, 2nd edn. (Cambridge University
Press, Cambridge, 1998)
11. S. Begum et al., Low cycle fatigue properties of an extruded AZ31
magnesium alloy. Int. J. Fatigue 31, 726–735 (2009)
12. S. Begum et al., Strain-controlled low-cycle fatigue properties of a
newly developed extruded magnesium alloy. Metall. Mater. Trans.
A 39, 3014–3026 (2008)
13. J.B. Jordon et al., Damage and stress state influence on the
Bauschinger effect in aluminum alloys. Mech. Mater. 39(10), 920–
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14. C.H. Cáceres, T. Sumitomo, M. Veidt, Pseudoelastic behaviour of
cast magnesium AZ91 alloy under cyclic loading-unloading. Acta
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15. F.A. Mirza et al., Low cycle fatigue of a rare-earth containing
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 Part X
Aluminum Alloys, Processing and Characterization:
Poster Session
 Corrosion of Al–Mg Alloys in Ethanol

Gustavo Raúl Kramer, Estefanía Gauto, Roberto S. Rozicki,

Claudia Marcela Méndez, and Alicia Esther Ares

Abstract
Technological changes driven to solve the energy problems existing in the world today,
offer a key opportunity for sciences related to the selection of materials. Specifically for
production industries and handling biofuel, it is crucial the effectiveness of materials
against corrosion, so in recent years the increase is denoted in corrosion studies of metallic
alloys applied in these industries. The aim of this work is to study the corrosion behavior of
aluminum-magnesium alloys, using potentiodynamic polarization and Electrochemical
Impedance Spectroscopy (EIS) tests in ethanol (99.5% v/v) at room temperature, evaluating
the effects of microstructure and percentage of magnesium addition. Furthermore, the
mechanisms involved in corrosion are proposed, compared to the different theories
suggested by other authors.

Keywords
Aluminum–Magnesium alloys Corrosion Structural parameters Ethanol

Introduction
The use of ethanol as a substitute for fossil fuels, has proven
to be a viable alternative, capable of mitigating emissions of
carbon dioxide.
Bioethanol is produced by fermentation from any raw
material rich in sugars. Alcohol-based biofuels have a high
miscibility with water and also can occur partial oxidation of
its components from exposure to the atmosphere, increasing
acidity, being therefore potentially corrosive. Moreover,
dehydrated ethanol can also cause corrosion problems,
mainly due to its hygroscopic nature. Furthermore, during
G.R. Kramer
E. Gauto
R.S. Rozicki
C.M. Méndez
A.E. Ares
Facultad de Ciencias Exactas, Químicas y Naturales (FCEQyN),
Universidad Nacional de Misiones (UNaM), Félix de Azara 1552,
3300 Posadas, Argentina
G.R. Kramer (&)
A.E. Ares (&)
IMAM (CONICET-UNaM), Posadas, Argentina
e-mail: grkramer@fceqyn.unam.edu.ar
A.E. Ares
e-mail: aares@fceqyn.unam.edu.ar
storage, ethanol can be oxidized to acetic acid and its acidity
increase, with consequent corrosive risk.
From this it can conclude that all metallic materials which
are in contact with bioethanol, from their production to their
use, are susceptible to corrosion.
According to various investigations, bioethanol is not
compatible with aluminum [1–3], but in these studies, cor-
rosion at low temperatures (below the boiling point of
alcohol) has not been thoroughly investigated [4].
In most industries related to bioethanol, either for pro-
duction or for handling, aluminum-based alloys are used as
structural material due to its good mechanical properties.
Commonly found based aluminum alloys containing silicon,
which stand out for their resistance to wear, and aluminum
base alloys containing magnesium, which have high hard-
ness and resistance [5].
The overall objective of this paper is to analyze the
problems and the proposed solutions regarding corrosion
experiencing different base alloys with magnesium alu-
minum as main alloying, produced by exposure of these
materials to ethanol systems. Corrosion mechanisms pro-
posed depending on the prevailing conditions of work in the

© The Minerals, Metals & Materials Society 2017 455

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_57
456
production and use of ethyl alcohol of plant origin were
analyzed.
Experimental Procedure
For this study based aluminum alloys were used as an
alloying magnesium (Al–2% Mg and Al–4% Mg) of dif-
ferent structures.
The surfaces of the samples were polished using SiC
papers with different granulometry (from #600 to #1500),
this process was carried out just before each test.
The corrosive medium used was anhydrous ethanol
(99.5% v/v).
Potentiodynamic tests were performed in a conventional
electrochemical cell of three electrode and using a Gamry
Interface 1000® potentiostat, with a potential scan rate of
0.16 mV/s from −300 mV against open circuit potential to
+0.2 mV, at room temperature and natural aeration, using
Ag/AgCl/KCl (sat) as a reference electrode and platinum
wire as the counter electrode, in a spiral form, for greater
contact area with the electrolyte solution. The spectrum of
Electrochemical Impedance Spectroscopy (EIS) was
obtained with an amplitude of sinusoidal potential of
±10 mV, relative to open circuit potential, from a fre-
quency of 1 MHz to a convenient frequency where the
data fidelity would not be affected (approximately 0.1 and
0.01 Hz), with a previous exposure of the specimen in
anhydrous ethanol during 16 h. A 1% p/p of Na2HPO4
was used as medium to avoid the low conductivity of
ethanol [2, 3].
The microstructures of the Al–2%wtMg and Al–4%wtMg
alloys are shown in Fig. 1. Also, the average grain size of
the different microstructures obtained by unidirectional
solidification is presented in Table 1. For all Al–Mg alloys
with equiaxed microstructures obtained in different regions
of the specimens were defined as E1, E2, E3, also those
Fig. 1 Photographs of the surface of the samples studied in the present research
G.R. Kramer et al.
obtained with columnar microstructure (C) and with
columnar to equiaxed transition (CET).
Results and Discussion
Potentiodynamic Polarization
In order to compare the influence of microstructure on the
corrosion resistance, in Figs. 2 and 3 are showed the
potentiodynamic polarization curves of Al–2wt%Mg and
Al–4wt%Mg respectively. With regard to Al–2wt%Mg, can
be seen that for the different structures the Ecorr are in a
wider range of values (between −600 and −960 mV), while
for the Al–4%wtMg are in a smaller range (between −775
and −900 mV). Generally, the latter has lower values of
Ecorr, which could be explained considering that the E0 of
Mg is less than Al (E0Al ¼ 1660 mV; E0Mg ¼ 2370 mV)
in aqueous medium.
With respect to the shape of the curve, can be seen that all
have an area of passivation and then there is a shot between
−300 mV and 0 V.
Ecorr values (corrosion potential) and Rp (Polarization
Resistance) obtained by the Method of Linear Polarization is
summarized in Table 2. Ecorr corrected by considering the
ohmic drop (Ru), due to the low conductivity of the medium
[6, 7] using Eqs. (1) and (2).
EIRdrop ¼ I  Ru ð1Þ
Ecorrect ¼ Emeas þ EIRdrop ð2Þ
For Al–2wt%Mg shows that the Rp is in the following
order: E3 > E2 > E1 > C > CET, showing that equiaxed
structures have greater corrosion resistance than columnar
and CET structures within an increased corrosion resistance
by increasing the grain size is observed. For Al–4wt% Mg
the RP behavior is: CET > E2 > E1 > E3 > C; unlike the
Corrosion of Al–Mg Alloys in Ethanol 457

Table 1 Average grain size of Alloy (mm) Alloy (mm)

alloys with different structures
Al–2%Mg Columnar (C) 2.8 Al–4%Mg Columnar (C) 1.11
Al–2%Mg Equiaxed (E1) 0.34 Al–4%Mg Equiaxed (E1) 0.32
Al–2%Mg Equiaxed (E2) 0.21 Al–4%Mg Equiaxed (E2) 0.46
Al–2%Mg Equiaxed (E3) 0.65 Al–4%Mg Equiaxed (E3) 0.98
Al–2%Mg (CET) 0.30 Al–4%Mg (CET) 0.60

Fig. 2 Potentiodynamic curves

comparing the effect of different
microstructures of Al–2wt%Mg

Fig. 3 Potentiodynamic curves

comparing the effect of different
microstructures of Al–4wt%Mg
458 G.R. Kramer et al.

Table 2 Parameters of corrosion behavior

Ecorr (mV) Rp (kX cm2) Icorr (µA/cm2) Vcorr (mm/year) Ru (X cm2)
Al–2wt%Mg E1 −606.72 1016.97 0.021 0.00023 15.000
E2 −958.17 1220.20 0.019 0.00021 15.000
E3 −728.63 1223.78 0.018 0.00019 15.000
CET −837.24 627.7 0.035 0.00038 5.000
C −705.99 849.20 0.027 0.00029 5.000
Al–4wt%Mg E1 −913.75 1353.08 0.019 0.00020 2.500
E2 −954.00 1739.21 0.012 0.00014 100.000
E3 −823.01 1040.76 0.021 0.00023 15.000
CET −849.91 1845.28 0.012 0.00013 15.000
C −775.88 953.77 0.025 0.00027 5.0

Fig. 4 Bode diagram of EIS of two grain structures. a Al–2wt%Mg and b Al–4wt%Mg
Corrosion of Al–Mg Alloys in Ethanol
Al–2wt%Mg alloy, the corrosion resistance of the CET
structure is greater than the columnar.
If the Al–2wt%Mg and Al–4wt%Mg are compared with
the same grain size, it is obtained as a result that the cor-
rosion resistance of Al–2wt%Mg is lower than the Al–4wt%
Mg for both E1 structure to CET structure.
Electrochemical Impedance Spectroscopy (EIS)
The spectra obtained for all grain structures of Al–2wt%Mg
alloy (see Fig. 4a) were adjusted until obtaining the equiv-
alent circuit common for all. This circuit is represented in
Fig. 5a, where Rs is the solution resistance, and there is a
contribution of the resistive element (R2) and a constant
phase element, Q2, with the respective identity coefficient,
n2. It can be inferred that in the Al–2wt%Mg alloys, the R2
element represent the electrical resistance of an oxide layer
formed on the surface of the alloy, and depending on the
value of Q2 and its coefficient of identity (n2), aims to be a
more compact than a porous layer (n close to unity) [8]. The
values of these parameters are summarizes in Table 3, and
can be observed that there is no significant difference
between them, that is, although varying the grain size of the
macrostructure of the Al–2wt%Mg alloy, the metal/solution
reaction mechanism is the same, for 16 h of immersion in
anhydrous ethanol.
The spectra obtained for all type of grain structures of
Al–4wt%Mg alloy were adjusted (Fig. 4b), and the same
equivalent circuit was obtained for all spectra (Fig. 5b). It is
composed of the own resistance of the electrolyte medium
Fig. 5 Models of equivalent circuits used to adjust the values of EIS
of: a Al–2wt%Mg and b Al–4wt%Mg
459
(Rs); the resistor R1 and the constant phase element, Q1,
proposing the formation of an external oxide layer, and also
a resistive contribution R2 and constant phase element Q2,
which would explain the formation of another layer of
internal oxide, with differently features that the outer layer,
but arranged contiguously. It should be noted that if it in the
presence of two layers of homogeneous and distinct com-
positions, well-defined and developed, the equivalent circuit
would be different [8], so it can be assumed that the inner
layer is formed. The values of these parameters are sum-
marized in Table 3.
According to Gollapudi [9] the oxide layer formed of
pure aluminum, with a wide distribution of grain size (in-
homogeneous grain size distribution) tends to be uniform,
compact in some areas, and not uniform in others (Fig. 6).
Taking account of the increase in Mg as alloying for Al–4wt
%Mg alloys, it can be assumed that oxides of Mg participate
in the formation of irregular layers (overlapping or adjacent),
and thus, increase the corrosion resistance since the specific
resistance (q) of MgO is one order greater than that of Al2O3
[10].
Since potentiodynamic polarization measurements
involve the system away from the stationary state, applying a
(overpotential) disturbance, it is likely that its results cannot
be compared using Electrochemical Impedance Spec-
troscopy technique. Even so, to estimate the corrosion rate;
while EIS interface allows 16 h study of samples immersion
and identify the mechanisms of oxidation of the interface.
However, in both tests can be observed a maximum in the
corrosion resistance for Al–4wt%Mg alloy, with CET grain
structure, considering the Rp resistance for polarization
potentiodynamic tests and R1 and R2 for EIS tests.
Observing the test pieces, in a Nikon® metallographic
optical microscope after 16 h of immersion in anhydrous
ethanol, no changes were observed on the surface.
Possible Reaction Mechanism of Al–Mg Ethanol
It has been reported that ethanol anhydrous corrodes the Al
through the following reaction (3) [6, 11–14]:
2Al þ 6CH3 CH2 OH ! 2AlðCH3 CH2 OÞ3 þ 3H2 " ð3Þ
The reaction mechanism of the dry corrosion may be
explained electrochemically [12], if divided into two reac-
tions, anodic (4) and cathodic (5):
Al ! Al þ 3 þ 3e ð4Þ
3CH3 CH2 OH3e ! 3CH3 CH2 O þ 3=2H2 ð5Þ
It is well known that aluminum forms a passivation slim
and compact film composed of Al2O3 [15]. Magnesium also
460 G.R. Kramer et al.

Table 3 Values obtained from measurements of EIS

Rs (X cm2) Q1 (S sn1/cm2) n1 R1 (X cm2) R2 (X cm2) Q2 (S sn2/cm2) n2
Al–2wt%Mg C 21.48 – – – 74.304 1.41E-05 0.90
E1 20.856 – – – 23.496 1.10E-05 0.90
E2 25.87 – – – 79.101 9.22E-06 0.92
E3 20.88 – – – 46.304 2.42E-05 0.83
CET 18.10 – – – 33.094 1.21E-05 0.91
Al–4wt%Mg C 23.01 9.64E-06 0.91 39.741 19.635 3.92E-06 1.00
E1 17.09 1.79E-05 0.93 22.440 19.404 4.62E-05 1.00
E2 27.62 1.14E-05 0.91 31.104 11.340 7.06E-06 1.00
E3 31.98 7.93E-06 0.91 81.012 24.121 1.38E-05 0.86
CET 16.38 7.09E-06 0.92 25.036 130.276 4.82E-06 0.73

Fig. 6 Schematic of passive layer formation in a fine grained microstructure and b large grain size distribution of the microstructure, in agreement
with [9]. The inhomogeneous formation of the oxide layers may also be due to the participation of Mg as an alloy

form an oxide film composed of MgO in the absence of water,
which is less protective than aluminum [16]. In samples of
Al–2wt%Mg alloy, the EIS measurements show a compact
oxide layer. For Al–4wt%Mg two layers were observed, the
interior more compact and the exterior more porous. It is
proposed that the inner layer is rich in oxides of Al and the
outer layer of Mg oxides [17]. This can be explained because
the layer is formed by the migration of the Al+3 and Mg+2 ions
to the outside, and that the relative mobility of Mg+2 is greater
than the Al+3 through the layer [18].
In addition, the affinity of Mg to oxygen is greater than
for Al (Energy metal-oxygen bond: Mg–O = 166 kJ/mol;
Al–O = 2802 kJ/mol) [18]. Note that the relative solubility
(water) in ethanol of O2 is 25.57 (at 25 °C) [19], so there is
oxygen necessary to form the oxide layers.
3. The results for both tests show that the increase of Mg as
alloying of Al, and selecting a transition macrostructure
achieve a maximum corrosion resistance of Al alloy base
against a medium consisting of anhydrous ethanol.
4. This work serves as the basis for future study of corrosion
behavior of these samples by varying the temperature and
the amount of contaminants in water and ethanol.
Acknowledgements This work was supported by CONICET and
Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT)
from Argentina under Grant PICT-2012-2952.The authors thanks to
San Javier sugar refinery, for donating samples of regional bioethanol.
E. Gauto thank the CEDIT through a scholarship for realize the present
research.

References
Conclusions
1. The corrosion resistance is higher in the Al–4wt%Mg
alloy for a similar grain size according to potentiody-
namic polarization tests.
2. The Al–4wt%Mg alloy after 16 h immersion in anhy-
drous ethanol, form two layers of different composition.
While the Al–2wt%Mg form one barrier layer.
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 Warm Pressing of Al Powders: An Alternative
Consolidation Approach

Peter Krizik, Martin Balog, Oto Bajana, Maria Victoria Castro Riglos,
and Peter Svec Sr.

Abstract
This paper presents the warm pressing as an alternative powder metallurgy approach to
conventional press-and-sinter or hot working (e.g., extrusion, forging) consolidations of Al
powders into complex near-net-shape parts with required mechanical properties. In this
study gas-atomized Al powders (A1050 and A6061) with various particle sizes were
consolidated by uniaxial pressing, with minimum plastic deformation induced, at
temperatures of 22 and 430 °C, respectively. The materials pressed at 22 °C showed poor
strengths, ductility and electrical conductivity. The properties were improved markedly
when pressing temperature increased to 430 °C and reached values comparable to A1050
and A6061 materials fabricated by conventional powder and ingot metallurgy approach.
Similarly, the properties of the materials pressed at 22 °C were improved after annealing at
300 °C for 2 h. This indicated the formation of sufficiently strong interfacial bonding
between native oxide layers on adjacent Al powder particles (i.e., grains) when processing
temperature increased to 300 °C. With interfacial bonding established, the fracture
mechanism changed from brittle to ductile character.

Keywords
Powder metallurgy Aluminum Pressing Consolidation Microstructure Mechanical
properties

M.V.C. Riglos
P. Krizik (&)
M. Balog
O. Bajana Centro Atómico Bariloche, Av. Bustillo 9.500,
Institute of Materials and Machine Mechanics, Slovak Academy 8400 Bariloche, Río Negro, Argentina
of Sciences, Dubravska cesta 9, 84513 Bratislava, Slovakia e-mail: viquiriglos@gmail.com
e-mail: peter.krizik@savba.sk
P. Svec Sr.
M. Balog Institute of Physics, Slovak Academy of Sciences,
e-mail: martin.balog@savba.sk Dubravska cesta 9, 84511 Bratislava, Slovakia
O. Bajana e-mail: peter.svec@savba.sk
e-mail: oto.bajana@savba.sk

© The Minerals, Metals & Materials Society 2017 463

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_58
464
Introduction
Aluminum (Al) powder metallurgy (PM) offers the follow-
ing advantages: (i) cost-effective production of (near)
net-shape complex products; (ii) the desired microstructural
features such as fine grains, fine phases, and a homogenous
microstructure, resulting in improved mechanical properties;
and (iii) the ability to produce various composites. In gen-
eral, a surface of atomized Al based powders is coated with
native amorphous (am)-Al2O3 layer with a thickness of
*2.5 nm regardless of the size of the powder and
atomization atmosphere [1]. It is widely accepted by PM
community that native Al2O3 layer on the powder surface
must be disrupted in order to create a “proper” metallurgical
bonding between metallic Al powder interiors. Otherwise
consolidated powder material lacks sufficient ductility and
toughness. There are two major consolidation approaches:
(i) diffusion based (e.g., sintering, HIP, etc.) techniques and
(ii) techniques which rely on induced plastic deformation
(e.g., extrusion, forging, rolling, etc.). During sintering of Al
powder (mixtures) native Al2O3 layers are reduced and
disrupted by chemical reaction [2]. However, typical PM Al
parts fabricated by conventional press-and-sinter approach
suffer from rather high porosity, which restricts service of
such parts for non-fatigue and low stress applications. In
case of plastic deformation based consolidation techniques
native Al2O3 layers are torn mechanically. Induced shear
deformation enlarges the surface of the powders, which
breaks up native Al2O3 layers [3]. In contrast to the sintering
approach, special furnaces that accommodate protective
atmospheres are not usually available for the heating of
Al-based powder green compacts at standard extrusion or
forging plants. As a result, heating to the desired consoli-
dation temperature is usually performed in air. Rather
complex powder surface phenomenon, which can yield
irreversible microstructural changes of powder and can
deteriorate the properties of the final part, takes place during
heating in air [4, 5]. Therefore, either complicated canning of
powder green compacts is necessary to include or processing
temperature has to be lowered under critical temperature in
order to avoid powder oxidation related problems. Never-
theless, canning operation raises extremely production
expenses as well as lowering consolidation temperature is
often not feasible due to high deformation resistance of
powder to plastic deformation realized at such low
Table 1 The particle sizes of Powder Size (µm)
used powders
A6061 <63
A1050a <63
A1050b – 1.2
A1050c – 0.2
P. Krizik et al.
temperature. Thus both are to be avoided especially if large
scale industrial production is concerned.
Recent research has shown that the ultrafine-grained
(UFG) materials prepared by hot quasi-isostatic forging
(QIF) of fine Al powders, named HITEMAL (high tem-
perature Al), exhibit excellent mechanical properties
despite the fact that the native am-Al2O3 layers remains
largely intact within the structure of the subsequent com-
pact [6, 7]. Microstructure of HITEMAL manufactured by
QIF consists of the UFG Al grains decorated by continu-
ous am-Al2O3 network, whereby the direct metallurgical
bonding between metallic Al powder cores is not created
[8]. Forged HITEMAL possesses excellent microstructural
stability, high strengths, reasonable ductility and creep
performance at relatively high service temperatures (up to
*400 °C).
Motivated by these factors, the objective of this study is
to present a cold (or warm) pressing with subsequent
annealing as an alternative consolidation technique for pro-
duction of near net-shape Al based parts realized at low
processing temperature. Potential of this cost-effective
technique is demonstrated on the compacts consolidated
from standard Al alloys A1050 and A6061.
Experimental
Gas atomized commercial purity (CP) Al (>99.7 wt%;
A1050) powders of three different particle sizes and alloyed
Al–Mg–Si (A6061) powder were used in this study
(Table 1). Particle size distribution (PSD) was measured
using Fritsch Analysette 22 MicroTec laser diffraction sys-
tem by wet dispersion. Obtained d10, d50 and d90 values,
which represent the particle diameters corresponding to 10,
50 and 90% cumulative undersize PSD, are summarized in
Table 1. The powders were cold compacted by means of
cold isostatic pressing (CIP) at 150 MPa. CIP compacts
pressed from coarse A6061 and A1050-a powders were
vacuum degassed at 350 °C for 2 h. CIP compacts pressed
from fine A1050-b and A1050-c powders were vacuum
degassed at 425 °C for 12 h. Degassed CIP compacts were
hot pressed at various temperatures in air using hydraulic
press with the ram speed of 0.5 mm s−1. Fabricated samples
with corresponding processing parameters are listed in
Table 2.
d10 (µm) d50 (µm) d90 (µm)
10 27.8 58.5
12.6 30.4 61.3
2.9 6
1.7 3.4
Warm Pressing of Al Powders: An Alternative Consolidation … 465

Table 2 Processing parameters Sample Powder Pressing temp. (°C) Pressure (MPa) Porosity (%)
(pressing temperature and
pressure), porosity and A6061-430 A6061 430 500 0
designation of prepared samples A1050a-430 A1050a 430 500 0.01
A1050a-RT A1050a 22 1200 0.04
A1050b-430 A1050b 430 500 0.2
A1050c-430 A1050c 430 500 0.5
A1050c-RT A1050c 22 1200 0.5

The microstructure and fracture surfaces were analyzed
using scanning electron microscopy (SEM, JEOL 7500
machine) equipped with energy dispersive spectrometry
(EDS, Oxford Instruments X-Max 50). The oxide layers
were observed using transmission electron microscopy
(TEM, FEI TECNAI G2 machine, 200 kV). The thin TEM
foils were prepared by wire electro discharge machining,
mechanical grinding, dimpling and finally ion milling using
Gatan PIPS machine. The density of the prepared samples
was measured using the Archimedes’ principle. Tensile tests
at room temperature (RT) were carried out using a ZWICK
Roell 1474 testing machine at a strain rate of 8  10−4 s−1.
Dog bone-shaped tensile specimens with the gauge of
2  5  20 mm3 were used. At least three measurements
were performed for each configuration. In order to generate a
bonding between adjacent powder particles, the samples
were annealed at 300 °C for 2 h under Ar atmosphere. In the
case of the sample A6061-430, heat treatments T4 (solution
treatment at 530 °C for 1 h) and T6 (solution treatment at
530 °C for 1 h + artificial aging at 175 °C for 8 h) were
applied.
The electrical resistivity of the samples with 1  4 mm2
cross-section and 55 mm length was measured by
four-probe methods using spring-loaded contacts spaced
10 mm between each contact. AC bridges from Linear
Research, model LR400, with digital voltmeter was used to
determine the resistivity values with accuracy of ±0.5 µX.
Specific resistivity was calculated using the spacing between
probes of 10 mm and average cross-section of the samples.
Results and Discussion
The representative microstructure of as-pressed A1050a-430
sample is shown in Fig. 1a. The corresponding EDS map of
oxygen (O) element reveals the network rich for O embed-
ded in Al matrix (Fig. 1b). The detailed microstructural
characterization of O rich network by HRTEM (Fig. 2)
confirms that the layers of network are mostly amorphous,
continuous and have a thickness of *8 nm. Occasionally,
some nano-scale crystallites nucleated within the layers are
seen. In line with previous works [8–10], those crystallites
are confirmed to be c-Al2O3. Thus the network is formed
in situ from native am-Al2O3 layers present on adjacent
powder particles which come in a contact during pressing.
Due to a limited plastic deformation induced native layers do
not fracture during pressing and continuous double
am-Al2O3 layer network forms. Polyhedral Al grains

a b

Fig. 1 a Representative SEM microstructure of sample A1050a-430 and b corresponding EDS map of oxygen element
466 P. Krizik et al.

a b

Al grain
Al grain

Al grain

Al grain
am-Al2O3

Fig. 2 a TEM image and b HRTEM detail of the am-Al2O3 network between two adjacent Al powder particles in sample A1050c-430

decorated with am-Al2O3 network suggest that originally
spherical Al powder particles deform only subtly during
pressing while they form polyhedrons. All fabricated sam-
ples show very similar microstructures without major dif-
ferences in terms of crystallographic state, thickness and
morphology of Al2O3 network. All materials show a very
low residual porosity of  0.5%.
The results obtained from tensile tests of materials con-
solidated from A1050a powders realized at RT are sum-
marized in Table 3. The as-pressed material A1050a-RT
fractures prematurely by brittle manner and exhibits irre-
producible strengths and no ductility. Conversely, the
as-pressed sample A1050a-430 shows ductile behavior and
reaches reasonable tensile properties, which are expected for
typical CP Al (e.g., YS0.2 = 82.6 MPa). Annealing realized
at 300 °C for 2 h changes the deformation behavior of
A1050a-RT significantly from brittle to ductile character.
Annealed A1050a-RT sample reaches the strengths and
elongation of as-pressed A1050a-430. In opposition,
annealing of A1050a-430 at 300 °C for 2 h does not change
the tensile properties markedly.
The surfaces of fractured tensile bars of the samples
A1050a-RT in as-pressed condition and after annealing at
300 °C for 2 h are shown in Fig. 3. The as-pressed sample
features a typical intergranular brittle fracture without any
signs of plastic deformation (Fig. 3a). The faces of polyhe-
drons correspond to polyhedral Al grains as determined by
EDS mapping (Fig. 1b). In line with tensile properties the
annealed material exhibits ductile surface fracture with
dimples and tearing edges (Fig. 3b). As published by Balog
et al. [8], am-Al2O3 network remains stable till transition
temperature of *430 °C, where massive transformation of
am-Al2O3 network to c-Al2O3 nano-scale crystallites, which
remains to occupy the same position at Al grain boundaries,
takes place. Thus no crystallographic and morphological
changes in am-Al2O3 network are expected to occur within
the materials in this study after annealing due to relative low
annealing temperature (300 °C). Similar change in the
mechanical behavior was observed also for cold spray Al
powder coatings, wherein induced annealing significantly
improves the mechanical properties [11, 12]. The reason for
this behavior is explained by authors as the recrystallization

Table 3 Room temperature Material Condition YS0.2 (MPa) UTS (MPa) A (%)
ultimate tensile strength (UTS),
yield strength (YS0.2) and A1050a-RT As-pressed a a
*0
elongation (A) of the materials A1050a-430 As-pressed 78.5 ± 4 100.7 ± 7 20 ± 6
pressed from A1050a powder
A1050a-RT Annealed at 300 °C for 2 h 94 ± 7 108.8 ± 3 18 ± 4
A1050a-430 Annealed at 300 °C for 2 h 82.6 ± 6 103.4 ± 5 24 ± 2
a
On a level of a few MPa; large scatter of values
Warm Pressing of Al Powders: An Alternative Consolidation … 467

Fig. 3 The fracture surfaces of the samples A1050a-RT in a as-pressed condition and b after annealing at 300 °C for 2 h

of heavily deformed Al structure due to a high impact

velocity of powder particles. Nevertheless, similar change
occurs also in the case of the compact consolidated from
ultra-fine powders [13, 14]. Herein, recrystallization is
completely suppressed due to a superior stabilizing effect of
Al2O3 phase, which prevents Al grain structure from grain
growth and static recrystallization up to relatively high
homologous temperatures [8]. Above described factors
indicate that a bonding between adjacent am-Al2O3 layers in
cold compacted Al powder materials creates during anneal-
ing. The established bonding is sufficient to provide load
transfer from one Al grain (i.e., initial powder particle) to
another grain and thus reasonable strength and ductility are
achieved. Nevertheless, further systematic study, which is
part of future scope to be published soon, is needed to
address exact origin and formation of such bonding between Fig. 4 The engineering stress-strain curves of the materials compacted
from the powder A1050c by: a pressing + annealing at 300 °C for 2 h,
thin am-Al2O3 layers. b hot quasi-isostatic forging (QIF) [6] and c hot direct extrusion
The representative engineering strain-stress curve of (DE) [1]
pressed A1050c-RT after annealing at 300 °C for 2 h at RT
is shown in Fig. 4 and compared to those of hot QIF [6] and
hot extruded [1] counterparts fabricated from the same MPa) compared to ingot wrought A6061 alloy (YS = 276
A1050c powder. Pressed A1050c-RT + annealed material MPa) in T6 condition, however at the expense of lower
possess the tensile properties which are on the level of those ductility (3%).
obtained for the material prepared by hot QIF. A slightly Figure 5 shows the electrical conductivity of the samples
higher strength and elongation of hot extruded material can prepared from A1050 powders as a function of the powder
be rationalized by the presence of finer Al grain size and size. With decreasing powder size the electrical conductivity
proper metallic Al–Al bonds, respectively [1]. The com- decreases due to higher content of grain boundaries deco-
parison of the mechanical properties and the densities of hot rated with continuous am-Al2O3 network, which acts as a
pressed A6061-430 samples with sintered PM Al–Mg–Si barrier. Electrical conductivity of coarse grained sample
and wrought A6061 alloy is summarized in Table 4. The A1050a-430 (31.8 MS m−1) is close to the one of CP Al
higher mechanical properties of A6061-430 result from their ingot material (35 MS m−1 [17]). The sample A1050a-RT,
full density after pressing. The inferior porosity of sintered where interfacial bonding between am-Al2O3 layers in net-
Al materials is standardly at the level of *5%. Hot pressed work is not established yet, reaches low value of electrical
A6061-430 samples exhibit also higher strength (YS = 316 conductivity (1.49 MS m−1).
468 P. Krizik et al.

Table 4 The mechanical properties of hot pressed A6061-430 samples in comparison with sintered PM materials of similar chemical composition
and wrought A6061 alloy
Material Condition Manufacturing route YS (MPa) UTS (MPa) A (%) Density (g/cm3) Ref.
601AB T4 Sintering 117 176 6 2.45 [15]
601AB T6 Sintering 230 238 2 2.45 [15]
602AB T4 Sintering 65 134 10 2.55 [15]
602AB T6 Sintering 172 186 3 2.55 [15]
A6061-430 As-pressed Hot pressing 95 ± 1 170 ± 1 12 ± 1 2.69 a

A6061-430 T4 Hot pressing 177 ± 3 278 ± 1 12 ± 1 – a

A6061-430 T6 Hot pressing 316 ± 3 341 ± 7 3±1 – a

A6061 T4 Wrought alloy 145 241 22 2.7 [16]

A6061 T6 Wrought alloy 276 310 17 2.7 [16]
601AB (Al–0.25Cu–1.0Mg–0.6Si) and 602AB (Al–0.6Mg–0.4Si) are commercial available Al PM premix with chemical composition similar to
A6061 alloy
a
The results of this study

• The cold pressed materials fractured prematurely during

Fig. 5 The electrical conductivity of pressed materials determined at
RT as a function of powder size
Conclusions
In this paper an alternative cost-effective powder metallurgy
approach for consolidation of Al-based powders was pre-
sented. The A1050 and A6061 powders of various particle
sizes were consolidated by uniaxial pressing at temperatures
22 and 430 °C. Within the limitations of this paper, the
following conclusions can be made:
• The microstructure of cold and hot pressed materials
consisted of Al grains decorated with continuous
am-Al2O3 network, with thickness of *8 nm, embedded
in Al matrix. Am-Al2O3 network formed in situ as a
result of native am-Al2O3 layers on adjacent Al powders,
which come to a contact during consolidation.
tensile tests by brittle manner and they showed poor
strengths and electrical conductivity.
• The properties increased abruptly when cold-pressed
materials were subsequently annealed at 300 °C for 2 h.
The properties reached the values comparable to those of
A1050 and A6061 materials fabricated by conventional
powder and ingot metallurgy.
• The properties comparable to those of cold pressed
materials annealed at 300 °C for 2 h were achieved also
for the materials hot pressed at 430 °C.
• The results indicated a formation of interfacial bonding
between am-Al2O3 layers on adjacent Al powder parti-
cles when processing temperature increased to 300 °C
and higher.
Acknowledgements Financial support from the ITMS 26240220088,
the SRDA APVV-0556-12, the VEGA 2/0065/16 and 2/0025/14, and
CONICET-SAS RD Nº 182/13 projects is gratefully acknowledged.
The authors thank to Lubomir Orovcik of IMSAS for help with SEM
characterization.
References
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3. M. Balog, C. Poletti, F. Simancik, M. Walcher, W. Rajner,
J. Alloy. Compd. 509S, S235–S238 (2011)
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Stepanek, M. Nosko, F. Simancik, J. Mater. Process. Technol. 214,
1165–1172 (2014)
5. A. Nylund, K. Mizuno, I. Olefjord, Oxid. Met. 50, 309–325 (1998)
Warm Pressing of Al Powders: An Alternative Consolidation …
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W. Rajner, D.S. Liu, F. Simancik, Mater. Sci. Eng., A 613, 82–90
(2014)
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3781–3789 (2010)
8. M. Balog, T. Hu, P. Krizik, M.V.C. Riglos, B.D. Saller, H. Yang,
J.M. Schoenung, E.J. Lavernia, Mater. Sci. Eng., A 648, 61–71
(2015)
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Thin Solid Films 418, 89–101 (2002)
10. M.A. Trunov, M. Schoenitz, X. Zhu, E.L. Dreizin, Combust.
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13. P. Krizik, M. Balog, M. Nosko, P. Svec Sr., Formation of interfacial
bonding between native amorphous Al2O3 layers in cold forged Al
powder, in MATRIB 2015: Materials—Tribology—Recycling,
Zagreb, Conference Proceedings (2015). ISSN 1848-5359
14. P. Krizik, M. Balog, unpublished results
15. M. Qian, G.B. Schaffer, Sintering of aluminium and its alloys, in
Sintering of Advanced Materials, ed. by Z.Z. Fang (Woodhead
Publishing Ltd., 2010), p. 316
16. http://www.matweb.com/search/QuickText.aspx?SearchText=
A6061. Accessed 23 Sept 2016
17. https://en.wikipedia.org/wiki/Electrical_resistivity_and_
conductivity. Accessed 23 Sept 2016
 Part XI
Aluminum Reduction Technology: Dry Scrubbing,
Alumina Transport and Dissolution
 Spreading of Alumina and Raft Formation
on the Surface of Cryolitic Bath

Csilla Kaszás, László Kiss, Sándor Poncsák, Sébastien Guérard,

and Jean-François Bilodeau

Abstract
It is a well-known phenomenon in aluminum industry that alumina powder, fed into the
electrolyte, tends to stay afloat on the surface of the bath. This hinders dispersion and direct
contact of most of the powder with the electrolyte, therefore delays dissolution. In addition,
large clusters of alumina particles sintered together during raft formation might lead to the
agglomerate piercing through the bath-aluminum interface, which should be avoided. Since
the interference between raft formation and alumina dissolution is significant, it deserves
more attention. Several experiments were conducted in a small carbon crucible in which
cryolitic bath was melted and alumina of different properties was fed. The injections were
recorded by a video camera above the bath. The spreading of the powder on the surface, the
infiltration of powder by the bath as well as the disintegration or the sinking of the raft was
observed and the results analyzed.

Keywords
Alumina raft Spreading Flotation

Introduction mechanisms behind dissolution. The investigated parameters

According to our observations, alumina powder could spread
and float on the surface of the molten bath. The phenomenon
and its effects have not been thoroughly investigated yet.
Research in this field mostly aims to determine and model
the dissolution rate of alumina and the dominant driving
C. Kaszás (&)
L. Kiss
S. Poncsák
Université du Québec à Chicoutimi, 555 Boulevard Université,
Chicoutimi, QC, G7H 2B1, Canada
e-mail: csilla-katinka.kaszas1@uqac.ca
L. Kiss
e-mail: laszlo_kiss@uqac.ca
S. Poncsák
e-mail: Sandor_Poncsak@uqac.ca
S. Guérard
J.-F. Bilodeau
Rio Tinto Alcan CRDA, 1955 Boulevard Mellon,
Jonquière, QC, G7S 4K8, Canada
e-mail: Sebastien.Guerard@riotinto.com
J.-F. Bilodeau
e-mail: jean-francois.bilodeau@riotinto.com
influencing the dissolution are mostly the properties of alu-
mina and those of the electrolytic bath; the most significant
factors were found to be superheat and agitation of the bath
[1–4]. Relevant articles noted that alpha-alumina sinks and
gamma-alumina floats [5]. Townsend and Boxall [6] pro-
vided tables about the duration of flotation of different types
of alumina powders, differentiated between soft (snow-like,
low mechanical strength) and hard (ice-like, high mechanical
strength) crust, but did not find clear correlation between
crusting tendencies and other, easily measurable properties
of the powder. Walker [7] reported in his dissertation that the
consistency of an alumina raft, or a “floating island” as he
put it, is mushy after 15 s in the bath. Its structure was found
to be composed of three different layers, namely the solidi-
fied electrolyte, alumina infiltrated by the electrolyte with
changing composition and dry alumina. Also, pockets of
infiltrated alumina in frozen bath were found in the layers.
He attributed the sinking of agglomerates (sub-islands) to the
breaking of the island caused by mechanical interferences,
like the splashing of the bath or another alumina injection.

© The Minerals, Metals & Materials Society 2017 473

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_59
474
Objects could stay afloat on a liquid surface due to
buoyancy and surface tension. The flotation limits of an
alumina particle for example can be calculated based on the
force balance [8]. When there are many particles, they all
distort the liquid surface around them and the exact solution
of the surface deformation becomes difficult to find [9].
However we know that floating particles tend to cluster on
the surface due to lateral capillary forces. On the other hand,
in some cases, seemingly the exact opposite can happen
when we add a batch of powder into a liquid (sprinkling
flour on water for example): a rapid spreading of the powder
on the surface. This phenomenon is also attributed to cap-
illary forces, and the dynamic effect of the impact of the
particles agitating the surface. Research on this topic is
mostly experimental. [10, 11]
What complicates the behavior of alumina on the bath
surface is that the cohesive forces like freezing bath, the
liquid bridges and sintering caused by gamma-alpha phase
transition could overcome the capillary forces pulling the
raft apart.
Experimental Setup
The cryolitic bath was melted in a carbon crucible; the free
surface of the bath was 7.6 cm  7.6 cm square with
rounded corners. The depth of the bath was 5 cm. The
prepared bath contained 83% cryolite, 11.5% AlF3 and 5.5%
CaF2 but due to impurities, there was some alumina present
in the bath from the beginning and as a result of the injected
alumina powder, the concentration of alumina was increas-
ing. The estimated alumina concentration at the beginning of
each series of experiments will be shown in the next section;
any change due to bath evaporation was neglected.
The alumina powder provided by Rio Tinto was weighed
with a Sartorius CPA 10035 analytical balance, and it was
fed into the bath through a steel funnel, with the vertical
outlet tube of a height of 3 cm, and an inner diameter of
1 cm. The injector was positioned above the center of the
crucible, 1 cm above the bath surface that gave a 4 cm drop
height for the powder. The surface of the bath was filmed by
a camera fixed above the crucible.
Occasionally, a thermocouple was inserted into the bath
and it showed approximately 10 °C less than the thermo-
couple inserted in the bottom of the crucible. After injection,
Table 1 Parameters of Initial alumina
experiments on spreading concentration (%)
A 1.6
B 1.6
C 4.6
C. Kaszás et al.
the temperature was decreasing due to the cold powder, but
this was inevitable with the small size and cost-effective
experimental setup. To reduce the heat loss towards the open
surface of the bath, the opening was covered with a quartz
plate during the sinking or disintegration of the raft.
The details of the different experiments are presented in
Table 1.
Spreading and Shape of Rafts
The video files taken by the top-view camera were treated
with Matlab® Image Processing Toolbox (Fig. 1). The
images for the analysis of the spreading and the shape of the
raft were extracted at the earliest possible moments—less
than 3 s after the injection, the time necessary to remove the
feeder and get a complete clear view of the surface.
The width of the crucible was used as reference to calculate
the area of the rafts.
Different assumptions could be made about the shape of
the rafts and the experiments with different quantities of
powders would either support or disprove them.
Theoretically there was no asymmetry in the setup,
therefore the powder should have spread in every direction
on the surface—but since in nature and real life perfect
symmetry does not exist and there was certain heterogeneity
in the particle distribution upon entering the bath, the upper
view of the raft was not a circle. It was round but not per-
fectly circular.
If the lateral capillary forces spread out the powder evenly
over the entire bath surface, the average thickness of the
alumina rafts (calculated with a density of 1.05 g/cm3, the
density of loose alumina powder) would have been equal.
The average thickness based on the powder-covered area,
obtained by the image processing, increased with increasing
quantities (Fig. 2).
While the 0.2 g doses spread out to the same surface area
regardless of the bath temperature, there was a difference
with the other rafts. With the 0.5 and 1 g doses, the area of
the raft was smaller when the bath was colder (A–B) and it
spread out the most at the highest superheat (C), probably
because the bonding effect of the solidification of the bath
was less intense with higher superheat. The 2 g rafts showed
the inverse tendency, although they already reached the wall
of the crucible that could stop further spreading.
Temperature of Injected quantities of
crucible (°C) secondary alumina (g)
980 2, 1, 0.5, 0.2, 0.1
990 2, 1, 0.5, 0.2
980 1
Spreading of Alumina and Raft Formation …
Fig. 1 Example of image
treatment process of photo of
alumina raft (series A, 1 g)
Fig. 2 Estimated average thickness of raft obtained by image analysis
using Matlab
Powders poured on a flat solid surface from a funnel
formed a heap of conical form. While with such small
quantities a heap could not have been shaped properly, and
even with larger quantities, the water vapour leaving the
powder would distort the heap; for the sake of investigation,
a conical form of the raft was proposed and the angle of the
cone calculated—the measured angle can be compared to the
475
Fig. 3 Angle of cone supposing conical shaped raft obtained by image
analysis using Matlab
30°–36° value, reported as angle of repose of the alumina in
the literature [12] (Fig. 3).
The behavior of granular matter is in some regard similar
to liquids and the shape of a liquid drop that partially wets a
flat solid surface is sometimes regarded as a spherical cap.
Supposing a symmetrical lens shape for the rafts, the
radius of curvature was calculated and plotted against the
476
Fig. 4 Radius of curvature of lens shaped rafts obtained by image
analysis using Matlab
injected mass (Fig. 4). These values are the most consistent
therefore describing the shape of the rafts more accurately
than the conical approximation.
It is possible to take a further step forward for describing
the shape of an alumina raft more precisely. While during
this experiment the doses were very small, a larger dose of
powder fed through a relatively small opening could form a
heap. The apex would be eroded; the slope less steep at the
bottom, but it would essentially be a cone. The differential
equation of the liquid surface curvature for axisymmetric
systems is available. The deviations and randomness of the
shape of the pile originate from the disorder in the powder.
The pressure distribution on the bottom depends on how the
heap was formed; it is not proportional to the height of the
heap at each point. But supposing the powder acts as a
Fig. 5 Approximate shape of the
cross section of the raft by Matlab
Powder
C. Kaszás et al.
liquid, in that sense that it exerts a hydrostatic pressure on
the bath and neglecting other possible effects, the shape of
the raft can be estimated by solving the differential equation
of axisymmetric interfaces [13] (Fig. 5).
Another source of uncertainty is that the angle of the
slope of a granular heap near the bottom is smaller than the
angle of repose even without the effect of capillary forces
that might carry of particles toward the edge of a raft.
Infiltration
Since there were multiple 1 g doses with different bath
properties, they were used for the analysis of infiltration and
disintegration of the rafts.
Right after the injection of the powder the infiltration
began. The first wave of wetting, the frontier between the
dry and wetted alumina powder approaching the center
of the raft was visible. A more subtle change happened
around the sides of the rafts a few seconds after the wetting
started: the powder got soaked gradually in the bath and a
thin layer of liquid formed over the alumina. The outer
region reflected the light diffusely which suggest that the
surface of the liquid is not smooth. It seemed to be com-
posed of plenty tiny droplets.
The transition between wet and soaked powder was
gradual, therefore selecting a border on the images would be
quite hard and quite arbitrary (Fig. 6).
The evolution of the wetting, the receding area of dry
alumina on the three different 1 g doses is presented in
Fig. 7. The advancement of the wetting front started at the
Liquid
Spreading of Alumina and Raft Formation …
Fig. 6 Structure of partially infiltrated alumina raft 1 g, 6.7 s after
injection, ‘C’
Fig. 7 Progress of wetting of 1 g alumina rafts
edges of the rafts where the powder was more exposed to the
bath. The rate of advancement toward the center of the rafts
was not uniform around the perimeter; in some places the
bath infiltrated a larger region than elsewhere during the
same time. The front of wetting presumably corresponds to
the thickness of the raft confirming its conical shape.
All of the rafts were wetted in only 10 s. The wetting of
raft A and B were identical despite the 10 °C temperature
difference of the bath. Raft C was infiltrated little faster than
the others possibly because it spread out more and its apex
was less high.
477
Disintegration
To track the disintegration of the rafts, the area of the rafts as
a function of time was obtained by processing the video
from the top view camera with Matlab (Fig. 8).
The size of the rafts decreased most rapidly right after the
injection; especially raft B and C. 25 s after the injection, the
rate of shrinking decreased to an almost unperceivable level.
The disintegration was visible around the edge of the rafts
but likely it happened with the same intensity on the bottom
of the raft. While the bath was far from saturation with
alumina, it was not directly agitated. The injected bath
induced some slight motion in the bath but it died out
quickly and then, after the bath got saturated with alumina in
the immediate vicinity of the raft, fresh bath arrived only by
natural convection that could explain the almost stagnant
state of the rafts during the second part of their lives.
Raft A did not sink by itself, naturally. The temperature
of the bath was close to its liquidus temperature and slowly
decreasing due to the upward heat loss. The raft continued
floating without any sign of inclination, which is a fore-
runner of sinking. When the bath surface was mechanically
disturbed, we could see that a very thin bath layer froze on
top of the raft, preventing it from sinking.
The flotation times of the alumina rafts are compiled in
Table 2. However, drawing conclusions from the flotation
time in itself might be misguiding since sinking usually
happened when the raft became hydrostatically unstable.
One side became flooded while the other still uncovered. All
these density and thickness asymmetries have their origin in
Fig. 8 Disintegration and shrinking of floating alumina rafts after
injection
478 C. Kaszás et al.

Table 2 Flotation time of alumina rafts For this reason; and because the quantity of alumina used in
Quantity (g) Flotation time (s) Area at the time this experience was so below an industrial dose; it would be
of sinking (cm2) useful to continue the experience on a larger scale.
A 2 649a 21.4
1 307a 11.5 Acknowledgements The authors acknowledge the financial support of
0.5 70 11.2 Rio Tinto Aluminium and the Natural Sciences and Engineering
0.2 49 6.5 Research Council of Canada that made this work possible.
0.1 196 4.7
B 2 305 11.3
1 66 12.2 References
0.5 35 9.2
0.2 10 0
C 1 390 8.7 1. L.A. Issaeva et al., Rates of dissolution of commercial aluminas
a
with different physical properties. Light Met. 507–512 (1998)
Forced sinking 2. X. Wang, Alumina dissolution in cryolitic melts: a literature
review. Light Met. 41–54 (2000)
3. B.J. Welch, R.G. Haverkamp, Modelling the dissolution of
the slight heterogeneities and disorder of powder during alumina powder in cryolite. Chem. Eng. Process. 37, 177–187
injection. (1998)
4. V. Dassylva-Raymond et al., Modeling the behavior of alumina
agglomerate. Light Met. 603–607 (2014)
5. X. Liu et al., Visualisation of alumina dissolution in cryolitic
Conclusions melts. Light Met. 359–364 (1994)
6. D.W. Townsend, L.G. Boxall, Crusting behavior of smelter
aluminas. Light Met. 640–665 (1984)
Image processing is a valuable tool to extract data from 7. D.I. Walker, Alumina in aluminum smelting and its behaviour
videos—in this case on alumina raft disintegration. The after addition to cryolite-based electrolytes, Ph.D. thesis, Univer-
resulting diagrams provide deeper insight into the process sity of Toronto, 1993
than flotation time measurement in itself would. 8. C. Kaszas et al., Behavior of powders on the surface of a liquid.
Light Met. 639–643 (2015)
There was not a significant difference between the wet- 9. P. Singh, D.D. Joseph, Fluid dynamics of floating particles. Fluid
ting dynamics of the rafts with different superheats. With 1 g Mech. 530, 31–80 (2005)
doses, the front of infiltration reached the center of the rafts 10. T.H. Nguyen et al., An analysis of the thermodynamic conditions
in 10 s. The disintegration of the rafts was faster with higher for solid powder particles spreading over liquid surface. Powder
Technol. 201, 306–310 (2010)
superheat, more intense in the first 30 s after the injection, 11. S. Gurupatham et al., Breakup of particle clumps on liquid
and then it slowed down. surfaces. Powder Technol. 217, 288–297 (2012)
It was found that the spreading depended on superheat, 12. K. Grjotheim, H. Kvande (ed.), Introduction to Aluminium
higher superheat resulted in larger rafts with the exception of Electrolysis, 2nd edn. (Aluminium-Verlag, 1993)
13. V.M. Starov et al., Wetting and Spreading Dynamics, Surfactant
the largest doses where the rafts reached the side of the
Science Series, vol 138 (CRC Press, Boca Raton, 2007)
crucible blocking further spreading, distorting the results.
 Fluoride Capture Capacity of SGA:
The Interplay Between Particle and Pore
Size Distributions

Gordon E.K. Agbenyegah, Grant J. McIntosh, Margaret M. Hyland,

and James B. Metson

Abstract
The Bayer process, storage and transport of smelter grade alumina (SGA) together
contribute to the unique particle size distribution of the SGA as received in a gas treatment
facility or in a reduction cell hopper. Pore size distribution analyses of alumina fractions
indicate that the +125, +90 to −125, +63 to −90 and +45 to −63 lm particles possess
similar total pore volumes. The total pore volume of −45 lm particle size fraction,
however, was found to be approximately 15% lower than the remaining bulk. Having
earlier studied the evolution of pore size distribution in the bulk SGA during fluoride
scrubbing, this work examines the interplay between particle and pore size distributions,
with focus on the impact of fines on scrubbing efficiency in a smelter GTC.

Keywords
Particle size distribution Pore size distribution Alumina HF Gas treatment

Introduction
The main feedstock for primary aluminum production is
smelter grade alumina (SGA or alumina) but it also utilized
as the primary adsorbent in a smelter gas treatment centre
(GTC) for the capture and return of particulate and gaseous
fluorides. Considering, the dual role of alumina, its quality
must meet the standards required for optimum operations of
the potroom and the GTC. Generally, the SGA quality
parameters reported on specification sheet include gibbsite
and alpha alumina content, particle size distribution, attrition
G.E.K. Agbenyegah
M.M. Hyland
Department of Chemical and Material Engineering,
University of Auckland, Private Bag 92019, Auckland,
1142, New Zealand
G.E.K. Agbenyegah (&)
G.J. McIntosh
M.H. Hyland
J.B. Metson
Light Metal Research Center, University of Auckland,
Auckland, New Zealand
e-mail: proffzee@yahoo.com
G.J. McIntosh
J.B. Metson
School of Chemical Sciences, University of Auckland,
Auckland, New Zealand
index, loose bulk density, BET surface area, loss on ignition,
sodium oxide content, silicon oxide and the concentration of
other impurities. The quality of alumina is vital to a smel-
ter’s endeavor to meet production targets, metal purity,
energy efficiency and environmental benchmarks.
Smelters fitted with GTCs specify alumina with optimum
surface area for maximized capture of fluoride fumes.
However, without pore size distribution data on the speci-
fication sheet, the BET surface area alone is misleading and
insufficient for predicting alumina performance in a GTC.
The importance of the presence of accessible pores has been
highlighted by earlier researchers [1] who unanimously
assert that the smallest pores may pose kinetic limitations
during dry scrubbing. McIntosh et al. [2] have demonstrated,
by modeling the evolution of the pore size distribution of
industrial and laboratory fluorinated aluminas, that pore
blocking and inhibition due to surface-diffusion are
responsible for the depletion of reactive sites. The authors
also posit that pores less than 3.5 nm are ineffective towards
removing fluorides from potroom exhaust gas streams and
advocate that a BJH surface area for pores >3.5 nm should
be reported on alumina specification sheets instead of an
averaged BET specific surface area.

© The Minerals, Metals & Materials Society 2017 479

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_60
480
The precipitation stage of the Bayer process (by which
SGA is produced) heavily influences the particle size dis-
tribution, whereas the calcination stage impacts the alumina
phase distribution and pore size distribution. During pre-
cipitation, the seeding, agglomeration and grain growth steps
determine the particle size distribution of the gibbsite pre-
cursor prior to calcination. However, it is also reported [3]
that depending on calcination technology, particle breakage
and attrition can produce the differences in fines content
observed between the starting gibbsite and the final SGA.
Fines are defined in the industry as particles <45 lm in
diameter. The residence time of the various gibbsite particles
and the heating rates during calcination yield a heteroge-
neous mix of agglomerates with phases ranging from gibb-
site to alpha alumina and a pore size distribution spanning
nano- to macro-porosity. Although HF capture and its effect
on the pore size distribution has been discussed [2, 4], the
evolution of pore size distribution for specific particle size
ranges have not been studied in-depth.
Coyne et al. [5] studied the influence of particle size
distribution on HF adsorption capacity on SGAs from dif-
ferent Bayer plants (three by flash calcination and one by
kiln calcination). The samples were sieved into +150, +125
to −150, +106 to −125, +75 to −106, +45 to −75 and +20 to
−45 µm fractions. The samples were reacted with 155 mg/
Nm3 HF in a fixed bed reactor at 120 °C for a one-hour
period and subsequently characterized for BET surface area,
alumina phases (c, D, h, v, a), surface acidity, MOI
Fig. 1 Fluoride adsorption
versus mean particle size for flash
calcined SGA (left) and kiln
calcined SGA (right) [5]
G.E.K. Agbenyegah et al.
(moisture on ignition), LOI (loss on ignition) and residual
soda content (Fig. 1).
Irrespective of calcination method, the 106 to −125 µm
fraction showed a maximum fluoride adsorption. The
authors found that only the MOI content of the various
particle size fractions followed a similar trend as fluoride
adsorption and showed a maximum F adsorption for the 106
to −125 µm fraction. Coyne et al., however, could not
explain why water easily removed by heating SGA to
300 °C i.e. MOI (25–300 °C) is highest in a particular
particle size fraction and its apparent correlation with the
amount of HF adsorbed. Interestingly, the fines (−45 to
+20 µm) consistently captured the least amount of F per unit
surface area.
Increased content of fines in SGA is known to be
responsible for a myriad of challenges in a smelter, including
dusting [6], reducing air-slide system capacity [7], anode
cover/crust collapse [8], alumina dosage, dissolution prob-
lems and increased anode effect frequency [9]. The inclusion
of under-calcined (gibbsitic) electrostatic precipitator
(ESP) dust in the final SGA product has been observed to
correlate with a bi-modal pore size distribution, high BET
surface area and increased HF generation [1]. Some calcin-
ers, by design and operation, may generate over-calcined
ESP dust which is expected to lower the BET surface area of
the bulk SGA upon inclusion.
With segregation and attrition taking place as primary
alumina is transported from port to pot, the impact of fines
Fluoride Capture Capacity of SGA: The Interplay Between … 481

on the performance of the dry scrubber also needs to be
reassessed.
Experimental Method
Breakthrough experiments for this study were carried out in
a lab scale scrubber. The reactor is a cylindrical stainless
steel column (16.5 cm height  1.5 cm diameter) with an
HF-resistant fluoropolymer coating. Sieved fractions of
smelter grade alumina were reacted with dry HF gas at a
temperature of 100 °C. The fractions are as follows:
• −45 lm
• +45 to −63 lm
• +63 to −90 lm
• +90 to −125 lm
• +125 lm
Results and Discussion
XRD patterns of SGA fractions in Fig. 2 indicate that alpha
content increased as particle size decreased.
Results published by earlier investigators [9] exhibit a
similar trend. Breakthrough curves (reactor exit concentra-
tion versus time) for the reactions of HF with the particle
size fractions are shown in Fig. 3.
It is evident from the breakthrough plots that the sub
45 lm particles captured the least amount of fluoride before
reaching breakthrough point. Generally, the particles
>63 lm perform to about the same extent in terms of F
captured. The table below shows the BET specific surface
area (SSA), cumulative pore volumes and the amounts of

One gram (1 g) of sieved Al2O3 fraction was reacted with

320 mg/Nm3 (*400 ppm) of HF until the breakthrough
point is attained, where the supply rate of the anhydrous HF
exceeds the rate of reaction up to *10 ppm. An excellent
signal-to-noise ratio is achieved at 10 ppm, hence the
specification of the number as the breakthrough concentra-
tion. HF concentration was continuously monitored by a
Boreal Laser™ tunable diode laser (TDL) in a Teflon-coated
gas cell. The path length of the gas cell is 20 cm. Reaction
temperature was 100 °C. A starting sample of alumina with
particle size ranging from +45 microns to −125 microns with
0.03% of −45 lm particles was utilized in a second set of
experiments. Incrementally, 10, 20, 30 and 40% of fines Fig. 2 XRD scan of sieved alumina particle fractions
(−45 µm grains) were added to the starting Al2O3 material.
The experiments were carried out with 320 mg/Nm3 HF. All
400
reactions were maintained at 100 °C. +125 micron +90 -125micron
+63 -93micron +45 -63micron
350 -45 micron
HF ConcentraƟon (mg/Nm3)

Characterization 300
Increasing parƟcle diameter
250
The fluorinated aluminas were characterized for surface area Increasing F uptake
and pore size distribution by N2 adsorption with a 200
Micromeritics Tristar 3000 equipment. The isotherm data
was subsequently utilized for constructing the pore size 150
distribution and modeling of the pore size evolution with
100
fluorination. Particle size fractions were confirmed after
mechanical sieving with a Malvern Mastersizer 2000 50
equipment. Phase identification and X-ray patterns of the
alumina fractions were obtained with a Panalytical™ 0
0 10 20 30 40 50 60
Empyrean diffractometer. A KRATOS® Axis Ultra X-ray
Time (mins)
photoelectron spectrometer (XPS) equipment was employed
for collecting chemical state information about the reaction Fig. 3 Breakthrough curves for reaction of HF gas with various
product formed on the alumina surface. alumina fractions
482 G.E.K. Agbenyegah et al.

Table 1 Results of surface SGA fractions (lm) Cumulative pore vol. Primary Fluorinated F captured
property changes with HF (cm3/g nm) BET SSA (m2/g) BET SSA (m2/g) (wt%)
reaction
−45 0.17 58 48 0.1
+45 to −63 0.18 63 62 0.2
+63 to −90 0.20 65 64 0.6
+90 to −125 0.20 67 65 0.7
+125 0.20 70 68 0.7

Fig. 4 a–e Pore size distribution -45micron Alumina FracƟon +45 - 63micron alumina fracƟon
of SGA fractions, primary and 0.01
0.012
reacted (fluorinated)
Pore Volume (cm3/g-nm)

0.009 Primary
0.008 a
b
0.01 Primary
Reacted

Pore Volume (cm3/g-nm)

0.007
0.006 0.008 Reacted
0.005
0.006
0.004
0.003 0.004
0.002
0.001 0.002
0
1 10 100 0
Pore Width (nm) 1 10 100
Pore Width (nm)

+63 - 90micron Alumina FracƟon +90 micron Alumina FracƟon

0.014
0.014
0.012
Primary 0.012
c
Pore Volume (cm3/g-nm)
d
Pore Volume (cm3/g-nm)

0.01
0.01
Reacted Primary
0.008
0.008
0.006 Reacted
0.006
0.004 0.004
0.002 0.002
0 0
1 10 100 1 10 100
Pore Width (nm) Pore Width (nm)

+125micron Alumina FracƟon

0.014

0.012
e
Pore Volume (cm3/g-nm)

0.01
Primary
0.008
Reacted
0.006

0.004

0.002

0
1 10 100
Pore Width

fluoride scrubbed at breakthrough for the individual particle breakthrough experiments, where fines are increasingly
fractions. added to the primary SGA. The following diagrams (Fig. 4
It is noteworthy that the BET SSA and cumulative pore a–e) show the pore size distribution of the different SGA
volume of sub 45 lm particles was the least when compared fractions (primary and fluorinated).
with the remaining fractions (Table 1). An equally instruc- The −45 lm particles have *15% less total pore volume
tive observation is the significant reduction in BET SSA of than the remaining fractions investigated (Fig. 5) which is
the fluorinated sub 45 lm fraction although it underwent the one of the probable reasons for the poor performance of the
least exposure to HF gas. The reason for the low HF capture fraction. It is also noteworthy that the fines fraction are likely
by the fines will be better explained with results of to include over-calcined super-fines (particles less than
Fluoride Capture Capacity of SGA: The Interplay Between … 483

Prim -45micron a
400
CumulaƟve Pore Volume (cm3/g-nm)

0.2 Prim+45 -63 micron

350

HF ConcentraƟon (mg/Nm3)
Prim +63 - 93 micron
300 Zero fines
Prim +90 - 125micron
0.15 10% fines
Prim +125micron 250
20% fines
200
30% fines
0.1
150 40% fines
50% fines
100
0.05
50

0 0
1 10 100 0 20 40 60 80 100
Pore Width (nm) Time (mins)

Fig. 5 Cumulative pore volumes of primary SGA fractions

b
40
20 lm) which were neither quantified nor analyzed for the 35 Zero fines
purposes of this study. HF ConcentraƟon (mg/Nm3)
10% fines
30
20% fines
25
30% fines
Incremental Fines Addition
20 40% fines
The presence of excessive fines in the primary SGA injected 15 50% fines
in GTC reactors and its ramifications for fluoride scrubbing
10
efficiency is sparsely documented. Smelters have managed
segregation and attrition by transporting alumina from the 5
port to silos by angled air-slides and by trucks. 0
Anti-segregation systems have been developed to mitigate 0 20 40 60 80
the impact of silo filling and emptying on the accumulation Time (mins)
of fines. For injection type scrubbers, fines in the primary
adsorbent SGA may change the dynamics of the alumina-HF Fig. 6 a Breakthrough curves for HF reaction with SGA of varying
reaction. Chandrashekar et al. [10] published data collected fines content. b Breakthrough curves showing the early inception of
breakthrough for high fines samples
from a smelter that showed that increase in fines content of
alumina directly resulted in increased emission of particulate
and gaseous fluorides. In order to ascertain the influence of fines in the bulk SGA
As earlier-mentioned, fines in SGA may be under- injected into the GTC reactor, breakthrough experiments were
calcined gibbsite which would increase hydroxyl content performed with increasing levels of fines in the adsorbent
resulting in increased continuous HF generation [11]. SGA. Breakthrough curves for the reactions are shown in
Gibbsitic fines possess not easily-accessible porosity, Fig. 6a, b (inlet [HF] = 320 mg/Nm3, T = 100 °C).
thereby making it more challenging when the same SGA A glass column of similar dimensions as the
with an over-estimated BET SA is also utilized in the GTC Teflon-coated steel reactor was used to observe the
as scrubbing material. When SGA fines are predominantly fluidization patterns/regimes of the increasing fines samples.
over-calcined alpha phase alumina, a low BET SA constraint Bed heights and minimum fluidization velocities were also
tends to limit the amount of fluoride that can be captured measured. N2 gas at 25 °C was the fluidizing gas.
with respect to the GTC kinetics. Notwithstanding the pre- Some effects of increased fines in the adsorbent alumina
dominant alumina phases (gibbsite or alpha) present in SGA are immediately obvious from the breakthrough curves
fines, powder fluidization issues such as minimum fluidiza- (Fig. 6). With the exception of the 10 and 20% fines sample,
tion velocity, flowability, dense phase voidage and pressure it is seen that reactor exit HF concentration does not stabilize
drop issues still pertain and could impact the scrubbing at zero during the reaction with the 30, 40 and 50% fines
efficiency. samples. As fines content increases, exit HF concentration
484
Increasing
fines
Fig. 7 Geldart chart [13]. The superimposed arrow shows changing
powder characteristics with increasing SGA fines content
reaches a value greater than zero significantly earlier and
steadily rises to attain the breakthrough value.
The 10% fines content sample performed better than the
zero fines sample even for repeat runs. It is likely that the
increase in particle number presents more reaction surface
area, hence the better performance translating to longer
breakthrough times. It is also suggested by Zenz and Othmer
[12] that fines acts as lubricants or miniature roller bearings
that assist the shear of coarser particles thereby lowering the
effective dense phase velocity.
Figure 7 shows the direction which increasing fines in
SGA would follow on a Geldart chart [13]. It was observed
during the fluidization experiment that the increase in fines
content progressively causes the alumina to change in flow
character from sand-like to cohesive. As the alumina
becomes more cohesive, increased inter-particle forces
reduce fluidization performance [14], resulting in the entire
bed being lifted as a bed or channels being created for ex-
iting unreacted HF gas. In a smelter, a similar situation may
be present when large quantities of SGA fines are introduced
into the GTC reactor to scrub the HF-laden pot exhaust
gases.
Occasionally, hikes in the fines content of primary SGA
are recorded as a result of attrition during transport and
handling or as a result of silo inventory management prac-
tices. This is likely to have the consequence of intermittent
increases in GTC stack emissions. The fluoride loading
estimated from the fines addition work show that up to
*65% of the scrubbing capacity can be lost as a result of the
presence of 50% fines in the bulk SGA (Fig. 8).
G.E.K. Agbenyegah et al.
1.60
Flouride captured (wt%)
1.40
1.20
1.00
0.80
0.60
0.40
0.20
0.00
0 10 20 30 40 50 60
Fines content (%)
Fig. 8 Fluoride loadings of SGA with varying fines content
Interplay Between Pore Size and Particle Size
Distribution of SGA
XRD analyses of the particle size fractions showed that three
alumina phases were consistently present in varying per-
centages, namely—gamma, theta and alpha alumina
(corundum). The breakthrough curves and the pore size
distribution measurements showed that the fines had the
greatest impact on the scrubbing capacity of the SGA, with
increasing fines lowering scrubbing capacity.
The mechanisms by which fines are generated differ from
refinery to refinery depending on the precipitation and cal-
cination technologies. Within smelters, attrition and segre-
gation during transport, handling and storage are the
common mechanisms for fines generation. The fines used for
this study contained mostly alpha alumina which have been
earlier characterized [15] and shown to possess larger
average pore width, lower total pore volume and lower
BET SA than the remaining fractions that were studied.
From Fig. 5, the lower cumulative pore volume of the fines
in the pore width between 1 and 10 nm lends credence to the
XRD results (Fig. 2) that the bulk of the fines are
over-calcined alumina. The pore size distribution plot in
Fig. 8 also shows the marginal reduction in pore volume as
fines are increasingly added (Fig. 9).
Although the pore size distribution of +45 to −63 lm
fractions was comparable to the fractions of larger particle
size, the amount of fluoride captured was as low as the
amount captured with the sub −45 lm (Table 1). This
observation cannot be explained with the available results.
Additional characterization, particularly MOI/LOI and
acid/base sites concentration of the fraction, would be ben-
eficial for understanding the cause of the low fluoride cap-
ture at breakthrough. It is expected that fines generated by
Fluoride Capture Capacity of SGA: The Interplay Between …
0.014
10% fines
0.012 20% fines
30% fines
Pore volume (cm3/g-nm)
0.01 40% fines
50% fines
0.008 zero fines
0.006
0.004
0.002
0
1 10 100
Pore Width (nm)
Fig. 9 Pore size distribution of primary SGA of varying fines content
particle breakage during post-refinery transport and handling
would maintain the pore size distribution and surface
chemistry of the parent particles. In this respect, it is likely
that the +45 to −63 lm particles may undergo attrition and
also contribute also to poor scrubbing performance of the
fines fraction.
Particle size fractions greater than 63 lm generally
exhibited same levels of HF scrubbing capacity. This is
traceable to the similarity in pore size distribution and total
pore volume. Generally, pore size distribution of SGA cal-
cined with the same technology is expected to have similar
pore size distribution unless blending with ESP dust, for
example, is a process consideration towards reducing dust
inventory.
Conclusion
A study of the pore size distribution of −45, +45 to −63, +63
to −90, +90 to −125 and +125 lm fractions of SGA has
been carried. The pore size distribution were not different for
the fractions in terms of the width and mode of the distri-
bution except for the −45 lm which exhibited low pore
volumes for the 1–10 nm pore size range. The fractions
predominantly consisted of alpha, gamma and theta phase
alumina. After reacting the SGA fractions with dry gaseous
HF, the fines were seen to perform the poorest in terms of
scrubbing capacity.
The results of an incremental fines addition test demon-
strated that the presence of excessive fines in SGA, modified
it into a cohesive material that is not easily fluidized, thereby
485
decreasing its effective contact with HF gas for optimal
scrubbing performance.
Fines are generally undesirable throughout a smelter due to
the attendant challenges with transport, dusting, dosage and
dissolution in bath. The outcome of this study makes yet another
argument for the minimization of the fines content of SGA.
Acknowledgements The authors are grateful to Hydro Aluminum AS
for permitting the use of data from a related project for this publication.
We also wish to thank Dr. Are Dyroy for his invaluable guidance in
writing this paper.
References
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on reaction with gaseous hydrogen fluoride. Langmuir 31(19),
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Assessing the role of SGA porosity in the HF scrubbing
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(Reinhold, New York, 1960)
13. D. Geldart, Types of gas fluidization. Powder Technol. 7(5), 285–
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 Predictive Formula for the Competitive
Adsorption of HF and SO2 on Smelter Grade
Alumina Used in Dry Scrubbing Applications

Stephen J. Lindsay, Neal R. Dando, and Stephan Broek

Abstract
Smelter grade alumina (SGA) is the preferred agent for recovering HF from pot exhaust
gases since the alumina also serves as feed to the electrolysis process, thereby allowing
return of the recovered fluoride to the process. This alumina-based recovery loop includes
sulfur that evolves from cells as SO2 and that is co-adsorbed on SGA that is not completely
saturated by HF. Previously, Dando and Lindsay (Light Met Miner Met Mater Soc 527–
531, 2016, [1]) reported on the competitive adsorption of HF and SO2 on smelter grade
alumina by investigating the temporal breakthrough behavior of both HF gas and SO2 gas
to quantify the mechanisms behind adsorption of both gases on the same particle of
alumina. In this paper follow-on work is presented where this research data is translated
into an empirical formula that can be used by engineers and technologists. Examples are
given of applications that may be practical in making predictions on the removal of SO2 by
alumina in a dry scrubber.

Keywords
Primary aluminum Adsorption Hydrogen fluoride Sulfur dioxide Dry scrubbing
Empirical formula

Introduction Lacroix of Pechiney who patented a similar device based on

In most primary aluminiums smelters the off gases from pots
and from anode baking furnaces, are cleaned in a dry
scrubbing process using SGA as the adsorbing agent. Over
60 years ago [2] two engineers almost simultaneously
patented the use of alumina for dry scrubbing of acid gases.
The first was Mr. Robert T. Pring of Wheelabrator
(September 1956) and one month later it was Mr. Séraphin
S.J. Lindsay
Alcoa Inc., 302 North Hall Road Mail Stop S-29, Alcoa, TN
37701-2516, USA
N.R. Dando
Alcoa Inc. (retired), 100 Technical Drive, Alcoa Center, Alcoa,
PA 15069-001, USA
S. Broek (&)
Hatch, International Tower, Al Karamah Street, Capital Centre,
Abu Dhabi, UAE
e-mail: stephan.BROEK@HATCH.COM
a fluid bed reactor. In 1957 the industrial design was
advanced by researchers at Alcoa who found ways to acti-
vate alumina and create an even larger number of active sites
for the adsorption of hydrogen fluoride gases. This led to the
development of the R-173 dry scrubber that by 1969 had
evolved to the A-398 technology.
Later research showed that the active sites on the SGA
not only reacted with hydrogen fluoride but also adsorbed
other gases such as sulfur dioxide (SO2). One researcher that
investigated this was William D. Lamb of Alcan who pub-
lished this work in Light Metals in 1979 [3]. According to
the recent work by Dando and Lindsay [1], reacted SGA at
commercial aluminum smelters typically contains *0.2–0.3
wt%S and *1.8–2.2 wt%F.
Because smelters are subject to emission limits for SO2,
there always has been an interest to develop better options to
control SO2 emissions. The ability of SGA to co-absorb SO2
was further investigated by GE (the former ABB Alstom

© The Minerals, Metals & Materials Society 2017 487

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_61
488
Power). GE technologists proposed a concept in which they
tried to separate an SO2 rich stream from reacted alumina in
order to create the opportunity for a compact SO2 scrubbing
process in combination with dry scrubber technology [4].
While this development in principle was very promising, the
pilot-scale application of desorbing SO2 from SGA by
exposing it to heat did not give the envisioned results and
developments halted. As of today, we still manage SO2
emissions using conventional technologies such as wet
scrubbers using seawater, lime or caustic soda.
However, this paper will show that the insights and
experiments by Dando and Lindsay create opportunities to
help smelter operators manage sulfur emissions in new
ways. Also, a tool is added to this fundamental work that
enables engineers and technologists to make reasonable
predictions on the capture of SO2 on SGA.
Prior Experimental Work
The reader is referred to the work of Dando and Lindsay [1]
for experimental data and results on the competitive ad-
sorption between HF and SO2. While minimizing repetition,
it is important that some key results are shown in this paper
so that we can establish a proper link and foundation for the
further development of this work.
The experiments included individual, sequential and
simultaneous adsorptions of HF and SO2 on SGA that were
performed under a laboratory hood. The fluidized bed
lab-scale scrubber was operated in a batch manner where
weighed aliquots of SGA were loaded on to a PFA (per-
fluoroalkoxy) filter supported by a PFA grid in the bottom of
a vertically oriented, temperature controlled PFA scrubber
body. HF and SO2 concentrations were monitored in real
time using an external gas cell with an open-path laser HF
monitor and an internal gas cell based optical SO2 monitor.
The objective was to characterize the temporal breakthrough
curves of both SO2 and HF.
In one set of experiments it was established that HF
adsorption is dominant. SGA that was preloaded (to satu-
ration) with SO2 exhibited an HF adsorption profile identical
to SGA that was not pre-exposed to SO2.
A further experiment showed that SO2 could be loaded to
0.49 wt% (expressed as S) while HF can be loaded to
2.14 wt% (expressed as F) or 2.54 wt% depending on the
type of SGA. This shows that SGA exhibits a greater
capacity for HF. This observation is likely the result of the
molecular size difference between SO2 and HF (*6:1) [5,
6].
The most practically relevant experiment is that where
unloaded SGA is simultaneously exposed to both SO2 and
HF gas. This represents conditions under which dry
S.J. Lindsay et al.
Fig. 1 Temporal co-adsorption of HF and SO2 on SGA (Dando and
Lindsay [1])
scrubbers are operated. The results of these experiments are
shown Fig. 1.
There are several observations to be made:
1. In the first 35 min there is no competition. Both HF and
SO2 adsorb to the SGA.
2. After 35 min all the readily available active sites are
taken and HF begins to desorb SO2.
3. The inlet SO2 concentration is 100 ppm. At after 35 min,
the outlet concentration is actually higher (*125 ppm)
due to the cumulative effect of inlet SO2 and SO2 that is
desorbing from the SGA surface. Eventually this drops to
a steady reading of 100 ppm showing that no new SO2 is
adsorbing on SGA and all adsorbed SO2 has been
desorbed.
4. The response of HF gas is as expected. It shows a normal
breakthrough point (*2.3 wt%), indicating that HF ad-
sorption is not hampered in any way by SO2.
In actual plant operations, the SGA feed rate to the dry
scrubber filter modules is normally balanced so that there is
more adsorption capacity available. If this balance is prop-
erly maintained, then typical values of reacted SGA are in
range of about 1.8 wt%F. This leads to the question if SO2
can remain adsorbed on the surface, or not.
Another experiment was to preload SGA with HF to
specific values and then to expose it to SO2 to see the
response. This is shown in Fig. 2.
Figure 2 shows that for certain pre-loadings of HF, SO2
can co-adsorb. This observation means that if the HF amount
adsorbed on SGA active sites is low, the SGA can load up
remaining actives sites with SO2. Later it will be demon-
strated that this is very useful for the application of alumina
scrubbing where lean HF concentrations exist in the gas like
in anode baking.
Predictive Formula for the Competitive Adsorption … 489

Loading of S and F on alumina

Dando & Lindsay data set
1.00

Loading of S on alumina (%)

y = 0.5324e-1.036x
R² = 0.996

0.10
0 0.25 0.5 0.75 1 1.25 1.5
Loading of F on alumina (%)

Fig. 2 Temporal SO2 breakthrough behavior for as-is and HF Fig. 3 Correlation of the amount of SO2 adsorbed as function of the
preloaded SGA (Ref. Dando and Lindsay [1]) amount of HF adsorbed on

SO2 Adsorption as a Function of HF

Adsorption
Loading of S and F on alumina
Based on the observations we can assume that HF gas dic- Lamb data set
1.00
tates what happens when both gases are in contact with Loading of S on alumina (%)
SGA. This means that if one variable is set, the other will y = 0.4529e-0.517x
R² = 0.9876
follow. Based on this relationship, we investigated if there is
a correlation between adsorption of both gases. 0.10
The following data set is considered [1]:

Data point wt%F wt%S

1 0.00 0.52 0.01
0 1 2 3 4 5
2 0.30 0.39 Loading of F on alumina (%)
3 0.60 0.30
4 1.20 0.15
Fig. 4 Correlation of the amount of SO2 adsorbed as function of the
amount of HF adsorbed on SGA based on the dataset from Lamb
When this data is applied in a regression, the following
chart is derived.
For an empirical formula to describe this correlation over
Figure 3 shows that there is a logarithmic correlation
the range of F and S loadings and also the specific surface
between the two parameters. Using this equation, we can
areas, the following equation is proposed:
make predictions on what levels of SO2 removal we can
S ¼ 0:50
eð1
F
72Þ
expect in certain applications. As
ð1Þ
Lamb also collected experimental data [3]. From his work
we derive the following data set: with:

Data point wt%F wt%S S wt%S loaded on the SGA

F wt%F loaded on the SGA
1 0.00 0.48
AS m2/g of the applied SGA
2 0.95 0.29
72 m2/g of the reference SGA
3 1.50 0.18
4 4.00 0.06 In order to verify that this model agrees with the exper-
imental data, the following plot is developed (Fig. 5).
The results shown in are in good agreement with the
When plotted on logarithmic scale (Fig. 4).
actual data and support use of the proposed empirical for-
Also here is a linear correlation found, but with different
mula to make performance predictions for industrial scale
coefficients owing to the lower specific surface (m2/g) of the
facilities.
SGA used in this work.
490 S.J. Lindsay et al.

Fresh Reacted Gas from

Parameter Unit GTC Inlet
Loading of S and F on alumina Alumina Alumina stack
Flow Nm³/hr 1,620,000 1,634,400
Model Results Temperature °C 120 110
2.00
HF concentration mg/Nm³ 400 0.5
Loading of S on alumina (%)

SO2 concentration mg/Nm³ 250 172

Alumina in stack mg/Nm³ 3.0
%F on alumina wt% - 1.46
%S on alumina wt% - 0.15
Mass flows
0.20 Alumina kg/hr - 41,197 41,192 4.90
HF kg/hr 648.00 647.18 0.82
Mo Mo
del SO2 kg/hr 405.00 124.12 280.88
de
l HF kg/ton 30.2 0.04
SO2 kg/ton 18.9 13.1
SGA with 72 m2/gr (Dando & Lindsay)
SGA with 41 m2/gr (Lamb)
Fig. 6 Mass balance for application in a GTC
0.02
0 0.5 1 1.5 2 2.5 3 3.5 4

Loading of F on alumina (%)

SO2 in roof SO2 in stack

Fig. 5 Experimental data plotted against the proposed empirical model

to predict adoption of SO2 on SGA Fresh
Anodes + S POTROOMS GTC
alumina

Next, we will look closer at some industrial applications

of our findings. Reacted alumina + SO2

Fig. 7 Recycle loop between pots and GTC

SO2 Removal in Potline Dry Scrubbers (GTCs)

If a GTC is considered, we use the following typical data as
example:
The GTC is connected to 180 pots. The pots operate at
380 kA with a cell efficiency of 93.5%. The metal pro-
duction is 21.46 t/h. Each pot is ventilated at a rate of
2.5 Nm3/s or 9000 Nm3/h. The air addition from alumina
handling and pulsing etc. is assumed to be 4.0 Nm3/s or
14,400 Nm3/h.
The system considered is the sum of all pots all the
way to the stack of the GTC. The sulfur in the pots is for
95% converted to SO2. The remaining 5% is COS that is
not removed in the GTC. In the example the pot exhaust
gases contain 250 mg/Nm3 SO2 and 400 mg/Nm3 HF.
The SGA has 60 m2/g surface area which is a more
practical value than the reference SGA used in the model
development.
The fresh alumina feed rate to the GTC is 1.92 times the
metal production, which equates to 41.2 ton/h. To simplify
the example, we discount any pre-loading of fluoride and
sulfur that takes place in the FTC. This does not change the
outcome but in a real world application should be included
in the calculations.
In order to fix the amount of HF that is adsorbed, the
outlet concentration of the GTC is set to a value of
0.5 mg/Nm3. This value is consistent with actual plant val-
ues and even if this value is different the impact is negligible
and the overall result is unchanged.
The loading of HF is 1.46 wt%F. The associated loading
of SO2 is then 0.15 wt%S. Based on the mass balance
(Fig. 6), the overall SO2 removal is thus 30 wt%.
Unfortunately, there is no net result because once the
reacted alumina is fed to the pots, the SO2 is released again
and caught in the exhaust that brings it back to the GTC.
This cycle is shown in Fig. 7.
A small amount of SO2 is lost through the roof ventilators
but the majority remains in the cell exhaust gases. This
elevates the SO2 concentration that reaches the GTC; how-
ever, on a mass flow basis the incoming sulfur in pots is
equal to the loss through the roof ventilators plus the loss
from the GTC stack. Therefore, SGA adsorption has no real
net effect on SO2 in this application.
One other aspect would be to consider increasing the fresh
alumina flow to establish a larger capture of SO2. However,
this is not an option here as the total alumina flow is directly
coupled to the production of metal. No sustainable variations
are possible without causing an SGA deficit or surplus.
Impact of Cascade Feeding of Alumina
in GTCs
In the ongoing search for a smarter solution for SO2
scrubbing technologies, one invention may have a positive
side effect. We refer to the patented cascade feeding tech-
nology from Fives Solios [7].
Predictive Formula for the Competitive Adsorption … 491

Normally, the fresh alumina is split and distributed over COMPARTMENT 1 2 3 4 5

Inlet conditions
each GTC compartment individually which results in reacted Flow Nm³/hr 162,000 162,000 162,000 162,000 162,000
alumina contents of all being at the 1.5–1.8 wt%F level. This HF mg/Nm³ 400 400 400 400 400
SO2 mg/Nm³ 250 250 250 250 250
means that the alumina is quite saturated with HF when in
contact with the raw gases. Cascade feeding is the principle HF kg/hr 64.80 64.80 64.80 64.80 64.80
SO2 kg/hr 40.50 40.50 40.50 40.50 40.50
of adding fresh alumina to the first filter compartment and Fresh Alumina kg/hr 20,602 20,683 20,845 21,077 21,360
Reacted Alumina kg/hr 20,683 20,845 21,077 21,360 21,697
then passing all alumina on to the next and so on until it F-load wt% 0.30 0.59 0.87 1.15 1.42
reaches the last compartment in a row. The original objective S-load wt% 0.10 0.19 0.23 0.18 0.14
Outlet conditions
of cascade feeding was to create a net reduction in HF Flow Nm³/hr 163,440 163,440 163,440 163,440 163,440
emissions. This concept is illustrated in Fig. 8. HF mg/Nm³ 0.20 0.20 0.20 0.30 0.50
SO2 mg/Nm³ 1 2 155 371 340
Given the empirical formula between fluoride and sulfur Al2O3 mg/Nm³ 3 3 3 3 3
loading, this also means that the SGA in the first compart- HF kg/hr 0.03 0.03 0.03 0.05 0.08
SO2 kg/hr 0.20 0.40 25.31 60.59 55.65
ments removes more SO2 than the last one. Since the SO2 is Al2O3 kg/hr 0.49 0.49 0.49 0.49 0.49
carried over into the compartments in series, the filter outlet SO2 removal wt% 99.50 99.00 37.51 (49.60) (37.40)

concentration of SO2 increases. The net effect is the same on

Fig. 9 Mass balance of 5 compartments using cascade feeding of
a mass flow basis but in cascade feeding the final compart- alumina
ment has proportionally more SO2 than the others (Fig. 9).
The idea is that the flow from the last compartments only
6 x 163,440 Nm³/hr 4 x 163,440 Nm³/hr
is directed to a SO2 scrubbing system as opposed to the full (60%) (40%)
flow of gases from a GTC. If the achieved removal of SO2
1 2 3 4 5
meets a desired target, then this could become a cost effec-
tive solution. 6 7 8 9 10
In this example the 180 pots are connected to a GTC with
a total of 10 filter compartments. Typically, there are 2 series
of 5 compartments so in this case it is assumed that the fresh
alumina is distributed of both sides with 5 compartments.
Our empirical formula shows that the first three com-
partments have virtually no SO2 in the outlet. Due to cascade Fig. 10 New concept for SO2 scrubbing in conjunction with a GTC
feeding the SO2 is shifted to the last two compartments that is provided with cascade feeding of alumina
where the concentrations are actually higher than the raw gas
inlet concentrations. This explains why the SO2 removal
efficiency is negative. study is required but at first glance this can lead to consid-
The significance of this is that a new technical concept erable cost savings if SO2 scrubbing must be applied.
can be considered for the application of SO2 scrubbing in If 40% of the gases are treated in a SO2 scrubber with
connection with a GTC. This is shown in Fig. 10. 93% removal efficiency, then the overall removal of SO2 is
Because the SO2 gases are concentrated in only 40% of about 80%.
the gases on one end of the GTC, the last compartments can Or, in a case where only a small reduction is required, if
be connected to a single SO2 scrubber that now only has to only 20% of the gases are treated in a SO2 scrubber with
scrub 40% of the total gases. A full technical feasibility 93% removal efficiency, then the overall removal of SO2 is
about 40%.

SO2 Removal in ABF Dry Scrubbers (FTCs)

Another application of alumina dry scrubbing is found at the

Fig. 8 Process schematic of cascade feeding of alumina
anode baking furnace (ABF). The fumes contain both HF
and SO2 gases as a result of the process of baking anodes. In
a so-called fume treatment center (FTC) the gases are con-
ditioned with water and then scrubbed with alumina.
The ratios of SO2 and HF are very different in the fumes
from the ABF. The fumes typically contain 200–
1000 mg/Nm3 of SO2 while the HF concentrations are
around 100 mg/Nm3 [8].
492 S.J. Lindsay et al.

When the SGA is added to the filter compartments it

scrubs the HF gases but because the amount of HF is rela- SO2 Removal as function of
tively low, the majority of active sites remain available on Alumina Feed Rate and HF Inlet
the SGA to adsorb SO2. So by default the FTC also removes Concentrations
some SO2.
70%
To demonstrate this application, we consider the fol-

SO2 Removal Efficiency (%)

60%
lowing example (Fig. 11).
HF Inlet
The SGA is also here 60 m2/g. The SO2 inlet is 50%
(mg/Nm3)
750 mg/Nm3. The stack typically contains 0.3 mg/Nm3 of 40%
50
HF. Alumina feed is small and kept at 3.5 ton/h. 30% 100
Figure 11 shows that 38% of the SO2 is removed. It is 20% 150

adsorbed to the alumina and taken to the potrooms where it 10%

is either directly fed to pots or mixed in with the fresh alu-
0%
mina fed to the GTCs. In all cases the SO2 attached to the 2000 2500 3000 3500 4000 4500 5000
alumina enters the pots where it becomes part of the exhaust Fresh Alumina Feed Rate (kg/hr)

gases, or it is released in the GTC filter compartments and

taken to the stack directly. There is no net scrubbing effect;
all SO2 removed in the FTC is released again but in a dif-
ferent place.
It must be noted that tars and other hydrocarbons are
absorbed on the surface of the SGA. This will reduce the
number of active sites. The model does not compensate for
that; however, modern firing systems produce very clean
fumes that enables the use of the model in those applications
without having to make corrections for the loss of active
sites. This may be an area for future improvement of the
model.
This can still have a practical application in case a smelter
has a limit on the SO2 concentration in the FTC stack.
Aluminium Bahrain is one such example [8]. It is reported
that they have a limit of 500 mg/Nm3 of SO2 in the stack. In
the same article is described how Alba had to manage var-
ious process parameters of the baking process in order to
meet this limit.
Knowing how alumina interacts with the HF and the SO2,
there is now another way available to manage the stack
Fig. 12 SO2 removal vs alumina feed rate at various HF
concentrations
emissions of SO2. With this knowledge, estimates can be
made to vary the flow of fresh alumina to optimize the
scrubbing of SO2 at the FTC. And while the net result is the
same, taking the SO2 from the FTC to the GTC may solve
issues where a location has stack-specific concentration
limits for SO2.
Using different input parameters, the following plot can
be produced for the example (Fig. 12).
By allowing additional fresh alumina to enter the FTC,
higher stack SO2 concentrations can be mitigated. And
because all HF is already adsorbed, the additional SGA will
almost exclusively adsorb SO2. The reacted SGA from the
FTC is taken to the GTC without compromising HF scrub-
bing capacity. This option is more a question of feed rate
capacity constraints, because older FTCs have usually lesser
spare capacity available, which means that some equipment
modifications may be required.

Gas from
Gas from Fresh Reacted Gas from
Parameter Unit Cooling
ABF
Tower
Alumina Alumina stack Conclusion
Flow Nm³/hr 100,000 105,000 110,000
Temperature °C 175 105 108
The work reported by Dando and Lindsay opens new
HF concentration mg/Nm³ 100 95 0.3 opportunities and ways to manage sulfur emissions in
SO2 concentration mg/Nm³ 750 714 425
Alumina concentration mg/Nm³ 0 0 5
smelters. By collaboration, a novel empirical formula has
been developed that can be used as a tool by engineers to
%F on alumina wt% 0 0.268
%S on alumina wt% 0 0.400
look into process concepts that until now were hard to pre-
dict. Experimental data, including that from Lamb’s work in
Mass flows
1979, correlates well with the proposed formula. However, it
Alumina kg/hr - - 3,500.0 3,537.7 0.55
HF kg/hr 10.00 10.00 0.03 should be regarded as a start and the hope is that also others
SO2 kg/hr 75.00 75.00 46.72 see opportunities to continue this work so that eventually it
SO2 removal wt% - - 38
may lead to even more new insights that can be used to
Fig. 11 Mass balance of a FTC dry scrubber showing the effect of optimize further the process in aluminium smelters.
alumina on SO2 gas
Predictive Formula for the Competitive Adsorption …
Acknowledgements The authors would like to thank Alcoa’s Primary
Metals and Hatch for encouraging publication of environmental
research and applied sciences.
References
1. N.R. Dando, S.J. Lindsay, The competitive adsorption of HF and
SO2 on smelter grade alumina. Light Metals, The Minerals, Metals
& Materials Society, 527–531 (2016)
2. S. Broek, M. Hyland, S. Lindsay, D. Wong, Control of potline
scrubber & fugitive emissions for aluminium smelters course,
module 4A: historical facts of GTC technologies. The Minerals,
Metals & Materials Society, (2016)
3. W.D. Lamb, The role and fate of SO2 in the aluminium reduction
cell dry scrubbing systems. Light Metals, The Minerals, Metals &
Materials Society, 889–897 (1979)
493
4. S.O. Strømmen, E. Bjørnstad, G. Wedde, SO2 emission control in
the aluminium industry. Light Metals, The Minerals, Metals &
Materials Society, 962–967 (2000)
5. K.A. Jensen, Almen. Kemi I., Jul., Gjellerups Forlag, Kobenhavn
(1965)
6. R.C. Reid, J.M. Prausnitz, T.K. Sherwood, The Properties of Gases
and Liquids (McGraw-Hill, New York, 1977), p. 629
7. H. Vendette, N. Dando, A. Moras, E. Marion, W. Xu, Alumina
dry-scrubbing technology: development of a cascade feeding system
for improved capture efficiencies. Light Metals, The Minerals,
Metals & Materials Society, 189–194 (2007)
8. H. Abbas, K. Khaji, D. Sulaiman, Desulphurization control during
baking: its impact on anode performance and operational
costs-alba’s experience. Light Metals, The Minerals, Metals &
Materials Society, 1011–1014 (2010)
 Pot Gas Treatment at High Gas Temperatures

Anders Sørhuus and Sivert Ose

Abstract
HF regeneration due to submicron fluoride particles trapped inside the filter cloth reacting
with the humidity in the pot gas is one likely mechanism that explains why the HF
emissions increase with gas temperature and humidity in the dry scrubbers. A significant
temperature effect is observed and gas cooling is in many smelters today necessary to keep
the emissions under control. The GE heat exchanger (HEX) technology is one of the
technologies that are now built and operated in full scale several places in the world.
Results from the first full scale GTC installation document the positive effect of the cooling
for the Abart GTC technology installed. The HEX cools the temperature with more than
25 °C down to less than 110 °C and HF emissions in the range 0.2–0.3 mg/Nm3 are
measured at ambient temperatures higher than 40 °C, and high humidity.

Keywords
Gas treatment center HEX Alumina Abart

Introduction stream before abatement reduces the efficiency of HF

One of the main challenges especially in hot and humid
climates is that the HF emission increases with temperature,
and as discussed in [1] a 10 °C increase in gas temperature
can double the HF emissions. One explanation for this is that
particulate materials containing fluorides such as NaF4 from
the bath react with humidity in the air and cause HF emis-
sions inside the dry scrubber filter bag material [2] (Fig. 1).
Various means of gas cooling has therefore been devel-
oped over the past years. Each method of cooling has its
benefits and drawbacks and adds more or less cost. Proven
gas cooling systems are now available such as the heat
exchanger (HEX) technology shown in Fig. 2, and discussed
extensively in [1, 3–5]. The main benefit of the HEX tech-
nology is that no dilution air is needed to reach acceptable
temperatures during summer. Addition of dilution air
requires added dry scrubber modules, and diluting the gas
A. Sørhuus (&)
S. Ose
GE Power Norway AS, Drammensveien 165, 0277 Oslo, Norway
e-mail: anders.sorhuus@ge.com
adsorption. In addition the HEX technology allows for heat
recovery of the large quantities of waste heat presently lost
to the atmosphere.
The recovered heat can be used for e.g. heating of
buildings etc. through a district heating network or power
production. Organic Rankine Cycle (ORC) machines for
converting the heat to electric power are now either in
operation [6] or under project execution and is always a
reliable method to utilize the heat. In hot climates
desalination and chillers are main alternatives for waste
heat utilizations as discussed in [7, 8]. Heat integration
with the thermal power plant is an option especially in the
Middle East, and some concrete examples are discussed
later.
The Abart can be equipped with external heat exchangers
as shown in Fig. 2. For new Abart installations, it is rec-
ommended to integrate the heat exchangers (IHEX) directly
with the filter (see Figs. 3, 4 and 5). This reduces the costs of
installation by eliminating additional foundations, bypass
duct and dampers.

© The Minerals, Metals & Materials Society 2017 495

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_62
496
Fig. 1 Chemical regeneration of HF from the filter cake as a function
of water humidity and gas temperature [2]
Fig. 2 Externally located heat exchanger-EHEX
Fig. 3 The Abart-C dry scrubber principle
The Abart Dry Scrubber Technology
The high specific surface of alumina together with its high
affinity to HF helps to capture the HF molecules contained in
the raw gas from the pots and is a decisive factor that allows
for the HF adsorption to take place. In addition the GTCs
A. Sørhuus and S. Ose
Fig. 4 The Integrated heat exchanger-IHEX
Fig. 5 IHEX in the reactor part of a filter compartment
must be designed to reliably mix the alumina and the raw gas
as efficiently as possible without causing too much attrition
to the fragile alumina particles. Retention times, mixing
lengths, concentration and flow profiles etc. must also be
favorable to achieve optimal adsorption. In addition erosion
and scaling must also be under control, as well as minimum
energy consumption.
Within all of the above restraints, the Abart GTC tech-
nology has proven to be very reliable over time and more
than 1000 Abart dry scrubbing modules are now in daily
24 h, 7 days per week operation worldwide. The main
characteristics of the Abart dry scrubbing system are shown
in Fig. 3.
The Abart (Aluminium Best Available Recovery Tech-
nology) from GE Power is based on a two-stage, counter
current cleaning technology where primary alumina is
injected into the filter to polish the remaining HF in the pot
gas after the main portion of HF is recovered in the reactor as
shown in Fig. 3. In the reactor, the alumina from the hopper
is recirculated into the reactor to adsorb the main bulk of HF
and enrich the alumina as much as possible. In the last stage
the primary alumina with the highest adsorption efficiency is
injected directly onto the filter bag surface to remove the last
HF fraction remaining after the gas has been treated in the
reactor stage. This two-stage counter current adsorption
system secures very low emissions.
Pot Gas Treatment at High Gas Temperatures 497

The mechanical recirculation feeder in the Abart reactor into the alumina particles. In addition, the inlet HF con-
allows for a unique optimization, control and measurable centration into the GTC is an important parameter as well as
recirculation rate that can be adjusted remotely from the suitable alumina properties regarding specific surface, pore
control room. The HF emission requirements can therefore distribution, fines content etc.
be met without too high recirculation rate thereby reducing The HF saturation in the alumina leaving the GTCs are
the pressure drop in the filter, and attrition of the alumina. often close to the practical maximum levels achievable and it
The recirculation feeder is also designed to break down is therefore not excessive play room for variations. Improper
scaling lumps that otherwise could obstruct the passages of gas and alumina mixing rates, or distribution in the reactors
alumina into the reactor etc. over time. or filter cake buildup can be crucial, and must be fine-tuned
for the best results.
Figure 6 shows the excursion in emissions observed when
Heat Exchangers for Gas Cooling
stopping the primary alumina feed to compartment number 3
out of a total of four compartments at a GTC located in
The trend towards high amperage pot technology results in
Norway. The normal HF emissions are very low (measured
high pot gas temperatures. To enhance scrubbing efficiency,
lower than 0.2 and sometimes below the detection limit of
and obtain sustainable working temperatures for the filter
0.1 mg HF/Nm3. The inlet HF concentration is ranging from
bags, reduction of the gas temperature is required.
320 to 340 mg/Nm3, and the alumina saturation levels are
Several technologies are in use to cool the gas as dis-
within normal ranges. The location of these measurements
cussed in [1]. In GE’s HEX technology, the gas is cooled by
are at a smelter in a cold climate, and the absolute humidity
water/gas heat exchangers that are placed either integrated
and gas temperature is therefore much lower than normally
with the filter (IHEX) or external (EHEX). The first full scale
observed in the summer time in hot climates.
EHEX was commissioned in 2015 [5].
One particular observation in Fig. 6 is that it takes
GE HEX technology consists of a shell, penetrated by a
approximately 1–2 h after the primary alumina feed is
number of straight tubes where the gas flows through the
stopped before the emissions increase dramatically.
tubes. The pipes are encompassed by water circulating in a
The HF “sniffer” measurements in Fig. 6 are described in
closed loop. Heat is transferred from the gas to the water,
more detail [9]. This “sniffer” system is capable of mea-
through the walls of the tubes. Principally there is no differ-
suring accurately the HF emissions from each compartment
ence between the IHEX or EHEX other than that the EHEX
individually. As discussed in the paper [9] the “sniffer”
may be easier to retrofit into existing GTC duct systems.
system is capable based on adding a SO2 sensor to predict
The IHEX unit is shown in Fig. 4. The tubes are designed
and give an early warning of the excursions long before it
to facilitate low pressure drop, and avoid wear and unde-
affects the HF emissions significantly.
sirable scaling. The IHEX is integrated into each filter
In hot climates the absolute humidity will typically be
compartment below the reactor and each IHEX can therefore
higher than in cold climates, and as shown in Fig. 1 this also
be isolated from the gas flow by the filter compartment inlet
affects the measured chemical regeneration of HF even
and outlet dampers for inspection or service.
though the influence of temperature is higher. The absolute
The IHEX is built into the lower part of the reactor,
humidity can however partly explain why the emissions are
upstream (below) of the point of entry for the alumina fed
higher in hotter climates even when cooling the gas.
into the reactor, as shown in Fig. 5.
Figure 7 shows some data measured from an Abart GTC
Due to the fact that the gas flows through straight tubes at
scrubbing the pot gas from a smelter located in the Middle
the inlet of the reactor, the flow conditions in the reactor is
East during the hot and humid season.
optimized with regard to mixing of alumina/gas for the HF
adsorption process, and the efficiency increases.
In Fig. 3 secondary dry air coolers for cooling the cir-
culating water to the required temperature are integrated on
the side of the GTC structure. However, this hot water can
also be utilized in various energy recovery systems as
described separately below.

Sources of HF Emissions from the GTC

Efficient mixing of alumina and HF gas is the first step

required in order to get the optimal contact and retention
times for the HF molecules to adsorb and diffuse properly Fig. 6 Emissions measured during a forced primary alumina stop [9]
498 A. Sørhuus and S. Ose

Similarly, the data points from Fig. 6 can be added within

A116_AT_320
Expon. (A116_AT_320)
0.4
0.2
y = 0.0076e0.0325x
R² = 0.2613
0 between approx. 70 and 90%. Such relative humidity
70 90 110 130
Fig. 7 Emissions in mg/Nm3 versus temperature in °C measured
during hot season in the Middle East from July 29 to August 1, 2016
The data points in Fig. 7 corresponds to 72 h of mea-
surements from July 29 to August 31, 2016 with measure-
ments taken every 2 h.
The inlet HF gas concentration was measured with a
handheld NEO gas analyzer to 330 mg/Nm3, and the alu-
mina saturation was normal, measured to 1.5%F.
As shown in Fig. 8 the gas temperature is cooled to
temperatures similar to the levels experienced in cold climate
smelters i.e. in the range 100–110 °C.
In Fig. 9 the data points in Fig. 7 is overlayed the data
in Fig. 1 (see data points encompassed the red oval).
the blue oval. The measurements are from similar Abart
GTC’s, and operation conditions. It is interesting to note
that the data points fit quite well with Fig. 1 especially
considering that as these data are based on laboratory
measurements done under different conditions from full
scale GTCs.
For the Middle East smelter, relative humidity was
results in much higher absolute levels of water in the gas in
the Middle East compared to the typical levels in cold
climates. Absolute humidity in Middle East could be
40 g/kg or more, whereas absolute humidity in cold climate
smelter locations (assuming 15 °C) is in the range of 10
times less. This is at least an indication that the higher
humidity in hot climates could contribute also to higher
emissions.
Heat Utilization, Additional Opportunities
20–25 MW thermal heat is removed from the pot gas in the
EHEX system in Fig. 2 and is available “free of charge” as
clean hot water at up to 90 °C that can readily be transported
to potential consumers of heat such as:

• Preheating of raw materials.

150 • Absorption cooling (chiller) systems.
• Desalination and demineralization plants.
100 • Preheating of feed water for boilers etc.

50 In the Middle East region predominantly aluminium

GTC inlet gas temperature, C smelters are connected to dedicated thermal power plants
EHEX inlet temperature, C based on gas fuel. An integrated power plant located adja-
0 cent to the pot-line represents a huge potential for recovery
0 10 20 30 40 of all and much more of the waste heat from the pot gas. The
integrated nature of the power plant and the electrolysis
Fig. 8 Gas cooling during the measurements in Fig. 7
process also calls for natural synergies.
A successful integration of the waste heat requires careful
consideration of the final layout, erection sequences and
available space etc. especially for the piping required to
transport the thermal heat to and from the EHEX system. In
addition the various heat consumer possibilities at the power
plant site must match the heat source at temperature level
A116_AT_320
provided. With these limitations in mind, the GE teams for
the smelter and power plant have jointly considered the
following options for use of the waste heat:

1. Preheating of the gas for the power plant

2. Preheating of feed water for the power plant
3. Treatment and production of demineralized water
Fig. 9 Abart HF emission measurements added in Fig. 1 4. Absorption chiller for cooling
Pot Gas Treatment at High Gas Temperatures
Fig. 10 Piping for distribution of hot water from the HEX to the
power plant gas preheater
1. Preheating of the gas for the power plant
For preheating of the gas approximately 4–5 MWth of the
heat can be utilized. The preheating of the gas reduces the
low pressure steam extraction required for this purpose
proportionally. The reduced steam extraction lowers the
overall fuel consumption for the power plant corresponding
by 78  109 kJ/year of fuel. Alternatively more electrical
power can be produced, in the range of 1.5 MWel depending
on the final overall mass and energy balance for the power
plant.
The cost for implementation of this option is mainly
limited to the cost of a heat distribution system, i.e. 2 times
an Ø300 mm pipe with approximately 1000 m length, as
indicated on the drawing below. The cost of this piping
could be offset by less cost on the dump heat exchangers
presently included on the GTC, and thus minimizing the
overall cost (Fig. 10).
2. Preheating of feed water for a typical integrated power
plant in the Middle East.
Approximately 20 MWth heat from the aluminium
smelter can be used for preheating the feed water. It is
assumed a 5% conversion of the 20 MWth, equivalent to
52  109 kJ/year of fuel saving.
3. Treatment and production of demineralized water
The power plant will also use large quantities of
demineralized water for wet compression and air inlet
saturation, in total up to 20 m3/h demineralized water that
can readily be produced with a Multi Effect Desalination
unit (Fig. 11).
In the figure a MED capable of producing 50 m3/h
demineralized water based on the heat input from the IHEX
499
Fig. 11 Multi effect Desalination (MED) unit for waste heat recovery
from the pot gas [7]
system is shown. Cost including investment is estimated to
1.5 US dollar/m3 [7]. Footprint of the MED is 18  8 m.
4. Absorption chiller for cooling
Producing cooling in absorption chillers has long been a
proven and technically robust solution for utilization of
industrial heat with a broad spectre of cooling applications.
The smelter and the power plant have a multitude of cooling
requirements where this cooling could be applied. Cooling
of the inlet air to the gas turbines is one application of
absorption chillers of particular interest [10].
Cooling of buildings and MCC rooms is another area of
particular interest especially at the smelter site due to the
close distances for transporting the hot water. Up to 800 kW
thermal cooling could be required for the MCC buildings,
and a traditional compressor based chiller will require a
power consumption in the range of 250 kWel to produce this
amount of cooling. For the same cooling application an
absorption chiller based on waste heat will only consume in
the order of 25 kWel for pumps and secondary cooling.
The 4 scenarios above can give the following advantages in summary
Scenarios Fuel gas saving Fuel saving in
(kJ/year) (USDa/year)
Fuel gas pre-heating 78  109 400,000
Feed water pre-heating 52  10 9
250,000b
Demineralized water 130  10 9
650,000
production (50 m3/h)
Absorption chiller for MCC 10.4  109 50,000c
room cooling (800 kWth)
a
Assuming 5 USD/MMBTU gas
b
The investment cost depends on the final technical solution selected
for demineralizing water for the power plant, especially if the process
investments considered for this scope can be combined in this
application
c
Absorption chillers are normally higher in investment, but have longer
lifetime than compressor based chillers
As a special note to the table it should be considered that
a multitude of cooling applications could be developed and
that more of the heat should be applied for this purpose.
500
Conclusions
Modern Abart (Aluminium Best Available Recovery Tech-
nology) dry scrubbers based on two stage counter-current
alumina injection are capable to capture 99.7% of all the
fluoride entering the GTC. HF emissions from an Abart
GTCs treating the potgas from a smelter in located in the
Middle East has been compared to a similar Abart GTC
installed at a smelter located in Norway. The HF emissions
measurements are slightly higher for the smelter located in
the hot humid climate even with cooling the gas into the
GTC down to similar levels. It is suggested that this differ-
ence is a result of higher absolute humidity in hot areas.
It is shown that in both cold and hot climates low HF
emissions in the range of 0.2–0.3 mg/Nm3 are achieved. Still
some HF gas is released to the atmosphere, and can affect the
wildlife and nature surrounding the aluminium smelters that
are in many cases located in areas with a fragile ecology. For
this reason the smelters undertake extensive investigations
including collection of local vegetation and soil samples etc.
to analyze the localized fluoride impact. In some cases
undesirable effects are documented, and this is a strong
driver for even stricter emissions. In hot climates this may
only be possible with cooling of the pot gas and also a higher
understanding of the temperature dependent mechanisms
leading to the chemical regeneration of HF in the filter bags.
Gas cooling with heat exchangers not only lowers the
emissions, but also releases the potential for heat from the
pot gas to be recovered. A multitude of recovery applications
for energy recovery can be developed. Cooling systems
A. Sørhuus and S. Ose
based on chillers or desalination applications represent
markets that are obvious in the Middle East region. Inte-
grated thermal power plants are will also have the potential
to absorb all the thermal energy from the pot gas.
References
1. H.A.A. Qassab, S.S.A.A. Mohammed, G. Wedde, A. Sørhuus,
Hex retrofit enables smelter capacity expansion, in TMS Light
Metals (2012)
2. A. Heiberg, G. Wedde, O.K. Bøckman, S.O. Strømmen, Pot gas
fume as a source of HF emission from aluminium smelters
laboratory and field investigations, in TMS Light Metals (1999)
3. A. Sørhuus, G. Wedde, Pot gas heat recovery and emission
control, in TMS Light Metals (2009)
4. A. Sørhuus, G. Wedde, K. Rye, G. Nyland, Increased energy
efficiency and reduced HF emissions with new heat exchanger, in
TMS Light Metals (2010)
5. A. Sørhuus, S Ose, B. Møller, Heat exchanger facilitates recovery
of 25 MW thermal energy at Alba, in TMS Light Metals (2016)
6. A. Sørhuus, S. Ose, G. Wedde, AHEX—a new, combined waste
heat recovery and emission control system for anode bake
furnaces, in TMS Light Metals (2013)
7. A. Sørhuus, G. Wedde, D. Breschi, N. Favel, G. Girault, Integrated
desalination and primary aluminium production, in TMS Light
Metals (2012)
8. S.R. Nordtvedt, R. Stenbro, P. Finden, Study of use of absorption
technology for utilization excess/waste heat from aluminium plant
for cooling especially with regards to use in hot or tropical areas.
IFE/KRvF-20tvt43-Confidential report (2011)
9. A. Sørhuus, S. Ose, Update on the Abart Gas Treatment Center
Technology. ICSOBA (2016)
10. R. Howell, Cooling arrangement. PCT/IB2008/000353
 Influence of Handling Parameter on Powder
Properties

Peter Hilgraf, Jan Paepcke, and Arne Hilck

Abstract
Handling and conveying of powderous material needs a detailed knowledge of the powder
properties itself combined with the knowledge how the conveying and handling effects the
powder properties. Ideally there is no measurable effect on the powder. For intermediate
storage in the plant and Material Distribution Systems alongside the pot room these effects
need to be considered. In this paper the influence of various parameter of pneumatic
conveying on the material properties is described. Comprehensive tests have been done to
evaluate the influence of changes in conveying parameters on the material and vice versa.
This paper concludes technical features presented on earlier TMS Annual Meetings and
compares them with results from practice. In order to improve the handling behaviour of
poorly-flowing fine-particle bulk materials, these can be mixed with a suitable
coarse-particle and free-flowing solid. On the other hand, the flow characteristics of a
coarse material are worsened by the particle attrition and/or fracture occurring during the
handling. To determine these effects in more depth for Alumina tests have been undertaken
with systematically varied material compositions. These data are compared with material
data from other industries with the aim to give general conclusions for the material
handling.

Keywords

Pneumatic conveying Aerated distribution system Material distribution system
Conveying Material quality Pot feeding system

Introduction
During the transport and handling of alumina from port to
pot the material properties can be affected in some ways [1].
Several phenomena are known to the industry. Attrition of
the particles affects the overall performance of a plant.
Segregation may happen in storage units and as well in
horizontally arranged Aerated Distribution Systems. During
P. Hilgraf
Hamburg University of Applied Science, HAW, Hamburg,
Germany
J. Paepcke
A. Hilck (&)
Claudius Peters Projects GmbH, Schanzenstr. 40, 21614
Buxtehude, Germany
e-mail: arne.hilck@claudiuspeters.com
the last years this was not seen as a problem, but with the
continuously growing distances and capacities for new pot-
lines, this has been identified as a challenge [2].
It is therefore an interesting question, how a change in
particle size distribution of a given material affects the
conveying parameter itself.
What effect does an accumulation of fine particles have
on the discharge behavior at the outlet of a silo?
It is readily comprehensible that a certain content of
free-flowing bulk material is required in the respective
mixture in order to compensate for the characteristics of the
poorly-flowing bulk material and transform the overall
mixture into a free-flowing condition. But what proportion
of the free-flowing coarse material is needed? Or to put it the
other way around: how much poorly-flowing fine material,

© The Minerals, Metals & Materials Society 2017 501

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_63
502 P. Hilgraf et al.

e.g. from particle attrition and fracture, can a free—flowing

coarse material tolerate without any significant change in its
flow characteristics?
To verify these effects extensive tests with several
materials have been performed [1, 4, 5].
In this particular investigation a sample of secondary
alumina was split in three fractions with different particle size.
The paper presents and analyses measurement results
which describe the flow behavior of mixtures whose com-
position had been systematically varied and each of which
consisted of a very fine (= cohesive) and a coarse
(= free-flowing) bulk material. To characterize the behavior
of the mixtures the results of shear tests are employed in
combination with bulk material fluidization tests.
This paper is the first part of an ongoing investigation,
where more details will be presented at a later stage.

Fig. 1 Relationship between relative voidage volume (vertical axis)

Theoretical Considerations and fines content (horizontal), (from [1])

The flow behavior of bulk materials is essentially determined
by the adhesive forces acting between the individual parti-
cles in relation to the external forces acting on the mass of
bulk material. This means that the respective packing
structure of each mixture, i.e. compacted, loosely packed,
fluidized etc., influences the behavior of the mixture. Mix-
tures of two dry, spherical monoparticulate fractions with a

shows that its void volume consists of larger voids between
particle diameter ratio of Rd ¼ dsf =dsg ! 0, dsf = diame-
ter of fine particles, dsg = diameter of coarse particles, are, in
theory, easy to describe and are used as a model for the bulk
material mixtures consisting of a very fine and a coarse
fraction which are examined here. A more comprehensive
approach is given in [1].
The mixtures are characterized by their mass share of fine
material xf:
MS;f
xf ¼ ð1Þ
MS;f þ MS;g
For the case analyzed here, Rd!0, the two lower curves
A and B apply.
All the eM-values of dual-particle mixtures consisting of
spherical or approximately spherical particles are located
between the three limiting curves A-B-C.
An analysis of the structure of the coarse particle fraction
the coarse particles and narrower connecting channels
between these voids (compare [1, 8]). Without causing any
expansion of the structure, only fine material particles with a
maximum diameter of ds,FK (filler particles) can fit into the
interparticle voids, while only fine material particles with a
maximum diameter of ds,SK (slippage particles). In the case
of practical, i.e. unstructured, dual—particle mixtures above
grain size ratios of Rd = (dsf/dsg) > 0.5 the addition of fine
particles almost always leads to an immediate enlargement
of the coarse particle structure. Consecutively there will be a

If an increasing quantity of fine material with a void

volume of ef is mixed into a coarse material with a void
volume of eg then the free space between the coarse particles
is initially filled by the fine material without causing any
increase in the total volume (VG + VS) of the mixture. As
the voids are filled, the packing density of the solid material
increases and the void volume of the mixture eM decreases.
When the available volume between the particles of coarse
material is completely filled up, any further addition of fine
material will lead to an enlargement of the particle structure,
i.e. the void volume of the mixture eM increases again. These
interrelationships are depicted in Fig. 1 for loosely packed
coarse ash/fly ash mixtures with eg = 0.5054, coarse ash, Fig. 2 Expected course of compressive strength versus share of fines
and ef = 0.6708, fly ash (compare [1, 3–7]). in the material, (from [1])
Influence of Handling Parameter on Powder Properties 503

Table 1 Material used for the Material Description

investigation
Secondary alumina Complete material sample
Secondary alumina very fine Screened d <20 µm
Secondary alumina fine Screened d <45 µm
Secondary alumina coarse Screened d > 100 µm
Secondary alumina very fine Screened d <20 µm
Alumina hydrate D50 = 90 µm
Primary alumina very fine Very fine fraction d <5 µm

continuous alteration of bulk material properties with
changing ratio of fine fraction xf.
From a certain point on the fines content is dominant and
a further increase does not result in an increase in strength
[1]. The expected course is shown in Fig. 2.
For the main investigation a larger sample of secondary
alumina was split into several fractions. Additionally other
material samples were used for further tests. The different
materials are listed in Table 1.
Measurement Results
Depending on the material different tests were initiated. The
following tests, listed in Table 2 are presented here.
Further tests will be performed with the second part of the
investigation. Focusing on the discharge behavior and the
conveying parameter at these will be published at a later
stage.
Shear Tests
Shear Tests allow for a reliable judgement of the storage and
handling behaviour of a powder. In the shear test the
material is compacted with a certain load in vertical direction
and sheared in horizontal direction. Shear tests allow for a
detailed insight into the storage and handling behaviour of a
powderous material [9–12].
Shear tests were carried out with the reference sample for
secondary alumina and several mixtures of fine and coarse
material.
The monoaxial compressive strengths fc are considered at
the compaction stress r1 = 4600 Pa. Different ratios of
mixtures of fine and coarse material are shown in Fig. 3.
It can easily be seen, that increase of the fines results in a
higher compressive strength of the material. In other words
addition of the fines results in an in general more cohesive
material. But with a small amount of fines added the effect is
nearly negligible. It needs to be noted that the results from
the tests correspond with the theoretical considerations, that
from a certain amount of added fines, the cohesion of the
fines fraction is dominant and the strength of the mixture is
on the same level as the complete fine fraction (compare [1]).
From these tests the flow factor ff is generated:
r1
ff ¼ ð2Þ
fc
with fc = compressive strength and r1 = Principal consoli-
dation stress.
A high number of the flow factor indicates a good
flowability, while a small number means a material with a
poor flowability (see Fig. 4)
As the consolidation stress is kept constant, a lower
compressive strength leads to high numbers for the flow
factor.
But even though there is a decrease in flowability with an
addition of fines, compared with other known materials, the

Table 2 Test covered in this Tests initiated Material

paper
Shear tests
Aeration behaviour
Aeration behavior
Deaeration behavior
Wear tests
Long time aeration
Several mixtures of fine and coarse secondary alumina
Mixture of alumina hydrate and primary alumina
Different grain sizes of secondary alumina
Various grain sizes of secondary alumina
Various tests with varying impact velocities
Secondary alumina
504
Fig. 3 Compressive strength of different weight share of fine material
Fig. 4 Flow factor versus weight share fine particles
fraction passing 45 µm is still material with a reasonable
flowability.
Aeration and Deaeration
The particle size does massively affect the fluidization
behavior [13]. The interdependence is well known in all
industries using fluidization technologies.
Smelter Grade Alumina is usually easy to fluidize, and
has a very high air permeability. When aeration air is stop-
ped the material will settle very fast.
If only separate particle fractions are fluidized the
resulting effect is different.
P. Hilgraf et al.
Fig. 5 Deaeration time versus particle size
For a comparison of this behavior the powder is fluidized
with a defined velocity, while there is pressure transmitter
installed in the air supply. The pressure will indicate the load
above the air column. When the air supply is stopped sud-
denly, the pressure will drop to zero. The timing for this
pressure drop will be stopped.
In Fig. 5 this was done for different material fractions.
One line shows the deaeration with stirred materials (mate-
rial in movement), while the second line shows the values
without agitating. The two large material sizes show a very
quick pressure drop. The fraction of particles <45 µm has a
very long duration to come to rest.
With a very fine fraction it is easily possible, that stable
channels are formed, therefore there is a huge difference
visible between stirred and unstirred aeration time on the left
side of the graph.
Another effect is shown in the next two graphs. The left
graph shows the aeration of a mixture of very fine alumina
hydrate and alumina (90/10 mass%). The right graph shows
a mixture with 10% more alumina based on mass (Fig. 6).
Even though there is only a small change in the mixture,
there is already a huge difference in the fluidizing behavior.
Permanent Aeration
Tests with a constant aeration of a material column with the
reference material secondary alumina were carried out. The
aeration was running for 1 h with a material column of
300 mm in height. After the aeration was stopped the
material was screened out in three different elevations
(Fig. 7).
With a long aeration time the fine material fraction
(>45 µm) obviously did not even travel upward in the
material, but easily it escaped into the deaeration. This
would be especially the very fine material less than 20 µm in
size.
Influence of Handling Parameter on Powder Properties
Fig. 6 Aeration velocity versus bottom pressure for two mixtures (90/10, left; 80/20, right)
Fig. 7 Loss in fine material at 3 different elevations of aeration pipe
Wear/Fracture Tests
With an YGP-test device, different impact velocities to a
material can be simulated. It mainly consists of a rotor with
an adjustable speed with attached wear plates and usually its
purpose is to help predicting a wear rate.
In this case it was used vice versa, do detect the impact
velocity, at which material starts to crack. This would help to
identify a velocity, which a pneumatic conveying should not
exceed to prevent massive attrition.
Outlook
Minimum Energy consumption and minimized effect on the
material are the key criteria for equipment design. Therefore
comprehensive knowledge of the material properties is
crucial.
Comprehensive laboratory tests have been made and the
theoretical considerations were verified.
Even though particle simulation plays an increasing
broader role in the design, the powder behaviour is still very
505
complex, and predictions need to use some safety margins or
very sound parameter.
With long distance pneumatic conveying or material
distribution, the critical particles are at both ends of the
Particle Size Distribution. The very coarse material may
settle in conveying lines. The fine material might be col-
lected because of its very low take off velocity.
Therefore a sound design of the equipment to all possible
cases is needed [14–21]
Further investigation will be presented at a later stage.
References
1. P. Hilgraf, Handling of bulk material mixtures. ZKG international,
46–59 (2008)
2. S. Pollé et al, The challenge to supply consistent alumina quality to
all pots on increasingly longer and higher capacity potlines. Light
Metals, 499–503 (2016)
3. O. Molerus, Schüttgut-Mechanik (Springer, Berlin, 1985)
4. I. Dangleterre, Systematische Untersuchung des Handhabungsver-
haltens von Schüttgutmischungen. Diplomarbeit, Hochschule für
Angewandte Wissenschaften Hamburg, Fakultät Life Sciences,
Studiengang Verfahrenstechnik (2007), unpublished
5. G. Li, Systematische Untersuchung des Handhabungsverhaltens
von Schüttgutmischungen. Diplomarbeit, Hochschule für Ange-
wandte Wissenschaften Hamburg, Fakultät Life Sciences, Studi-
engang Verfahrenstechnik (2008), unpublished
6. R. Jeschar, Druckverlust in Mehrkornschüttungen aus Kugeln.
Archiv für Eisenhüttenwesen 35(2), 91–108 (1964)
7. K. Schönlebe, H. Seewald, Fließverhalten binärer Kohlemischun-
gen. Aufbereitungs-Technik 32(7), 335–343 (1991)
8. P. Schmidt, Die dichte Lagerung körniger Stoffe, insbesondere im
feindispersen Bereich. Aufbereitungs-Technik 5(7), 355–365
(1964)
9. A.W. Jenike, Storage and flow of solids. Bull. no. 123. Utah
Engng. Exp. Station, Univ. of Utah, Salt Lake City (1964)
10. J. Tomas, Modellierung des Fließverhaltens von Schüttgütern auf
der Grundlage der Wechselwirkungskräfte zwischen den Partikeln
und Anwendung bei der Auslegung von Bunkeranlagen. Ph.D.-
Thesis (TU Bergakademie, Freiberg, 1991)
11. P. Hilgraf, Schüttgüter: Eigenschaften und Handhabung, Teil 1
und 2. ZKG international 59(9), 58–69 and 59(10), 73–81 (2006)
506
12. D. Schulze, Powders and bulk solids (Springer, Berlin, 2008)
13. D. Geldart, Gas fluidization technology (Wiley, New York, 1986)
14. M. Karlsen, A. Dyroy, B. Nagell, G.G. Enstad, P. Hilgraf, New
Aerated Distribution (ADS) and Anti Segregation Systems
(ASS) for Alumina. TMS Annual Meeting 2002. (Seattle, USA,
2002) February 17–21. P.5. A. (02-1000-8)
15. A. Wolf, P. Hilgraf, M. Altmann-Rinck, A new alumina distribu-
tion and feeding system for aluminium reduction cells. TMS
Annual Meeting & Exhibition 2007. (Orlando, Florida/USA,
2007) February 25–March 01, Collected Proceedings: Light
Metals—Alumina Reduction, pp. 223–228
16. A. Wolf, P. Hilgraf, FLUIDCON—a new pneumatic conveying
system for alumina. TMS Annual Meeting 2005. (San Antonio TX,
USA, 2005) March 13–17. P.5. A. (02-1000-8)
17. P. Hilgraf, FLUIDCON—a new pneumatic conveying system for
fine-grained bulk materials. Cem. Int. 2(6), 74–87 (2004)
P. Hilgraf et al.
18. A. Wolf, P. Hilgraf, A. Hilck, S. Marshalko, Operational
experience with a brownfield expansion project in Sayanogorsk,
Russia. TMS Annual Meeting & Exhibition 2007. (Orlando,
Florida/USA, 2007) February 25—March 01, Collected Proceed-
ings: Light Metals—Alumina Reduction, pp. 223–228
19. J. Paepcke, A. Hilck, S. Marshalko, Operational experience of
advanced alumina handling technology in a Russian Smelter. TMS
Annual Meeting & Exhibition 2013. (San Antonio, TX, 2013)
Collected Proceedings: Light Metals—Alumina Reduction,
pp. 753–759
20. A. Hilck, M. Karlsen, A. Dyroy, Segregation effects during
transport and storage, Presentation at ICSOBA, Belem, 2012
21. J. Paepcke et al, Startup and tuning of material distribution system
at aluminium smelter in Qatar. Light Metals, 743–746 (2014)
 Part XII
Aluminum Reduction Technology: Anode Effect and
PFC Emissions
 Preventive Treatment of Anode Effects Using
on-Line Individual Anode Current Monitoring

Lukas Dion, Charles-Luc Lagacé, François Laflamme,

Antoine Godefroy, James W. Evans, László I. Kiss, and Sándor Poncsák

Abstract
Anode effects (AE) are considered a nuisance for aluminium production due to the
numerous negative impacts that they generate in an electrolysis cell. Previously, great
efforts have been deployed to minimize the occurrence of this event. Using online anode
current monitoring, Alouette introduced an algorithm to detect abnormalities prior to an
AE, allowing sufficient time to apply a corrective action before its occurrence. Several sets
of strategies were tested to evaluate the best approach to correct the situation without
generating additional problems in the cells. Finally, individual anode currents measure-
ments were connected to the cell control system of two pots to automatically launch
preventive treatment of AE. A decrease in the total number of anode effects along with an
increased cell stability is noticeable. Other indicators, such as anodic incidents, alumina
dosage and metal purity were also compared to make sure that no deterioration in the cell
conditions occurred over time.

Keywords
Anode effect PFC emissions Individual anode monitoring Preventive anode effect
treatment

Introduction primary source of GHG (carbon dioxide) is inherent to the

In the past decades, great efforts have been deployed to
reduce the greenhouse gases (GHG) emitted by the primary
aluminium industry. For smelters using carbon anodes, the
L. Dion (&)
Université du Québec à Chicoutimi, 555 boulevard de
l’Université, Chicoutimi, QC G7H 2B1, Canada
e-mail: lukas.dion@uqac.ca
C.-L. Lagacé
F. Laflamme
A. Godefroy
Aluminerie Alouette Inc, 400 chemin de la Pointe-Noire,
C.P. 1650, Sept-Îles, QC G4R 5M9, Canada
J.W. Evans
Wireless Industrial Technologies, 4096 Piedmont Ave. #193,
94611, Oakland, CA G4R 5M9, USA
L.I. Kiss
S. Poncsák
GRIPS, Université du Québec à Chicoutimi, 555 Boulevard de
l’université, Chicoutimi, QC G7H 2B1, Canada
production of aluminium because the carbon participates in
the electrolysis reaction. However, another kind of GHG is
also associated with the primary aluminium production,
namely the perfluorocarbons (PFCs). CF4 and C2F6 are
known to have a respective global heating potential 6630
and 11,100 higher than the CO2 [1]. PFCs are periodically
produced during an event called anode effect (AE) occurring
when insufficient alumina is present in the electrolytic bath.
For this reason, the molten fluoride electrolyte will dissociate
to support the passage of electric charges and PFCs will be
generated during this reaction. The occurrence of an AE is
dependent on the electrolysis process conditions and the
total number of AEs can theoretically be minimized down to
zero, even if the alumina concentration is kept below satu-
ration in order to prevent sludge formation. Hence the reason
why the efforts of the industry have been able to reduce
significantly the total amount of PFCs emitted between 1990
and 2010 [2].

© The Minerals, Metals & Materials Society 2017 509

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_64
510
This paper describes the most recent efforts deployed by
Aluminerie Alouette to reduce significantly the AE fre-
quency, hence the total PFCs emissions. Using on-line anode
monitoring, it is possible to use an algorithm to anticipate
abnormalities that are indicating upcoming anode effects.
Once the information is known that an AE is imminent, it is
important to react quickly and efficiently to eliminate the
abnormalities in the cell without generating perturbations
that can generate other problems over a long-term period.
Manual tests were performed with three different preventive
AE mitigation strategies to evaluate their efficiency at
unblocking alumina feeders that were not distributing alu-
mina properly.
Finally, the system has been running automatically for
almost a year on two cells equipped with online anode
monitoring and very good results were achieved. Key per-
formance indicators prior and during the test are shown and
described in the last section of the article.
Early Detection of the Anode Effects
The production of primary aluminium requires the passage
of a constant electric current through an electrolysis bath.
Passage of these electric charges is made possible by the
redox reaction 1 that occurs in the presence of alumina.
However, if the alumina concentration is not sufficient,
reaction 1 alone cannot withstand the passage of current and
other reactants will be electrolyzed by reactions 2 and 3.
2Al2 O3 þ 3C ¼ 4Al þ 3CO2 ð1Þ
4Na3 AlF6 þ 3C ¼ 4Al þ 3CF4 þ 12NaF ð2Þ
2Na3 AlF6 þ 2C ¼ 2Al þ C2 F6 þ 6NaF ð3Þ
When CF4 and C2F6 are generated, they will most likely
stay under the anodes due to the high adhesion of those
gases under carbon anodes. Because these gases have an
important electrical resistivity, the electrical current will be
redistributed among the other anodes, increasing their
respective current density. Consequently, the alumina will
deplete faster in that area, eventually leading to the spreading
of reactions 2 and 3 in the cell. Hence the overall mechanism
that generates PFCs is auto-amplifying if no significant
change is applied to the process strategy.
As the number of anodes under which PFCs are trapped
increases, it will lead to an increase of the overall cell
voltage as well. However, Wong et al. [3] calculated that the
voltage increase is not significant if PFCs are only located
under a limited number of anodes. It was calculated that
when the voltage of detection of an AE is reached at 6 V,
almost half of the anodes are already in contact with PFCs.
For this reason, PFCs are very hard to detect in the initial
L. Dion et al.
phase of its formation, that is to say when a small number of
anodes are affected. The International Aluminium Institute
[4] recently adopted the term Low-Voltage Anode Effects
(LVAE) to describe all PFCs emissions occurring below the
voltage of detection, set by each smelter (generally 6 or
8 V). If the threshold is reached, all PFCs generated by this
cell are then considered as High-Voltage Anode Effects
(HVAE) for the duration of the AE.
Knowing that the cell voltage is a bad indicator to detect
LVAE or foresee upcoming HVAE, additional information
is necessary to eventually detect these abnormalities. Rye
et al. [5] demonstrated that a low alumina concentration can
have an impact on the current distribution among the anodes.
More importantly, it was shown that prior to an anode effect,
several anodes will significantly change their current load,
indicating that the event (AE) can be detected prior to the
usual shift in cell voltage. Other studies confirmed [6, 7] that
online measurements of individual anode currents is a viable
solution to preventively detect anode effects. Figure 1
illustrates that the local current drops significantly for some
anodes during LVAE. In this case, as the CF4 concentrations
rose from 0.2 ppb up to 1.5 ppm, the current from anode
A16 and A17 respectively decreased by 50 and 15%. After
this quick surge in emissions, CF4 remained under A16 and
A17 and thus increased the local electrical resistance. Hence
the current has been redistributed according to the respective
resistances of all anodes and the production of aluminium
continued under these new conditions. The same phe-
nomenon occurred two more times before the cell finally
reached an HVAE six hours later. Only at that moment, the
anode effect stopping procedure was started to resolve the
problem. Any similar procedure launched during any of
the three LVAE that occurred before the HVAE could have
eliminated several hours of PFC emissions as well as the
HVAE itself.
For this reason, an algorithm was developed to detect any
sudden change in individual anode currents that are related
to an anode effect, with the main focus being the prevention
of HVAE. Two different sets of conditions need to be
reached for the cell to be considered close to an AE. The first
condition is similar to the methodology published in 2015 by
Dion et al. [7]. It involves the use of a short-term (1–5 min)
and a long-term moving average (15–25 min) for each
individual anode. It is possible to observe in Fig. 2 that the
current behaviour is significantly different in the short-term
moving average (STMA) with comparison to the long-term
moving average (LTMA) used as the reference. Henceforth,
once the ratio STMA/LTMA has reached a predetermined
threshold for a specific number of anodes, the first condition
of the algorithm becomes satisfied.
Using exclusively the first condition is sufficient to detect
upcoming anode effect but it can also generate false alarms
by detecting other events in the cell such as anode change,
Preventive Treatment of Anode Effects Using on-Line … 511

Fig. 1 Individual anode currents

and CF4 concentration from a A19 A18 A17 A16 A15 CF4
single electrolysis cell during
LVAE 1.5 4

1.3
3.5
1.1
3

Anode normalized current

CF4 concentra on (ppm)

0.9
2.5
0.7

0.5 2

0.3
1.5
0.1
1
-0.1
0.5
-0.3

-0.5 0
8:52 9:00 9:07 9:14 9:21 9:28 9:36 9:43 9:50 9:57

Fig. 2 llustration of a cell

behavior leading to preventive
AE treatment. Upstream side.
(Stars represents maximum
current values reached for each
individual anodes during the short
period)

metal tapping or cell instability. To maintain the same
detection sensitivity, an additional condition was established
which can be attributed most likely to the generation of
PFCs. This second condition investigates the maximum
current value of each anode within a short period similar to
the STMA. It was observed that the current value of each
anode tends to reach a higher value than its reference state
during an AE. This phenomenon is linked to the current
redistribution that occurs when resistive gas is moving under
the anodes and can occur very quickly (less than 5 s). Hence
it might have no significant effect on the average value of
each respective anode. Figure 2 clearly demonstrate that 6
anodes out of 10 temporarily reached a maximum higher
than the anode that is driving the most current in the LTMA
period. Moreover, all the maximum values were measured
within a two-minute interval.
Finally, if both conditions are satisfied for a specific cell,
it is highly plausible that PFCs are generated under its
anodes. Hence, if adequate actions are undertaken at this
moment, the PFC emissions from this cell can be signifi-
cantly reduced.
Establishment of the Preventive AE Treatment
Numerous elements have to be considered to develop a
preventive AE treatment. It has to react quickly enough to
eliminate any imminent AE but the treatment itself must be
512
controlled so that it does not bother the cell significantly
over a long period if numerous preventive AE treatments are
launched. AE are essentially caused by an insufficient
amount of alumina dissolved in the bath in a small region or
in the entire cell. This lack of alumina can be caused by
conditions such as low bath height or low bath temperature
in the cell that makes the transport or dissolution of particles
difficult in certain regions of the cell. The preventive AE
treatment should be designed to assure a decent amount of
alumina dissolves into the bath under a short time period to
correct the situation.
In another case, an insufficient amount of alumina can be
fed to the cell to compensate the necessary consumption
from the electrolysis. This problem generally occurs when
an alumina feeder hole is obstructed by an excessive amount
of alumina. This phenomenon occurs when bad dissolution
conditions are present and thus the alumina becomes com-
pacted by the repeated actions of the crust breaker. Under
such conditions, the alumina is shaped like a mound, starting
from the cathode up to the alumina feeding chute. Simula-
tion performed by Dassylva and al. [8] showed that if the
alumina is clumped, the dissolution efficiency is significantly
reduced. In the reality, such circumstances cause even poorer
conditions than that suggested by the simulations, therefore
the alumina dissolves slower than it is fed, causing an
accumulation. Usually, a manual intervention is necessary to
resolve the problem in such situation. However, the pre-
ventive AE treatment should be designed to unblock the
majority of feeders facing this problem.
Preventive AE Treatment Parameters
To design the preventive AE treatment, the ensemble of
parameters that can be controlled are divided into three
different categories. For each of them, there are specific
considerations to take into account when establishing the
preventive AE treatment.
Alumina feeder actions: once an alarm is sent to the cell
control system, commands such as “stopping or changing
the rate of injection” can be sent to the crust breakers and the
alumina feeders. Knowing that a lack of alumina is probably
the root cause of the problem, launching an overfeeding
appears as the logical step to quickly solve the problem.
However, such action could easily make the cell’s conditions
worse for two sets of circumstances that are likely to occur.
If a feeding hole is blocked, this solution will only increase
the pile of alumina above the crust. It will also increase the
risk of blocking other feeders. Additionally, if a false alarm
occurs, the additional alumina could increase the alumina
content in the bath close to the solubility limit. Therefore, the
preventive AE treatment could generate muck in the cell,
which would likely increase the instability and might cause
L. Dion et al.
additional false alarms, and so on. For these reasons, actions
from the feeders should be defined with great care and at the
same time, other ways to route alumina should be
considered.
Quenching procedure: movement of the anode beam has
been used for years in the industry to help cure AE. Gen-
erally, quenching is composed of several up-and-down
motions of the anode beam to help clear out the gas from
under the anode. In addition to this positive effect, it
increases the movement of the bath, in favor of the disso-
lution of alumina. Moreover, as the anodes are immersed
into the bath, the liquid level is higher and bath can get more
easily in contact with the crust. This crust is composed of a
substantial amount of alumina which then contributes to the
alumina input. However, excessive movements of the anode
beam can cause severe disruptions in the anode cover,
exposing the anodes to increased oxidation while threatening
the thermal balance of the cell. Downward movements can
also compress the anode against the side ledge, causing
solidified bath to stick under the anodes, increasing insta-
bility and eventually leading to anodic incidents (spikes).
Finally, in the worst case scenario when bath levels are low
and when anode beam movements are badly set up (e.g.
significant displacement upwards), it could lead to a rupture
of the circuit (anode out of the bath); an event that must be
avoided at all cost. Therefore, movements of the anode beam
need to be set correctly for the treatment to assure an ade-
quate solution.
Additional energy input: Another adjustable element is
the energy input in the cell. It is possible to increase the
anode-cathode distance (ACD) for several hours in order to
increase the internal heat in the cell generated by Joule
effect. Additional energy will play a positive role in the
dissolution of the alumina. Moreover, the additional volume
of bath under the anode (higher ACD) will favor the trans-
port of alumina to a region further away from the feeders. On
the other hand, additional energy might disrupt the thermal
balance of the cell. More importantly, it can melt away the
side ledge and expose the sidewalls of the cell to the elec-
trolyte. Energy inputs are not a short-term solution to pre-
vent imminent AE and could be used as a final step to the
preventive AE treatment.
Efficiency of AE Treatments to Unblock
Feeder Holes
By considering the numerous elements presented in the last
section, Aluminerie Alouette tested three different preventive
AE treatment algorithms to evaluate their respective effi-
ciency to unblock feeder holes. During the duration of all the
3 treatments, no alumina is fed into the cell. However, the
action of the crust breaker is maintained active in order to
Preventive Treatment of Anode Effects Using on-Line …
push some alumina into the bath while movements of the
beam allows for an increased contact between the electrolyte
and the undissolved alumina. The main difference of the
treatments resides in the quenching pattern illustrated in
Fig. 3. The goal was to test a “non-aggressive” (A) and two
“aggressive” treatments (B & C) respectively. Treatment B
has a high number of quenching cycles and treatment C has
a larger amplitude in the movements of the anode beam. No
additional energy was added to the cell after these
treatments.
During several weeks, manual tests were performed to
evaluate the capability of each treatment to unblock feeder
holes. When a feeder was observed in conditions similar to
Fig. 4A, a preventive AE treatment was manually initiated
on this cell to observe its effect on the feeder hole. In
addition, the bath level was measured prior and after the
treatment for supplementary information.
The results shown in Table 1 indicate that the three pre-
ventive AE treatments were successful in unblocking feeder
holes for the majority of the cases. Results from treatment B
showed an important increase in the efficiency of the pre-
ventive AE treatment to unblock the holes while the results
from treatment C were slightly lower than the results from
treatment A. Therefore, it is possible to determine that the
Fig. 3 llustration of three different preventive anode effect treatment procedure
513
number of quenching cycle is the most important parameter
in favor of unblocking feeder holes. Moreover, a certain
amount of time is necessary to allow for the dissolution of
anode cover material and alumina. The results from treat-
ment C indicate that a larger amplitude of anode beam
movement is not as efficient as a longer quenching period.
Bath level measurements performed during the tests
indicate that the bath level difference occurred after treat-
ment B was applied to the cell. On the other hand, the
average bath level difference between each group is signif-
icantly smaller than the respective standard deviation of each
treatment. For this reason, the average bath level difference
between each group can’t be considered as significant.
It is important to take into considerations that these tests
represent the conditions subsequent to a preventive AE
treatment. In some cases, it is possible that the feeding holes
might be blocked again, thus the interest in temporarily
adding some energy to the cell. Moreover, the preventive AE
treatment will not be efficient enough if a mechanical
problem is present in the cell (e.g. feeder malfunction) or if
the bath level remains significantly too low. However, the
preventive AE treatments are registered as an intervention in
the cell control system. Hence, multiple preventive AE
treatments will send an alarm to the process technicians and
514
Fig. 4 llustration of a feeder
before and after a preventive AE
treatment. a Blocked feeder.
b Unblocked feeder after a
successful treatment
Table 1 Success rate and the
difference in bath levels for the
tested preventive AE treatments Success rate (%)
Average bath level difference (after—before) (cm)
Bath level difference standard deviation (cm)
Number of feeders tested
actions can be undertaken to address the problem. Hence-
forth, the preventive AE treatment allows for additional time
to operate without the negative impacts of AE occurring in
the cell.
Key Performance Indicators of Cells
with Automatic AE Treatment
To evaluate correctly the effectiveness of the preventive AE
treatment, the algorithm was connected to the cell control
system on two cells to launch automatically the preventive
AE treatment when required. A close follow-up of the per-
formance indicators of the selected cells will allow for a
better evaluation of the overall efficiency of such treatment
during several months of operations.
To perform this analysis, two cells were implemented
with automatic AE detection and preventive AE treatments.
For comparison, 5 other cells were monitored as a reference.
All of these 7 cells are part of the AP40LE technology, using
four point-feeders and prebaked anodes. The current inten-
sity of all these cells remained at the same level for the entire
period. Finally, process parameters such as bath and metal
L. Dion et al.
Treatment A Treatment B Treatment C
68 90 60
−0.25 0.30 −0.39
0.73 1.30 0.95
57 30 25
level, temperature target, etc. were also similar for all the
cells.
For comparison, four different periods were selected.
Period #1 was the reference period where no actions were
taken on the cell related to the preventive AE treatment. In
period #2, preventive AE treatment was active for both test
cells in the preliminary phase of the project. Then in period
#3, optimisations were performed on the system to increase
the detection efficiency. For periods #2 and #3, preventive
AE treatment A was activated once an imminent AE was
detected. Finally, in period #4, the same parameters
remained for the detection of AE but preventive AE treat-
ment B was active. However, one of the two test cells was
excluded from period #4. For this cell, the results were not
representative of the preventive AE treatment’s real potential
due to a significant number of mechanical problems that
occurred in this cell.
The specific duration of each period is listed in Table 2
and the key performance indicators for all periods are listed
in Table 3.
The principal performance indicators that were investi-
gated are the total number of anode effects and the anode
effect overvoltage. The results (illustrated on Fig. 5) clearly
Preventive Treatment of Anode Effects Using on-Line … 515

Table 2 Details on the four periods selected for testing the preventive AE treatments
Periods Active treatment protocol Start date End date Total number of days
1. None 2015/09/01 2015/12/10 101
2. Treatment A 2015/12/17 2016/03/31 106
3. Treatment A (with optimized detection) 2016/04/01 2016/06/14 75
4. Treatment B (with optimized detection) 2016/06/15 2016/08/20 66

Table 3 Comparison between the test group and reference cells over four periods
Period #1 Period #2 Period #3 Period #4
Reference Test Reference Test Reference Test Reference Test
cells cells cells cells cells cells cells cells
Total number of AE (AE/cell*day) 0.89 0.90 0.68 0.36 0.49 0.18 0.68 0.16
Standard deviation 1.51 1.48 1.17 0.79 1.02 0.45 1.11 0.44
Anode effect overvoltage (mV) 1.81 2.39 0.92 1.05 2.08 0.39 1.18 0.70
Standard deviation 6.25 7.30 2.44 5.23 21.85 1.37 3.06 2.90
Cell instability (nanoOhms) 121 94 102 64 95 55 124 58
Standard deviation 74 71 56 24 58 28 63 40
Additional energy input (nanoOhms) 0.056 0.046 0.051 0.034 0.049 0.032 0.053 0.030
Standard deviation 0.036 0.028 0.028 0.024 0.049 0.018 0.023 0.018
Daily mass of bath produced (kg/cell*day) 50 29 52 42 94 130 48 60
Standard deviation 292 224 334 209 290 260 297 230
Number of alumina doses (doses/day) 5692 5684 5753 5781 5628 5617 5679 5688
Standard deviation 347 323 358 218 398 258 362 203
Parasite alumina feeding indicator 5.81 6.55 4.85 4.55 6.50 7.41 5.93 5.88
Standard deviation 3.80 4.25 4.01 1.94 3.67 2.67 4.56 1.63
Iron level in aluminium (ppm) 650 475 506 516 678 582 800 720
Standard deviation 182 106 123 72 139 162 123 263
Number of anodic incidents (Normalized to 165% 110% 131% 72% 81% 65% 146% 7%
potline average)
Standard deviation 329% 223% 279% 182% 234% 187% 308% 55%
Bold values represent average value for each parameters and italics represents the standard deviation values of the same parameter

Fig. 5 Performance indicators

related to anode effects for the 2.00 2.50
overvoltage (mV/cell)
Number of AE
(AE/cell*day)

2.00
Daily anode effect

four periods of testing 1.50

1.50
1.00
1.00
0.50 0.50
0.00 0.00
period #1 period #2 period #3 period #4

Number of AE (Reference) Number of AE (Test)

Anode effect overvoltage (Reference) Anode effect overvoltage (Test)

indicate that a significant change occurred once the system in periods #3 and #4. It illustrates the effectiveness of the
was fully operational. The daily number of AE was similar algorithm to detect AE as well as the efficiency of the pre-
to the reference cells in period #1 and dropped significantly ventive AE treatment to eliminate the threat before the event
516
occurs. Moreover, the AE overvoltage significantly dropped
alongside the total number of AE indicating that the mag-
nitude of the anode effects that still occurred was not worse
than usual. Hence by considering that the total PFC emis-
sions are calculated based on a linear relation between a
predetermined factor and this indicator, the results confirms
that fewer PFCs are produced when using this system.
However, to accurately quantify the reduction, on-line gas
measurements monitoring should be performed to account
for the low voltage anode effects as well.
A positive effect was observed on the cell stability when
using preventive AE treatments. Even if the instability of the
test cell were lower than that of the reference in the control
period, the difference increased while the preventive AE
treatment was active. More importantly, the standard devi-
ation of this variable was reduced significantly indicating
that values are less scattered and closer to the average, hence
confirming the increase in cell stability. With the active
preventive AE treatment, it is launched in the beginning
phase of LVAE or HVAE. Therefore, the cell can recover
quickly and remains stable, instead of being unstable for
plausibly several hours. Additionally, when the cell is
unstable, a resistance increase is introduced into the cell by
the control system, consequently increasing the ACD and
thus adding some extra energy to the bath. In periods #2, #3
and #4, this additional energy input was significantly
reduced due to an increased stability.
The quenching effect of the procedure is designed to
consume part of the anode cover. For this reason, the daily
production of bath is higher with the active preventive AE
treatment. However, when this treatment will be applied to
multiple cells, it will be possible to adjust the crushed bath
and alumina ratio from the anode cover material to account
for the effect of the preventive AE treatments. A correlation
can be observed between the daily mass of bath produced
and the parasite alumina feeding indicator. Therefore, even if
the number of alumina feedings slightly decreased for some
period, it was simply replenished from another source.
Overall, the alumina fed to the electrolysis cell remained
similar to the reference cells, hence we can assume that the
metal production was equivalent as well.
Finally, the quenching of the anode beam could lead to an
increased bath exposure of the anode stubs or to an increase
in the frequency of anodic incidents. However, during our
tests, no undesirable difference between the reference and
the test cells was observed. Therefore, it indicates that under
the tested conditions, the preventive AE treatment generates
no negative effect regarding these indicators. It is important
to mention that some data were intentionally excluded from
this analysis if the iron contamination came from an exces-
sive exposure of the stubs that was not a result of the
quenching procedure. Such exposure could be caused by a
failure of the clad or if the anode detached from its stubs.
L. Dion et al.
Conclusion
A successful preventive treatment procedure was presented
in this paper to minimize the occurrence of anode effects.
This procedure is based on an algorithm that detects the
variation in the individual anode currents that indicates an
anode effect is about to occur. It is effective to detect both
low voltage and high voltage anode effects. This algorithm
then sends an alarm to the cell control system and a pre-
ventive AE treatment can be initiated on the cell to avoid the
negative impact caused by an AE.
Three different preventive AE treatment procedure were
tested to evaluate their ability to unblock feeder holes.
A success rate ranging from 60 to 90% was observed.
Additionally, two different preventive AE treatment proce-
dure were tested and automatically launched on two cells for
several months to assess the overall performance of these
cells on a long-term basis. The results indicate that a sig-
nificant decrease in the total number of AE is observed. This
outcome is also observed in the anode effect overvoltage
which confirms that fewer PFCs are generated from high
voltage anode effect on the cells with the preventive AE
treatment active.
Moreover, a positive effect was observed regarding the
cell stability and for this reason, a smaller amount of extra
energy was added to the cell. However, bath production
increased with the preventive AE treatment. No negative
effect from the preventive AE treatment was observed
regarding the total number of alumina doses, the total
number of anodic incidents or regarding iron contamination.
With the positive results obtained in the initial phase of
this project, Aluminerie Alouette plan on stepping up the
number of cells using the proposed methodology in the near
future. More cells will allow to correctly evaluate the eco-
nomic gain from such procedure for a whole pot room,
hence justifying a part of the investment cost necessary to
implement continuous anode current monitoring across the
entire smelter.
Acknowledgments The support from Aluminerie Alouette to publish
and present these results is greatly appreciated.
References
1. G. Myhre et al., Anthropogenic and natural radiative forcing, in
Climate Change 2013: The Physical Science Basis. Contribution of
Working Group I to the Fifth Assessment Report of the Intergov-
ernmental Panel on Climate Change, ed. by T.F. Stocker et al.,
(Cambridge University press: Cambridge, United Kingdom and
New-York, NY, USA, 2013)
2. M. Fischedick et al., Mitigation of Climate Change. Contribution of
Working Group III to the Fifth Assessment Report of the Intergov-
ernmental Panel on Climate Change (Cambridge University press:
Cambridge, United Kingdom and New-York, 2014)
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3. D. Wong, A.T. Tabereaux, P. Lavoie, Anode effect phenomena
during conventional AEs, low voltage propagating AEs &
non-propagating AEs, in Light Metals (San Diego, USA, 2014),
pp. 529–535
4. International Aluminium Institute, in Workshop on Low Voltage
Emissions of PFC, Workshop attendees (London, UK, 2015)
5. K.Å. Rye, M. Königsson, I. Solberg, Current redistribution among
individual anode carbons in a Hall-Heroult prebake cell at low
alumina concentrations, in Light Metals (1998), pp. 241–246
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6. B.J. Welch, Quantifying PFC emissions from smelter cells, in
Proceedings of the 10th Australasian Aluminium Smelting Confer-
ence (Launceston, Tasmania, 2011)
7. L. Dion et al., On-line monitoring of anode currents to understand
and improve the process control at alouette, in Light Metals
(Orlando, USA, 2015), pp. 723–728
8. V. Dassylva-Raymond et al., Modeling the behavior of alumina
agglomerate in the Hall-Héroult process, in Light Metals (San
Diego, USA, 2014), pp. 603–608
 Reduction in EGA Jebel Ali Potroom GHG
Emissions

Daniel Whitfield, Sergey Akhmetov, and Najeeba Al-Jabri

Abstract
EGA’s Jebel Ali smelter hot metal production has increased above 1 million tons per annum
since 2010 and produced a record 1,045,255 tons in 2015 and with forecast total production
of 1,065,280 tons for 2016. Jebel Ali Potrooms has also strived to minimize its
environmental impact with significant effort to reduce the three main sources of GHG
emissions; power consumption, anode carbon and CO2e emissions from AE PFC’s (anode
effect perflurocarbons). Specific energy has decreased from 14.82 DC kWh/kg to 14.29
DC kWh/kg, net carbon has reduced from 0.434 t/t Al to 0.423 t/t Al and AE PFC
emissions have reduced from 0.263 CO2e/t Al to 0.071 t CO2e/t Al. This has resulted in
reducing annual GHG emissions by 798,065 CO2e tons and was achieved despite
increasing annual hot metal production by 63,266 tons since 2010. This achievement
demonstrates EGA’s vision for operational excellence and continuing efforts to minimise its
environmental footprint.

Keywords
Environment Emissions GHG Efficiency

Introduction Hence the consumption of electricity indirectly results in

In 2010 EGA Jebel Ali Smelter annual hot metal production
increased above 1 million tonnes per annum for the first
time, making it one of the largest single site smelters in the
world. Every year since then it has increased further with a
record 1,045,255 tons produced in 2015 and 1,065,280 tons
forecast for 2016. Despite the increase in metal output there
has been significant effort to reduce the total greenhouse gas
(GHG) emissions of Potrooms.
Two of the main sources of GHG emissions from the
aluminium smelting process are the CO2 emissions from the
consumption of anode carbon and the generation of PFC
emissions during AE. EGA Jebel Ali Smelter also derives its
electricity from an onsite thermal power station of 2.35 GW
installed capacity that is fuelled by natural gas.
D. Whitfield (&)
S. Akhmetov
N. Al-Jabri
Emirates Global Aluminium (EGA), Dubai, United Arab Emirates
e-mail: dwhitfield@ega.ae
significant CO2 emitted by the power plant, contributing to
78.6% of total Plant GHG emissions (Fig. 1).
Efforts to reduce the smelter’s GHG emissions have
focused on these three main sources through limiting power
consumption and increasing energy efficiency, lowering the
net anode carbon consumption and reducing the emission of
PFCs due to AE.
Energy Efficiency
To reduce energy consumption and hence GHG emissions
attributable to power generation, the specific energy con-
sumption at the Jebel Ali Operations smelter has been
decreased further from 14.82 DC kWh/kg in 2010 to 14.29
DC kWh/kg in 2016 (July YTD) (Fig. 2).
This reduction has been achieved through several
initiatives:

© The Minerals, Metals & Materials Society 2017 519

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_65
520
Fig. 1 EGA Jebel Ali GHG emission sources
Fig. 2 EGA Jebel Ali Operation smelter specific energy
• Gradual implementation of longer anodes in all cell
technologies to increase cross-sectional area, reducing
the cell voltage by 65 to 80 mV [1–3].
• Phase in of lower resistance graphitic (for D18 and
D18+ and fully graphitised (CD20, D20 and DX) cath-
odes, reducing the cell voltage by 30 to 60 mV [1, 3, 4].
• Implementation of D18+ technology cells in Potline 1
[3, 5], resulting in specific energy reducing from 15.0
13.0 DC kWh/kg to 13.0 DC kWh/kg (Fig. 3).
• Additional busbar to the D18 cells, reducing the external
voltage drop by 60 mV [6, 7] (Fig. 4).
Fig. 3 Potline 1 D18+ cells
D. Whitfield et al.
Fig. 4 D18 additional busbar
• Changing from round to rectangular cross-section col-
lector bars [2, 3] with higher cross-section, lowering cell
voltage by 30–40 mV (Fig. 5).
• Fine-tuning and optimising cell resistance set points after
amperage increase [8].
• Changing from 225 mm deep transverse (Fig. 6) to
380 mm deep longitudinal (Fig. 7) anode slots to better
aid gas release and reduce bubble resistance.
As well as reducing the specific energy consumption in
Potrooms, GHG emissions have been reduced through
greater emissions efficiency from the power plant, reducing
from 0.485 CO2e t/MWh in 2010 to 0.431 CO2e t/MWh in
Fig. 5 Change from round to rectangular collector bar
Fig. 6 225 mm deep traverse
anode slots
Fig. 7 380 mm deep
longitudinal anode slots
Reduction in EGA Jebel Ali Potroom GHG Emissions
Fig. 8 EGA Jebel Ali power plant emissions efficiency
2016 (July YTD) (Fig. 8). This has been achieved both by
investments in new capability and optimisation of the
existing plant generation.
Net Carbon Consumption
To reduce the consumption of anode carbon and conse-
quently reduce CO2 emissions, several initiatives have been
taken to reduce the net carbon consumption (NCC) from
0.430 t/t Al in 2010 to 0.423 t/t Al in 2016 (July YTD)
(Fig. 9).
• Improving dressing and redressing practices by Potroom
Operations [2] (Fig. 10).
• Improving follow-up auditing of anode dressing and
redressing by Process Control.
• Discontinuing centre-break alumina feeding in Potlines 1
and 3 (Fig. 11).
AE PFC Emissions
To minimise the frequency and duration of anode effects and
reduce the generation and mission of PFCs, considerable
development work has been performed with the cell control
logic and with operational practices. Despite already being at
Fig. 9 EGA Jebel Ali net carbon consumption
521
Fig. 10 Redressing of air burnt
anodes
Fig. 11 Centre-break alumina
feeding
already low levels, AE PFC emissions have been reduced
further, and are now at the lowest level ever for the Jebel Ali
Potrooms, down from 0.086 t CO2e/t Al in 2014 to 0.069 t
CO2e/t Al achieved for 2016 (July YTD) (Fig. 6).
The measures taken to maintain and reduce AE PFC
emissions include (Fig. 12):
• Fine-tuning alumina feed parameters at higher amperage
operation.
• Reviewing and improving the new cell alumina feeding
strategy.
• Improving the Potroom air supply so that it does not
reduce below the agreeing on minimum air supply
pressure of 6.0 bar.
• Optimising the AE quench sequence [1, 3] (Fig. 13).
• Improving the reliability of the alumina feed air slide
system.
• Discontinuing of centre-break feeding in Potlines 1 and 3
and converting to pseudo-point feeding [2, 3].
Fig. 12 EGA Jebel Ali AE PFC emissions
522
Fig. 13 Original and revised AE quench sequence [3]
• Implementation of D18+ cell technology in Potline 1.
• Fine-tuning and optimization of D18+ start-up strategy in
Potline 1.
Potroom GHG Emissions
Continued and considerable effort from Jebel Ali Potrooms
have enabled the reduction in the rate of Plant GHG emis-
sions to reduce from 9.96 t/t Al in 2010 to 8.49 t/t Al in 2016
(July YTD). The Potrooms GHG emissions due to specific
energy, net carbon consumption and AE PFC’s have reduced
from 9.01 t/t Al to 7.72 t/t Al in the same period (Fig. 14).
The annual Jebel Ali Potrooms GHG emissions reduced
to 8281 kT in 2015 and are forecast to reduce to 8226 kT for
2016, a reduction of 798 kT since 2010. This will be
achieved despite increasing hot metal production by 63,266
tons since 2010 (Fig. 15).
This significant reduction has been achieved from all
three main contributors sources for Smelter GHG emissions;
power, anode carbon and AE PFC emissions (Fig. 16).
This considerable achievement reflects the ongoing
efforts of the Jebel Ali Potrooms to continue to develop and
improve their smelter operations to achieve operational
excellence and minimise the environmental footprint. These
efforts are a good example to other smelters on how to
Fig. 14 EGA Jebel Ali Plant GHG emissions
D. Whitfield et al.
Fig. 15 EGA Jebel Ali Potroom GHG emissions and hot metal
production
Fig. 16 EGA Jebel Ali Potroom GHG emissions 2010–16
achieve successive and continual reduction in smelter envi-
ronmental impact as well as achieving direct economic
benefit.
Future
While significant reduction has been achieved in EGA Jebel
Ali Operations’ GHG emissions, further decreases are
expected from further initiatives already underway:
• Stabilising Potline 1 D18+ cells and further implemen-
tation of D18+ in Potline 3.
• D20+ cell technology.
• Technological advances in collector bar and cathode
design to reduce cell voltage and specific energy
consumption.
• Continued effort to minimise AE’s and their duration
though control logic enhancement and improved opera-
tional practices.
Conclusion
Significant reduction has been achieved in EGA Jebel Ali
Potrooms from all three main contributors sources for
smelter GHG emissions; power, anode carbon and AE PFC
emissions.
Reduction in EGA Jebel Ali Potroom GHG Emissions
Total annual Jebel Ali Potrooms GHG emissions have
reduced by 798,065 tons since 2010. This was achieved
despite increasing annual metal production by 63,266 tons
during the same period.
Acknowledgments The successful reduction in smelter GHG
emissions has been achieved through a combined effort of many
departments at EGA Jebel Ali as well as Potrooms. We are most
thankful to the support and exemplary work that has been performed
without which this achievement would have not been possible.
References
1. D. Whitfield, S. Akhmetov, M.M. Al-Jallaf, J. Blasques, K. Al
Aswad, I. Baggash, From the least to the most energy efficient
DUBAL potline—The P69/D18 developments. 11th Australasian
aluminium smelting technology conference, 6–11 Dec 2014, Dubai,
UAE (2014)
2. D. Whitfield, M.M. Al-Jallaf, S. Akhmetov, G. Meintjes, A.
Jassim, H.R. Devadiga, T. Al Midfa, Challenges with amperage
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increase in lines 7 & 9 at DUBAL. 11th Australasian Aluminium
smelting technology conference, 6–11 Dec 2014, Dubai, UAE
(2014)
3. D. Whitfield, S. Akhmetov, M.M. Al-Jallaf, J. Blasques, K.
Al-Aswad, I. Baggash, From D18 To D18+: Progression of
DUBAL’s original potlines. Light Met. 499–504 (2015)
4. M.M. Al-Jallaf, A. H. Mohamed, A. Kumar, M.S.W. Ali, Evolution
of CD20 reduction technology towards higher amperage plan at
DUBAL. Light Met. 451–454 (2009)
5. S. Akhmetov, D. Whitfield, M.M., Al-Zarouni, A. Al-Jallaf, A.
Al-Redhwan, W.A. Sidou, D18+: Potline modernisation at
DUBAL. Light Met. 561–566 (2013)
6. D. Whitfield, A.A.M. Said, M.M.K. Al-Jallaf, A.H.A. Mohammed,
Development of D18 cell technology at DUBAL. Light Met.
477–481 (2009)
7. D. Whitfield, T. Majeed, S. Akhmetov, M.M. Al-Jallaf, K.
Al-Aswad, I. Baggash, A. Al-Zarouni, Update on the develop-
ment of D18 cell technology at DUBAL. Light Met. 727–732
(2012)
8. A. Kumar, M.M. Al-Jallaf, M.T. Boraie, M. Al Faraj, S. Akhmetov,
Productivity with limited electrical energy availability in aged
side-riser cells. 11th Australasian aluminium smelting technology
conference, 6–11 Dec 2014, Dubai, UAE (2014)
 Partial Anode Effect in a Two-Compartment
Laboratory Alumina Reduction Cell

Henrik Åsheim, Thor A. Aarhaug, Wojciech Gębarowski,

Espen Sandnes, Asbjørn Solheim, and Geir M. Haarberg

Abstract
Most laboratory systems investigating the aluminium production process utilize a single
anode set-up. When approaching alumina depletion under constant current conditions in
such a system, the potential will increase to high levels (>10 V) and initiate an anode effect
and perfluorocarbon generation. However, it has been discovered by industrial measure-
ments that perfluorocarbon generation may also occur at normal cell voltages. With the use
of a two-anode setup in parallel with an electronic load this phenomena was investigated in
the laboratory. The results indicate that as long as the rest of the cell can acquire the extra
load, partial passivation of one or more anodes is possible and can be accompanied by
small amounts of PFC evolution (0–3 ppm mol CF4). Individual anode potentials can be
highly elevated, albeit the changes get buried in the total cell voltage. Only when the total
load becomes too large the voltage rises abruptly and substantial amounts of PFC can be
produced (
1000 ppm mol CF4).

   
Keywords
PFC Partial anode effect Non-AE PFC Low cell voltage PFC Aluminium
electrolysis

H. Åsheim (&)  W. Gębarowski  E. Sandnes  G.M. Haarberg

Department of Materials Science and Engineering,
Norwegian University of Science and Technology,
7491 Trondheim, Norway
e-mail: henrik.asheim@ntnu.no
W. Gębarowski
e-mail: wojciech.gebarowski@ntnu.no
E. Sandnes
e-mail: espen.sandnes@ntnu.no
G.M. Haarberg
e-mail: geir.m.haarberg@ntnu.no
T.A. Aarhaug  A. Solheim
SINTEF Materials and Chemistry,
SINTEF, 7465 Trondheim, Norway
e-mail: thor.a.aarhaug@sintef.no
A. Solheim
e-mail: asbjorn.solheim@sintef.no

© The Minerals, Metals & Materials Society 2017 525

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_66
526
Introduction
Aluminium is produced industrially by reduction of alumina
from a melt based on Na3AlF6–AlF3–Al2O3, often together
with several wt% CaF2 and/or MgF2 at about 960 °C [7].
Under normal conditions aluminium metal is produced at the
cathode and CO2 with a fraction of CO is formed at the
anode [6, 17]. The reversible potential for the reaction pro-
ducing CO2 (1) at the anode is about 1.2 V. Due to a rather
large anodic activation overpotential [11] and several ohmic
drops through the electrolyte and cell, the total cell voltage is
usually about 3.8–4.5 V.
0 lifetime, wear of anode slots will vary and this will influence
2Al2 O3 þ 3C ¼ 4Al þ 3CO2 E1000  C ¼ 1:17 V ð1Þ
Should the alumina content drop too much, polarisation
will increase to sustain the reaction, eventually extending so
far that other reactions become possible. Feasible combina-
tions include the two main anode effect reactions producing
the perflurocarbons (PFCs) CF4 (2) and C2F6 (3) [13, 18],
although, before the potential reaches such levels the anodic
production of COF2 (4) is thermodynamically also possible
[5]; a gas that readily reacts with water, carbon, or even self
decomposes at working temperatures.
3 3
Na3 AlF6 þ C ¼ 3 NaF þ Al þ CF4
4 4 ð2Þ
0
E1000 C ¼ 2:56 V
1 anode will vary with several factors like age, temperature,
Na3 AlF6 þ C ¼ 3NaF þ Al þ C2 F6
2 ð3Þ
0
E1000  C ¼ 2:76 V
1 1 3 3 3 segments, or parts of them. Any current redistribution will
Na3 AlF6 þ Al2 O3 þ C ¼ NaF þ Al þ COF2
2 4 4 2 4 ð4Þ
0
E1000  C ¼ 1:90 V
PFCs have gained much focus from governments and
environmentalists in later years due to their high global
warming potentials and long atmospheric lifetimes, making
them potent greenhouse gases [9]. The existence of PFCs not
related to the conventional anode effect with voltages of 8 V
and above, combined with an erratic current distribution, has
been documented for a variety of different technologies [3,
12, 21, 24]. Industrial measurements have shown that PFC
production may begin on one anode and under the right
conditions propagate to the entire cell [10].
Components of the Cell Voltage
Consider a laboratory cell with one anode and a cathode.
The total cell voltage of that system would be composed of
the anodic and cathodic electrode potentials, together with
H. Åsheim et al.
ohmic drops (IR) over the electrolyte, the bubble layer,
through the anode carbon and cathode lining, as well as any
other external current carrying parts (omitted in this repre-
sentation). It can be described by the following relation
VCell ¼ EA þ jEC j þ Itot  ðRA þ RBubble þ REl: þ RC Þ ð5Þ
An industrial cell, however, has a large number of anodes
(20–40+) connected in parallel. In the ideal case all the
parallel segments are the same and share an equal part of the
total current. Nevertheless, reality is that there are as many
different cases as there are anodes [4, 22]. Anodes are being
consumed and their resistance, RA , will vary throughout their
bubble overvoltage, and the anode to cathode distance
(ACD) might vary with magnetohydrodynamics (MHD).
Alumina concentration gradients can also develop due to
poor mixing, blocked feeder holes or work practices.
Keeping in mind that the voltage over the segments has to be
equal, it is clear that the current can develop unbalanced over
the anodes. Inasmuch as the molten aluminium is uniform
and inhabits high electrical conductivity, its potential can be
assumed equal for all parallel circuits. Hence, on a per anode
basis the cell voltage becomes:
VCell ¼ EA;i þ Ii  ðRA;i þ RBubble;i þ REl:;i Þ
ð6Þ
þ jEC j þ Itot  RC
Thus it can be inferred that the current-flow through an
electrolyte mixing and work practices like anode change.
Any change in current of one segment will induce an equal
and opposite change that will be distributed over the other
produce an increase in cell voltage; an increase that dimin-
ishes as the number of segments increases, as modelled by
Wong et al. [23] for two theoretical smelters. It is hence
evident that a segment carrying low current will have an
elevated interfacial electrode potential, and since little
overpotential is associated with the cathode it will display as
heightened anodic potential. If the anodic potential rise is of
sufficient magnitude co-evolution of fluorine containing
gases like CF4 becomes possible.
Methods and Equipment
Cell and Electrodes
The experiments were conducted in an electrically heated
vertical laboratory furnace with a mullite inner tube and
alumina heat radiation shields. A cylindrical block (∅
90 mm) of graphite (Schunk-Tokai) was used as cathode
material. From this block two equally shaped electrolyte
Partial Anode Effect in a Two-Compartment Laboratory … 527

compartments were machined, with a depth of 110 mm and Gas sampling

tube
separated by a 5 mm wall. Two matching steel plates
Reference el.
(*1 mm smaller than electrolyte compartment, 5 mm
Thermocouple
height) were added to the crucible base to improve
cathode/aluminium wetting and give a flatter and more Anode current
lead
uniform metal pad. The non-circular shape of the electrolyte
compartments makes it difficult to shield the sides from stray
currents, however, it was necessary to include space for
reference electrodes and gas sampling tubes.
The electrolyte was made up of cryolite (Na3AlF6,
Aldrich), aluminium fluoride (AlF3, industrial grade, sub-
limed at 1090 °C) and alumina (Al2O3, Merck/Aldrich). The
Anode carbon
alumina concentration in the different compartments was
often selected as 5 wt% and 1 wt% at the beginning of an Electrolyte
experiment, with occasional additions after heavy anode
Steel plate
passivations. The cryolite ratio (CR, NaF/AlF3) was adjusted
Crucible and
to 2.3, being somewhat altered throughout due to con- cathode
sumption of alumina and evaporation of electrolyte con-
stituents [8]. All electrolyte components were dried at Fig. 1 Experimental setup of two-compartment crucible. Each com-
200 °C prior to the experiments. partment has its own anode, reference electrode and electrolyte.
The anodes were made from graphite (Schunk-Tokai) (Reference and gas sampling tube placed beside anode for clarity, in
reality they are in front and behind)
cylinders (∅ 22 mm, height 40 mm) that were electrically
connected by a steel tube (∅ 6/8 mm). The anodes were
submerged 10 mm, giving an approximate surface area of
10.7 cm2. Within the steel tube and 10 mm into the anode
a b
carbon thermocouples were placed to read the anode tem-
PSU
perature. Additionally, a short piece of alumina tube
(50 mm, ∅ > 8 mm) was placed around the steel current EL EL EL
carrier just above the anode carbon to protect it from cor-
rosion due to electrolyte splashing or condensation. cell
Two aluminium reference electrodes were used, one for
each electrolyte compartment. The bottom exterior was
produced from a milled out BN rod (∅ 5/10 mm) of length Fig. 2 Electric circuit representation of the electrochemical cell. EL
electronic load, PSU power supply; a two electrodes under test,
70 mm that was threaded on to a steel tube (∅ 8/10 mm). b simulation of anodes in parallel
Aluminium to cover 15 mm of inner height when molten
was placed inside the BN rod and a hole (∅ 2 mm) was
drilled 5 mm above the aluminium level. Electrical con- (Chroma 63201, 300 A). Electronic loads (Agilent N3302A
nection was provided with a tungsten wire (∅ 1 mm) in Agilent N3301A chassis) were also added in series with
shielded by an alumina tube (∅ 1.5/3 mm), except for the the real anodes to add an ohmic drop so the total cell voltage
bottom 5 cm that would otherwise be in contact with elec- was elevated to industrial levels. All loads were set to
trolyte and aluminium, which was shielded with a BN tube operate in constant resistance mode. A diagram of the
of similar diameter. A sketch of the complete electrode electric circuit is presented in Fig. 2.
set-up can be viewed in Fig. 1. Data were logged with National Instruments Com-
pactRIO 9074 with modules NI 9229 and NI 9205 for
voltage logging, as well as thermocouple module NI 9211.
Electrical Equipment and Data Loggers The currents flowing through the different segments were
captured from the current monitor outputs on the loads. The
The current was supplied with a system power supply Chroma load output was passed through a polynomial
(Agilent 6682A, 240 A). The positive terminal was split in function to correct for the slightly non-linear output. Data
three parts; the two real anodes and load balancing with were sampled at 10 Hz (thermocouple data limited to
“virtual anodes” by a high amperage electronic load 3.5 Hz) through LabView software.
528 H. Åsheim et al.

Table 1 Specifications of the Parameter Gasmet CR 4000 ProtIR 204M

two different FT-IRs
Cell volume/l 0.4 2.7
Path length/m 5 6.4
Spectral range/cm−1 600–4200 400–8000
Resolution/cm−1 8 1
Absorbance 0–3 –2 to 4
Detector MCT–LN2 MCT–Peltier

Gas Analysis 6 0.25

CF4
1281 cm-1
Two FT-IRs were used in these experiments, one for each 5
0.2
anode chamber. They are somewhat dissimilar as two equal

Concentration / ppm
4
instruments were not available. Details on the equipment are

Absorbance
0.15
given in Table 1. Gas samples were taken from about 3 cm
3
above the electrolyte surface, approximately 0.5 cm off the
0.1
side of the anodes.
2
The furnace was continuously being served argon at a
small overpressure. This pressure produced a flow of 1
0.05

*300 Nml min−1 through the ProtIR connected to ch. 1, and

a flow of *150 Nml min−1 through the Gasmet of ch. 2. No 0 0
0 2000 4000 6000 8000 10000
other exhaust ports were being used. The gas to each Time / s
instrument passed through two 15 lm particle filters con-
nected in parallel, a Drierite® filter for water removal, and an Fig. 3 Response of Gasmet FT-IR when applying 5 ppm mol CF4
reference gas diluted through Environics 4000 gas mixer to different
active alumina filter for HF removal. The flow rate through
concentrations. T90-response of about 248 s
the instruments were approximately the same during elec-
trolysis. Gas production during electrolysis at 10 A was
approximately 35 Nml min−1 when considering CO2 and 1
CF4, and twice that with CO as the only anode product. An Gasmet 1281 cm-1
0.9 Linear reg.
Environics 4000 gas mixer was employed for calibration ProtIR 1281 cm-1
0.8 Linear reg.
purposes together with a 5 ppm mol CF4 reference gas
0.7
cylinder.
Absorbance

0.6

0.5
Results and Discussion 0.4

0.3
The response and dynamics of the gas analysis equipment is
0.2
given in Fig. 3 for the Gasmet FT-IR. It shows the absor-
bance of a 5 ppm mol CF4 reference gas cylinder that was 0.1

diluted to concentrations 1 through 5 ppm mol with an 0

Environics 4000 mixer. Gas was input at the anode position
of the furnace at ambient temperature. T90-response for the
Gasmet and ProtIR is estimated to be 248 and 300 s,
respectively, with first visible change occurring from 106
and 50 s.
The most prominent absorption line for CF4, 1281 cm−1,
is plotted for both Gasmet and ProtIR in Fig. 4. The lower
concentrations for Gasmet are data produced with the gas
mixer, the rest are previous reference data. Beyond the
concentrations presented the absorbance data quickly
become increasingly non-linear and for higher concentra-
tions other absorption lines have to be considered.
0 5 10 15 20
Concentration / ppm
Fig. 4 Absorbance response of CF4 at wavenumber 1281 cm−1 for
different FT-IRs. Beyond these concentrations the absorbances at this
wavelength became increasingly non-linear
The same mixing procedure as that of Fig. 3 was con-
ducted in-between electrolysis with the furnace heated to
1000 °C, and no CF4 response was visible on either FT-IR.
The pathway between inlet and detector was in this case
longer, as it passed from the bottom of the furnace, past heat
radiation shields and around the crucible before it finally left
Partial Anode Effect in a Two-Compartment Laboratory …
through the sampling tubes by the anodes. CF4 might
decompose over solid substrates like tungsten and steel as
discussed by Rogers et al. [15], or over SiO2 according to
Siegemund et al. [16], and decomposition over activated
alumina has been shown by Thonstad et al. [19]. Øygard
et al. [14] extracted gas both directly from the anodes and
from the gas duct and found that a large part of the PFC
decomposed on its way out of the cell. Thermal decompo-
sition has also been found to begin at about 800 °C [16]. In
the furnace the radiation shields were composed of alumina
and the tube was made from mullite, a mineral of alumina
and silica. From an environmental point of view it is good
that the PFCs get broken down, however, it also makes it
difficult to investigate conditions with low concentration
PFC production. High temperature residence time is a key
parameter that needs to be kept low in order to detect the
lower concentrations.
Figure 5 shows an IR spectrum recorded directly after 5 g
alumina (undried, *1 wt% H2O) was fed to the cell.
Overlaid is a plot of a 1000 ppm mol CH4 reference that
shows a clear match. Several methanation routes are possible
e.g. H2O + C = CO + H2 and subsequently H2 + C = CH4
as discussed by Walker [20]. Before alumina addition the
corresponding anode had previously run into AE and was on
a “passivation” current of 3.1 A (29% of initial) with an
anode potential of 4.6 V. The abrupt initial partial passiva-
tion produced a peak of 1.5 ppm mol CF4 while it thereafter
hovered around 0.2 ppm mol for *1 h. During feeding of
(wet) alumina there is a small peak at 1281 cm−1 not well
accounted for in the methane reference spectrum. Inasmuch
as water is not visible in the spectrum, the added absorption
is considered to be due to presence of CF4. Multiplying the
reference spectra with 1.25 to make a better overlap and then
2.5
During alumina feed
1000 ppm CH4 reference
2 current of about 2.3 A, Anode 1 was initially wobbling
1.5
Absorbance
1 spectral lines. In this experiment only the Gasmet FT-IR was
0.5
0
-0.5
1000 1500 2000 2500 3000 3500
Wavenumber / cm-1
Fig. 5 IR spectrum from Gasmet during feeding of (wet) alumina with
an overlaid 1000 ppm mol CH4 reference. There is a clear overlap in
the CH4 absorption region around 1300 and 3000 cm−1. The rest of the
spectra is CO/CO2 with a small CF4 peak at 1281 cm−1
529
taking the difference in absorbance, gave a coarse estimate of
3.3 ppm mol CF4 released during feeding. Current and
voltage changed to 4.9 A and 4.1 V for that particular anode.
No PFC was found to be released when feeding dry alumina.
Figure 6 shows an event from the two-compartment
set-up where at 9800 s the external electronic load has its
resistance doubled in a two step manner (too low voltage
set-point for PSU gave short downward bump in load current
before treated). In practice this halved the number of “virtual
anodes” and approximately doubled the pressure on the real
elements. Before this step the two anodes had been partially
passivated for 22 min (Anode 1) and 32 min (Anode 2),
both passing about 1.7 A (16% of initial). The cell voltage
rose from 5.4 to 10.7 V and initiated a rocking motion of
both current and voltage for Anode 2, not unlike the oscil-
lations seen by Åsheim et al. [2] previously, albeit at less
elevated potential. Anode 1, on the other hand, just notice-
ably increased to between 2 and 3 A.
Anode 2 is clearly producing a lot of CF4, well past the
linear part of 1281 cm−1. Absorption at 1536 cm−1 was used
to estimate the concentration to upwards of 1400 ppm mol.
The absorbance also markedly increased for CO, which is
not uncommon [1], while CO2 appeared to be produced to a
lesser extent. At Anode 1 there is only marked change in CO
and to some extent CO2, no visible PFC detection. In an
industrial cell Anode 1 would have been influenced by
mixing from the oscillating gas production at Anode 2, but
with completely separated chambers this is not possible here.
Figure 7 shows an anode going from partial passivation
to regular production and back to partial passivation again.
Entering the plot both anodes had previously been passi-
vated and subsequently fed more alumina, with the theo-
retical concentration being 4.5 wt% and 3.7 wt% for ch. 1
and ch. 2, respectively. Throughout, compartment 1 was
theoretically depleted at 21,800 s while compartment two
had a theoretical concentration of 1.6 wt% at the right end of
the plot. While Anode 2 looks steadily passivated with a
between 7.5 and 10 A before it observed about 50% partial
passivation and a much higher noise. At the same time there
was a marked drop in CO and a very tiny increase of PFC
employed, and placed in ch. 2; even so, it is evident from the
gas analysis that without the second FT-IR much of the gas
produced in ch. 1 also flow to the FT-IR on ch. 2. It is
believed that some CF4 was formed under these conditions,
and mostly at Anode 1 with the higher current. However, the
4000 added gas path and residence time are not beneficial for
detection, as discussed above.
Sometime before 20,000 s there is a big change in the
system and Anode 1 spiked back to regular production with
much less noise. The increased production most likely gave an
initial pressure effect that is visible in the FT-IR data. Anode 2
530 H. Åsheim et al.

Absorbance 2 Ch 1 CF4 1281 cm-1 * 100

Ch 2 CF4 1281 cm-1

0.6 Ch 1 CO2 3736 cm-1 * 10

Absorbance

Ch 1 CO 2177 cm-1
0.4
Ch 2 CO2 3736 cm-1 * 10
0.2
Ch 2 CO 2177 cm-1

0
Temperature / °C

1030 Anode 1
Anode 2
1020

1010

1000
12
10 Anode 1
Voltage / V

Anode 2
8 Cell voltage
6
4
2
15
Anode 1
Current / A

10 Anode 2
Virtual anodes (20)

0
0.95 0.975 1 1.025 1.05 1.075 1.1 1.125 1.15
4
Time / s 10

Fig. 6 Two anodes that already were partially passivated have their degree of parallel elements decreased by almost half. Anode 2 started to
oscillate in current and voltage and produced upwards of 1400 ppm mol CF4. Anode 1 showed no detectable change in CF4 level

1
Absorbance

0.8 Ch 2 CF4 1281 cm-1 * 100

0.6 Ch 2 CO2 2360 cm-1
0.4
Ch 2 CO 2177 cm-1
0.2
1030
Temperature / °C

1020

1010
Anode 1
1000 Anode 2
990
5
Voltage / V

4
Anode 1
3 Anode 2
Cell voltage
2
15
Anode 1
Current / A

10 Anode 2
Virtual anodes (20)
5

0
1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
Time / s 104

Fig. 7 Current, voltage, gas and temperature profiles of two anodes. was passivated to about 20% of the initial current throughout the plot
Anode 1 experienced a change from regular production, through partial with just a few current humps that get visualised as small hills in CO
passivation, back to regular production before ending up at partial absorbance
passivation again. Absorbance of CF4 is very slightly elevated. Anode 2

also peaked in current, albeit quickly crept back to its former throughput of 5–7 A, again coupled with a very slight
value with only some distant spikes that are visualised as increase in CF4 absorbance. Due to the degree of parallel
humps in the CO gas data. After a while Anode 1 was depleted elements of the system, the cell voltage merely varied between
of alumina and turned back to partial passivation with a 5.09 and 5.34 V during these events.
Partial Anode Effect in a Two-Compartment Laboratory …
Clearly, as long as “the rest” of the cell is able to acquire
the load, several anodes can be partially, or even fully pas-
sivated. A full conventional anode effect will not be initiated
until the critical current density has been reached on a large
number of anodes, producing a large upswing in voltage.
Such a condition cannot be reached in the present set-up
with a high degree of parallel segments with electrical ele-
ments (20:2). The load can easily accompany the extra
current of the real anodes with a relatively small increase in
voltage (*0.5 V). Only when approximately halving the
number of “electrical segments” (10:2) is something
resembling the conventional industrial anode effect visible,
with high cell voltage (>10 V), considerable production of
CF4 and an erratic current distribution. Even still, for one of
the anodes this potential drive was not enough to break away
from low current constant passivation.
Conclusions
By increasing the degree of parallel segments of a laboratory
cell with additional anodes and/or electric elements it is
possible to investigate the phenomena of partial anode effect
in the laboratory. The results indicate that as long as the rest
of the cell (or load) is able to pass most of the current, only
small amounts of PFC are produced (0–3 ppm mol CF4),
even with one or more anodes completely passivated. Indi-
vidual anode potentials of a small number of anodes can be
elevated far into the PFC territory, but the changes get buried
when looking at the total cell voltage. However, when the
total load for the cell is too high and the voltage increased by
a large margin substantial amounts of PFC can be produced
(
1000 ppm mol CF4).
The anodic production of PFC is likely somewhat higher
than what is released to the environment as at high tem-
perature it will decompose on several substrate materials
used in the aluminium industry.
References
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 Co-evolution of Carbon Oxides and Fluorides
During the Electrowinning of Aluminium
with Molten NaF–AlF3–CaF2–Al2O3 Electrolytes

M.M.R. Dorreen, M.M. Hyland, R.G. Haverkamp, J.B. Metson, Ali Jassim,
B.J. Welch, and A.T. Tabereaux

Abstract
The recent finding of continuous background PFC co-evolution during apparently normal
operations of large operating smelting cells has raised the question as to whether or not
these arise from a different reaction mechanism since they occur at similar cell voltages to
what is considered to be below the threshold when calculating greenhouse gas emissions
emanating from cells. The analysis presented from this combination of studies suggest that
all PFC emissions are triggered by the anode potential approaching that necessary for
COF2(g) formation, with the intermediate formed on the electrode surface decomposing to
release an increased amount of CO(g) as well as CF4(g) according to the overall reaction

Al2 O3 þ 2Na3 AlF6 ðl) þ 9=2C ¼ 4Al þ 3CO(g) þ 3=2CF4 ðg) þ 6NaF ð1Þ

Because of the difference in kinetics of discharge of the two anions, and the extra thermal
energy necessary to satisfy the overall enthalpy, partial passivation of the electrode surface
can occur when it is under cell voltage control. The situation also applies to individual anode
in large cells and therefore gives rise to PFC co-evolution through spatial variations. As the
spatial changes propagate the same process leads to a full anode effect in the operating cell.

 
Keywords
Anode reactions PFC co-evolution Anode potentials

M.M.R. Dorreen  M.M. Hyland  R.G. Haverkamp

J.B. Metson  B.J. Welch
LMRC, University of Auckland, Auckland, New Zealand
M.M.R. Dorreen  M.M. Hyland
University of Auckland, Auckland, New Zealand
A. Jassim  B.J. Welch
Chemical Engineering, University of New South Wales,
Sydney, Australia
A.T. Tabereaux (&)
Independent Consultant, Florence Ala, USA
e-mail: attaber@aol.com

© The Minerals, Metals & Materials Society 2017 533

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_67
534
Introduction
During the last two decades the aluminium industry has
made extensive advances for reducing the amount of
fluorocarbons (PFC’s) that are co-evolved during an “anode
effect” (AE), which is typically linked with the depletion of
the alumina concentration in the electrolyte below a critical
level, and a significant increase in the cell voltage. The
common interpretation represented in texts and publications
is for the primary electrochemical reaction to be:
2Al2 O3 ðdissolvedÞ þ 3C ¼ Al þ 3CO2 ðgÞ ð1Þ
which has a standard reversible/reaction initiating potential
of 1.191 V transitioning to the potential for direct formation
of CF4(g) as a consequence of electrochemical depletion of
the alumina in the electrolyte. The latter has been assumed to
be by either the reaction
4=3Na3 AlF6 ðlÞ þ C ¼ 4NaF(l) þ CF4 ðg) þ 4=3Al ð2Þ
or
4NaF(l) þ C ¼ CF4 ðg) þ 4Na ð3Þ
these reactions having initiating potentials in the band 2.5 to
2.7 V.
As first observed by Bunsen [1] the phenomena referred
to as an “anode effect” or AE can be induced by increasing
current density beyond a “critical value” in all molten
halides using carbonaceous anodes. The phenomena are
inevitably associated with either the formation of halocarbon
compounds or passivation of the surface blocking current
flow. When induced under constant current control the AE is
associated with substantial sudden cell voltage increase. In
contrast when the electrochemical cell is under cell voltage
or electrode potential control a substantial decrease in cur-
rent occurs. Aluminium smelting cells operate under a
mixture of these two types of control. The total current to a
given cell is constant but voltage drop for each anode pair is
constrained because of the high electrical conductivity of the
anode beam and aluminium metal pad as illustrated in
Fig. 1. However localised variations can occur for the
resistance and electrode potential components of each anode
Fig. 1 The equivalent circuit of
the modern multi-electrode
pre-bake anode cells
M.M.R. Dorreen et al.
beam to metal pad current path so consequently the current
distribution between anode’s can shift.
The voltage influencing components that can change for
each electrode to metal pad pair include electrolyte resis-
tance—through anode setting reference, anode potential—
through alumina concentration temperature or solvent com-
position gradients, and consequentially the bubble resistance
through the changed electrode current.
Changes in anode currents at normal operating voltages
associated with PFC release preceding AE’s have been
report by several researchers [2–5]. This highlights that
using a the present magnitude of voltage rise to an AE ini-
tiating estimates of the amount of fluorocarbons released to
the atmosphere in the electrowinning process is questionable
since the products formed dependent on individual electrode
potential not cell volts. A better understanding of the reac-
tions and associated responses that initiate PFC co-evolution
is needed for defendable prediction of the GHG emissions.
Calandra et al. [6] when performing fast sweep-rate cyclic
voltammetry in the Al2O3–NaF–AlF3 system identified a
peak attributed to COF2(g), a gaseous component cited in the
JANAF Thermochemical database. The reversible standard
state potential for the formation of this gas at 1233 K
according to the equation
Al2 O3 þ 2Na3 AlF6 ðlÞ þ 3C ¼ 4Al þ 3COF2 ðgÞ þ 6NaF(l)
ð4Þ
is 1.861 V. However since this gas is thermodynamically
unstable in the presence of carbon, potentially decomposing
according to the reaction:
2COF2 ðgÞ þ C ¼ 2CO(g) þ CF4 ðg) ð5Þ
where DGo1233 K = − 45.77 kJ. The depolarising effect of
Eq. 5 provides a mechanism for even lower voltage PFC
formation at individual electrodes that have undergone
increased polarisation due to localised depletion of the alu-
mina concentration in a multi-electrode cell.
Hitherto the co-evolution of PFC’s at low voltages have
been described differently in publications, and questions
exist as to whether or not they are formed via the same
process and by the same reactions existing when a normal
Co-evolution of Carbon Oxides and Fluorides … 535

anode effect occurs. A better understanding of the mecha- one expects a change in rate of increase in current with
nistic paths and cell conditions is needed in order to develop voltage whenever there is initiation of a new reaction.
suitable methodologies for quantifying the environmental
impact.
This paper arises from four different investigations which R&DFindings
when combined present strong evidence that not only sup-
ports the mechanism according to the Eqs. 4 and 5, but also
indicates it is the most dominant mechanistic path for all
PFC evolution in aluminium smelting cells. (a) Single Electrode—Constant Current Control
The four different techniques used are: Electrolysis

(a) continuous monitoring of the evolved gases in during
constant current electrolysis of an externally heated
(approximately 50 A) single electrode laboratory cell,
during which the alumina concentration is depleted at a
constant rate,
(b) continuous monitoring of the evolved gases from a
multi-electrode internally heated operating pre-bake
cells under total current control during various work
practices and stages of self-control,
(c) an analysis of fast sweep voltammetry transition
potentials of electrode reactions, and
(d) linking the potentials to the operational causes for ini-
tiating background PFC formation.
Table 1 presents the thermochemical analysis of possible
reactions associated with evolution of fluorocarbons in alu-
minium smelting cells. Electrochemically, the voltages
derived from the Gibbs energy indicate reversible electrode
potentials and therefore the minimum needed to initiate the
reaction. However because gases are formed there is addi-
tional energy required—referred to as entropic energy
(TDSreaction)—for completion of reaction and this can be
provided either by additional heat transfer or electrode
potential if isothermal conditions prevail. Electrochemically
A specially designed 50–100 A laboratory cell [7] was
used in order to simulate smelter operating conditions for the
gas release. A close fitting boron nitride sleeve lining
the cathodic crucible plus a boron nitride protective cap
on the top and sides of the 75 mm diameter anode, mini-
mized the ability of the evolved gases to undergo secondary
reactions.
The current was supplied by two Hewlett-Packard Model
6672A programmable DC supplies interfaced in series giv-
ing a voltage capability of zero to 40 V and current capa-
bility of 0 to 100 A. The cell voltage could be recorded at
10 kHz while a specially designed circuit interfacing the DC
power supply to the cell had a fast action (sub-microsecond)
current load switch, thus enabling estimation of the cells
total ohmic voltage component as well as the combined
electrode potentials (see Fig. 2). The gas stream was led
directly to the automatic sampling valve of the Ametek
Dycor MA100M quadrupole mass spectrometer and gas
samples were analysed at 40 s intervals.
The experimental procedure was to charge the crucible
with a fixed mass of solvent electrolyte and the required
amount of alumina to give the desired starting concentration.
After thermal equilibration the oxide was electrochemically
depleted at constant current until after the fluorocarbons

Table 1 Thermochemical analysis for the initiation and completion energy requirements for the various fluorocarbon formation reactions
Eqn. Reaction DGo1233 K Eo1233 K DHo1233 K Heat deficit at Isothermal
# V = 1.8 V + iRexternal Voltage
*kJ/mole Volts *kJ/mole kJ/2 g atom Al** Visothermal at
Al2O3 Al2O3 1233 K
4. ½Al2O3 + Na3AlF6(l) + 3/2C = 2Al + 3/2COF2(g) 1078.8 1.864 1438.0 396 2.484
+ 3NaF(l)
6. ½Al2O3 + Na3AlF6(l) + 9/4C = 2 Al 1044.6 1.806 1530.3 488 2.646
+3/2CO(g) + ¾CF4(g) + 3NaF(l)
2. 2Na3AlF6(l) + 3/2C = 6NaF(l) + 2Al + 3/2CF4(g) 1467.4 2.534 1709.7 668 2.953
3. 4NaF(l) + C = 4Na + CF4(g) 1041.2 2.697 1291.7 740 3.150
7. 2AlF3(l) + 2C = 2Al + C2F6(g) 1417.4 2.449 1504.5 462 2.599
8. 2Na3AlF6(l) + 2C = 6NaF(l) + 2Al + C2F6(g) 1593.4 2.752 1774.8 732.6 3.065
*Where some of the metal is produced from fluorides, the calculation is based on the equivalent number of molecules of alumina
**All these equations involve producing some of the Al from a fluoride and therefore this is represented per 2 g atoms of Al produced
536 M.M.R. Dorreen et al.

normal anode effect with the cell voltage rising extremely

rapidly and exceeding 8 V. Linked with the voltage rise was
the appearance of fragments consistent with CF4 formation.
Figure 3 shows fluorocarbon fragments expected to be
formed from COF2 started appearing approximately five
minutes before the cell displayed the characteristics of a
normal anode effect with the cell voltage rising extremely
rapidly and exceeding 8 V. Linked with the voltage rise was
the appearance of fragments consistent with CF4 formation.
Using the current interruption when the anode current
density was of 0.55 A cm−2 and electrolyte contained
6.5 wt% Al2O3 gave a combined potentials was
1.65 ± 0.02 V. Doubling the current to 1.1 A cm−2 this
increased to 1.68 ± 0.02 V. As expected cell voltage
increased with the alumina concentration depletion and this
is illustrated in Fig. 4, where PFCs were detected before
100 min, and progressed to a full anode effect after 105 min.
Fig. 2 The I–V response with fast switching during constant current The cell voltage rise for this, and for other experiments, from
electrolysis
that existing at 3% alumina concentration was less than
200 mV before PFCs are co-evolved.
were detected by the gas analyser. Because of self-heating The ratio of carbon monoxide to carbon dioxide was
the temperature increased with resulting superheats being in found to increase several minutes before the anode effect
excess of 20 °C. By performing a continuous oxygen bal- with the ratio increase becoming substantial once the anode
ance, the alumina concentration and current efficiency could effect occurred.
also be determined continuously.
During the early phase of electrolysis for each system (b) Comparable anode gas studies in smelting cells
studied the only gases evolved were a mixture of carbon
monoxide and carbon dioxide, with the carbon monoxide A syringe was used to take regular samples of the cell gas
concentration being higher than at the equivalent current flowing through a pipe inserted in a hole drilled through an
density for a normal operating smelter cell, but the oxygen anode of an operating 180 kA pre-bake anode cell. Both a
balance was consistent with higher rate of CO generation as conventional gas chromatograph and an Extrel ELQ-400
expected as a consequence of the higher superheat [8]. GC-MS unit were used for the analysis.
Figure 3 shows fluorocarbon fragments expected to be During normal electrolysis the typical anode gas
formed from COF2 started appearing approximately five composition detected was in the band 70 to 85% CO2 and
minutes before the cell displayed the characteristics of a 15–30% CO. This trend is illustrated in Fig. 5 for two cells
that had anode effects induced by stopping adding alumina.

Fig. 3 Fluorocarbons detected before and after the cell having an Fig. 4 The change in cell voltage during the electrochemical depletion
anode effect of alumina
Co-evolution of Carbon Oxides and Fluorides …
Fig. 5 Analysis of gas samples from an anode before and through a
AE’s in 180 kA cells
The two noticeable features of these graphs are the
indication of a small decrease in CO2 concentration prior to
the AE and before the appearance of the fluorocarbons fol-
lowed by a substantial increase in proportion of carbon
monoxide when the perfluorocarbons are coevolved.
In order to quantify and further understand this trend, the
sampling frequency of gases being evolved was increased
before another anode effect occurred in the cell until several
minutes after when the gas composition had stabilised. The
resulting trends are presented in Fig. 6.
After initiation of the anode effect, co-evolution of both
CF4 and C2F6 was observed with the latter diminishing
below the detection limits while the CF4 concentration
increased to 16%. Simultaneously the CO concentration
increased to *67%, while the CO2 decreased to *17% over
the first five minutes of the anode effect. This gives more
than a twofold increase in CO per mole of CF4. When the
Faradaic yields and equivalent amount of charge transfer for
the different components is taken into account Table 2
demonstrates the increase in CO evolution is compatible
with Eqs. 4 and 5 after allowing for the higher interfacial
thermal energy [8].
(c) Determining PFC Transition potentials
Calandra et al. [5, 10] identified peaks consistent with
COF2 for both the system Na2O–NaF and Al2O3–NaF–AlF3,
formation using very fast linear sweeps, and proposed sur-
face passivation with a fluorocarbon intermediate was the
537
Fig. 6 Results from high frequency sampling and analysis of gases
emitted from anodes of a 180 kA cell
primary cause of an anode effect. More recently a C-F
intermediate has also been identified on the anode surface
[11]. This latter finding is also consistent with visual
observations of anode effects in operating smelting cells
which are maintained at constant current. The heat genera-
tion associated with the higher interfacial voltage drop
would provide thermal energy to complete the reaction sat-
isfying the entropic energy deficit highlighted in Table 1.
However for a better understanding of PFC evolution under
all situations there is a need to ascertain whether the
“background PFCs” formation mechanism is the sole reac-
tion or other dominating reactions occur during an anode
effect. Consequently we have re-analysed unpublished
results from voltammetric studies, which were primarily for
electroanalytical purposes [9]. In that research the total
surface of the small (0.75 cm−2) graphite electrode was
vertically oriented in order to prevent blockage by any gas
bubbles formed electrochemically. The graphite crucible
counter electrode had a large surface area, so that it did not
polarise. The cell voltage was increased over a 5 V range, at
an average sweep rate of 20 V per second, and then reversed
at approximately 200 V per second. The current during each
sweep cycle was recorded by a data acquisition at 2 kHz.
The solvent electrolyte used was of similar composition to
that commonly used in smelting in electrowinning, but with
dissolved oxide concentrations from 0.75 to 4.55 wt%
Al2O3 to encompass the range normally experienced in
smelting cell operation.
538
Table 2 The change in Gas
proportion of electrochemically
generated gases during anode Gas % before AE
effect Gas % after AE
Change
% current before AE
% current after AE
The rapid fall in current once the “critical current density”
(the peak value for a given sweep) is reached, confirms
formation of a passivating film on the electrode surface.
Once the current drops to the very low value there is
insufficient thermal energy generated to complete the reac-
tions according to Table 1. The passivation must originate
from the discharge of another anion, presumably F−, and this
initiates from the inflections below 2 V in the forward
sweeps for alumina concentrations below 1.75 wt%.
The illustrated voltammograms include a contribution
from the ohmic resistance of the electrodes and circuitry
which ranged between 0.31 and 0.35 X.
Therefore at any instance in the sweep the, voltage can be
simply represented by the following equation.
V ¼ ENernst þ ganode þ iRCircuit þ IRanode surface film :
Consequently in order to get a closer estimate of
the potentials for the change in electrode process
(E Nernst + ηanode) to fluoride anion co-oxidation, the volt-
ages below the critical current density for the sweeps pre-
sented in Fig. 7 were adjusted to allow for the ohmic drop
and the results gave a consistent inflection—indicating a
change in electrode process—at 1.82 ± 0.25 V. This is also
consistent with earlier studies [12] For the high alumina
concentrations sufficient oxy-anion were being discharged
with the fluoride anions to delay full passivation enabling
higher currents and voltages even though PFC’s were being
co-evolved. However once passivation occurred
Fig. 7 Voltammograms from fast linear sweep cell voltage at various
alumina concentrations (increasing at 20 V s−1 reverse at 200 V s−1.)
M.M.R. Dorreen et al.
CO2 CO CF4
71 29 0
17 67 16
−54 +38 +16
83 17 0
26.1 50.3 23.6
electrochemical stripping of the layer did not initiate until
the cell and electrode voltage dropped below approximately
2.3 V for all alumina concentrations.
These curves demonstrates not only the anode effect is
due to full passivation with fluoride anions, but also thermal
energy is required to remove the passivation film and enable
oxy-anion co-deposition to complete the reaction. There is
no indication of any other reaction contributing to the
fluorocarbon co-evolution other than the combination of
Eqs. 4,5, and 6.
This also provides an explanation of why C2F6 is only
formed in the short period following the increase in voltage
or an anode effect.
(d) Operational Causes and Voltages of low-level PFC
ð9Þ co-evolution in smelting cells..
The magnitude of the cell potential change necessary to
initiate PFC co-evolution without the consequences of an
anode effect, has been determined by monitored both indi-
vidual anode currents and the composition of the cell gases
in a *200 kA, 20 anode operating cell when various per-
turbations are introduced that can bring about localised
spatial variations in cell conditions.
In perturbation trial for a cell operating smoothly with a
balanced current between anodes and without emitting any
detectable PFCs the average dissolved alumina concentra-
tion of the cell was decreased approximately 0.3% fairly
quickly by reducing the amount of alumina added during an
over-feed cycle. The switching trigger limits were main-
tained, with the switching from underfeed to overfeed being
based on the same conditional voltage rise after going to the
under feed. As illustrated in Fig. 8 the cell gas composition
soon changed from having no PFC co-evolution, to a situ-
ation where PFC’s appeared. In this operating mode the
emission rate is seen to be dependent on the variation in
dissolved alumina concentration as is evident from the
operating feeding cycle. This situation was reversed and the
PFC emissions ceased by lifting the alumina concentration
through increasing the duration of the over-feed to revert to
the same average alumina operating concentration.
The cell voltage only transgressed out of the normal
control band once for a short time (and by less than 10 mV.
This give further supports that the transition to PFC
Co-evolution of Carbon Oxides and Fluorides …
Fig. 8 The onset of low-level PFC co-evolution following lowering
the average concentration in the electrolyte
co-evolution occurs at an anode potential voltage (versus
aluminium reference) in a band near 1.80 V.
The consequences of changing two adjoining anodes
adjacent to a point feeders causing local spatial concentra-
tion variations and hence anode potential changes that ini-
tiate PFC co-evolution has already been demonstrated. In
that instance no measurable change in the cell voltage could
be detected.
Conclusions
The combination of the four sub-studies linked to PFC
co-evolution in aluminium smelting cells suggests that sev-
eral common interpretations used to both explain the anodic
processes and also quantify the extent of the fluorocarbon
release during the “anode effects” that occur in commercial
cells have technical limitations.
These include:
– There is a band of cell operating conditions whereby low
levels of PFCs can be emitted continuously at normal cell
voltages. These include average alumina concentration,
the operating temperature and aluminium fluoride con-
centration, anode carbon quality, current density (and
hence anode immersion depth in the electrolyte).
– Outside this band, spatial variation of process conditions
can also facilitate the co-evolution of PFCs. Some of
these variations are initiated by work or control practices.
– The required anode potential for co-evolution of PFCs is
significantly lower than any predicted for direct forma-
tion of CF4, but is closely linked with those that involve
formation of COF2 either directly or as an intermediate.
– The common explanation of the reason for CO2 being the
dominant gas during normal electrolysis, despite CO
being more thermodynamically favoured at normal
operating temperatures, is questionable, and interfacial
heat transfer [13] at the anode surface plays an important
539
role in determining the proportion of electrochemically
evolved CO.
– The commonly accepted industrial definition of an anode
effect—the cell voltage exceeding 8 V, while being a
useful common identifier is inadequate for initiating
quantitative calculations of the extent of pollution. The
disparity will all grow as the size of cells grow because of
the intensification of spatial properties through the
reduced number of feeders per kA, lower superheats, and
the greater distance required for electrolyte mixing in the
short time span.
Acknowledgments The various phases of this extensive study has
been supported by several colleagues and Industrial companies who
have also provided financial, technical and analytical support. Without
their skilful contribution to experimental design, we would not have
succeeded in getting the range of data necessary. They are too
numerous to mention here.
References
1. R.W. Bunsen, Annawek 92, 252 (1854)
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processing of anode current signals: an opportunity for improved
cell diagnosis and control. TMS Light Met. 1225–1232 (2001)
3. L. Dion, C-L Lagace, J.W. Evans, R. Victor, L. Kiss, On-line
monitoring of individual anode currents to understand and improve
process control at Alouette. Light Met. 723–728 (2015)
4. A. Jassim, S. Akmetov, B.J. Welch, M. Skyllas-Kazacos, J. Bao,
Y. Yao, Studies on background PFC emission in Hall-Héroult
reduction cells using online anode current signals. Light Met. 545–
551 (2015)
5. D. Wong, A. Tabereaux, P. Lavoie, AE phenomena during
conventional AEs, low voltage propagating AEs and
non-propagating AEs. Light Met. 529–534 (2014)
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tal and theoretical analysis of the anode effect in industrial cells.
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8. M.M.R. Dorreen, N.E. Richards, A.T. Tabereaux, B.J. Welch role
of heat transfer and interfacial phenomena for the formation of
carbon oxides in smelting cells. Light Met. 2017 (at press)
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method for measuring the dissolution rate of alumina in molten
cryolite. Bull. Electrochem. 8(7), 334–340 (1993)
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Transf. 59, 191–197 (2013)
 Part XIII
Aluminum Reduction Technology: Cell Lining
Materials
 Chemical Stability of Thermal Insulating
Materials in Sodium Vapour Environment

Raymond Luneng, Søren N. Bertel, Jørgen Mikkelsen,

Arne P. Ratvik, and Tor Grande

Abstract
The most typical thermal insulating materials used in the cathode lining in aluminium
electrolysis cells are Moler, calcium silicate, or vermiculite. The thermal insulation is
important for the overall thermal and dimensional stability of the cell. The chemical
stability of the thermal insulating materials is important, especially in cases where the
refractory layer above the thermal insulation layer becomes fully penetrated by sodium
vapour. The chemical degradation of thermal insulating materials by sodium vapours has
been investigated in a laboratory test resembling the environments in the cathode lining.
The exposed materials were investigated with respect to changes in the microstructure and
chemical and mineralogical composition by a combination of optical and electronic
microscopy and powder X-ray diffraction. These investigations revealed different reaction
patterns for the three materials and the formation of new mineralogical phases were
identified. Finally, these findings were compared with chemical reactions with sodium
based on computational thermodynamics.

Keywords

Thermal insulating materials Aluminium electrolysis cell Sodium vapour Moler
Calcium silicate Vermiculite Degradation

Introduction moved towards both high amperage cells, as well as energy

The production of primary aluminium is an energy
demanding process that takes place by molten salt electrol-
ysis. Even today, the basic concept is very much the same as
the one introduced in 1886 by the chemists Charles Martin
Hall and Paul Louis Toussaint Héroult. However, the design
and technology of the electrolysis cells are constantly
evolving to yield higher productivity, and the industry has
R. Luneng (&)
T. Grande
Department of Materials Science and Engineering, NTNU
Norwegian University of Science and Technology,
7491 Trondheim, Norway
e-mail: raymond.luneng@ntnu.no
S.N. Bertel
J. Mikkelsen
Skamol A/S, Østergade 58-60, 7900 Nykøbing Mors, Denmark
A.P. Ratvik
SINTEF Materials and Chemistry, 7465 Trondheim, Norway
efficient cells. In a modern cell, the sidewalls are designed
with materials having high thermal conductivity in order to
form a frozen layer of bath, the side ledge, which will protect
the sidelining and potshell from the corrosive nature of the
bath. The bottom of the cell, however, is designed with
materials having low thermal conductivity, which will
minimize the heat loss as well as reduce possible solidifi-
cation of the bath towards the cathode. For low energy cells,
the heat formation in the cell will be reduced and better
insulation is needed to maintain operational temperatures.
This may cause extra strain on the insulation materials, both
from higher temperature at the interface between refractory
and insulation materials, as well as chemical attack from
penetrating volatile species and bath components.
The bottom insulation layer is most typically made of
Moler (diatomaceous earth), calcium silicate, or vermiculite
based materials [1]. The bottom lining is critical for both the

© The Minerals, Metals & Materials Society 2017 543

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_68
544 R. Luneng et al.

thermal as well as the dimensional stability of the cell. The
insulation materials have very poor resistance towards any
bath components that may penetrate through the carbon
cathode blocks, and therefore, a refractory layer is placed in
between these two layers to protect the insulation from
chemical attack by bath or volatile gases formed during
electrolysis [1].
Under normal circumstances, the lifetime of modern cells
is in most cases limited by the wear of the cathodes, which
has become a major challenge with today’s high amperage
cells [2, 3]. One way of increasing the cell lifetime is to
increase the carbon cathode thickness, at the expense of the
thickness of the refractory and insulation layers. Such new
cell designs will put higher demand on the insulation layer
and alter the thermal profile of the cell. In addition, volatile
species such as Na and NaAlF4 may penetrate the refractory
layer and react with the highly porous insulation materials.
Sodium vapour has been observed to be the first chemical
species diffusing through the refractories [4, 5]. The subse-
quent reaction with the bottom lining can alter the dimen-
sional and thermal stability of the insulation materials, and
ultimately change the performance of the electrolysis cell.
Moler, calcium silicate, and vermiculite based materials
used in the aluminium industry were subject to sodium
vapour exposure at elevated temperatures in a laboratory test
inspired by Allaire et al. [6]. Both pristine materials and
sodium exposed samples were investigated by a combination
of optical and electron microscopy, as well as powder X-ray
diffraction.
Experimental
The insulation materials investigated were Moler (SUPRA),
calcium silicate (SUPER-1100 E), and vermiculite [V-1100
(475)], products by Skamol A/S. The weight and dimensions
of the pristine samples, prior to sodium exposure, are given
in Table 1.
The typical chemical composition of the pristine materi-
als, as a product average by X-ray fluorescence measure-
ments, are provided in Table 2. The chemical composition
data has been collected from the materials data sheets. The
weight and dimensions were measured before and after the
sodium vapour test. The bar shaped materials were placed
inside a steel box with the surfaces facing a carbon crucible,
as illustrated in Fig. 1. 200 g NaF and 100 g Al were used as
reactants in the carbon crucible to form cryolite and sodium
vapour, by Eq. (1).
6NaF(s) þ Al(1) ¼ Na3 AlF6 ðs) þ 3Na(g) ð1Þ
The steel box was put in an oven, heated to 970 °C, and
held for 48 h. The Moler material was heated to 850 °C, due
to a limited service temperature of 950 °C. The test exposed
the insulation materials to much greater sodium vapour
pressures than can be expected under normal operating
conditions in the electrolysis cell, and must be seen as an
accelerated test procedure.
The three insulation materials are manufactured in dif-
ferent ways, and the Moler material is the only material that
is exposed to temperatures close to normal operating tem-
peratures during the production process. Therefore, the loss
on ignition (LOI) for the Moler material is much lower
compared to the calcium silicate and vermiculite based
materials, as seen in Table 2. A thermal reference sample for
the different materials were made by exposing them to the
same temperature and length as the sodium vapour test, but
without sodium exposure.
A bar of approximate dimensions of 5  1  1 cm3 was
cut from the upper part of the materials at the side closest to
the carbon crucible, as illustrated with a red square in Fig. 1.
The material was crushed, sieved, and X-ray diffraction
patterns of the materials were recorded using a Bruker AXS
D8Focus X-ray diffractometer.
A horizontal cut of approximate height of 1 cm was made
at the top of each bar, as illustrated in the lower right corner
of Fig. 1 for the V-1100 (475) vermiculite material. The

Table 1 Dimensions and weight H (mm) W (mm) L (mm) M (g) Density (kg/m3)
of the pristine insulation
materials, prior to the sodium Moler 50.2 48.7 149.6 285.8 781.4
vapour test Calcium Silicate 60.2 50.8 181.3 142.8 257.6
Vermiculite 60.4 51.1 179.6 255.5 460.9

Table 2 Typical chemical Product SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O SO3 TiO2 LOI*
composition of the insulation
materials investigated, from the SUPRA (Moler) 77 9.0 7.0 1.3 0.8 0.4 1.6 1.0 0.7 1.0
respective data sheets, given SUPER-1100 E (calcium 47 0.3 0.3 0.6 43 0.1 0.1 N/A N/A 8
in wt% silicate)
V-1100 (475) (vermiculite) 46 7.0 5.5 19.0 3.5 0.2 10.0 N/A 0.7 7.0
LOI* Loss on ignition given at 1025 °C
Chemical Stability of Thermal Insulating Materials …
Fig. 1 Setup for the sodium vapour test with the materials facing the
carbon crucible holding the reactants. The red square indicates the part
cut out and used for X-ray diffraction analysis. The lower right picture
shows a horizontal cross section cut from the sodium exposed
vermiculite material (Color figure online)
specimens were broken to create fracture surfaces to be
investigated by scanning electron microscopy, SEM (Hitachi
S-3400N). Both secondary electrons and back-scattered
electrons were used for SEM imaging.
Results
The macroscopic appearance of the pristine insulation
materials changed significantly after sodium exposure in the
laboratory test, as seen in Fig. 2. Pristine materials are
shown in the left pictures, and sodium exposed materials in
the middle and right pictures.
The Moler material (upper three pictures in Fig. 2)
changed from an orange colour to brown/grey, with a darker
side facing the carbon crucible during the test. The calcium
silicate material (middle three pictures in Fig. 2) changes
colour from grey to white before and after heat treatment
(thermal reference sample not shown). Black areas and spots
are observed after sodium exposure. The vermiculite mate-
rial (bottom three pictures in Fig. 2) has a pronounced gra-
dient on the side facing the carbon crucible during the test.
As seen in the lower right corner of Fig. 1, the side facing
the carbon crucible has changed colour. This part is close to
1 cm thick.
The changes in dimensions and weight of the materials
after the test are provided in Table 3. The weight loss was
lower for the sodium exposed samples compared to the
thermal reference samples, pointing to reactions with sodium
in the material during the experiments. A small part of the
bottom of the Moler SUPRA sample was stuck to the steel
box after the test, thus not providing the correct weight of the
545
Fig. 2 From top to bottom: Moler SUPRA, SUPER-1100 E calcium
silicate, and V-1100 (475) vermiculite. The left picture of each material
shows the pristine material, while the others show the material after the
sodium vapour test. The middle pictures show the side of the bar facing
the carbon crucible
sample. For the SUPER-1100 E calcium silicate material, the
sodium exposed sample had a weight loss of about 4 wt%
less than the thermal reference. The V-1100 (475) vermi-
culite material had a weight loss of about 2 wt% less than
the thermal reference. The calcium silicate material was
heavily deformed after the test, demonstrating thermally
activated creep.
X-Ray Diffraction
The XRD measurements revealed different phases for the
pristine samples, the thermal reference samples, and the
sodium vapour exposed samples for all three materials, as
illustrated in Figs. 3, 4 and 5.
The XRD results for the Moler material is shown in Fig. 3.
Moler is burned at high temperatures during manufacturing
and therefore no difference was observed between the pristine
and the thermal reference materials. The large broad feature
in the XRD patterns for the Moler material points at the
presence of amorphous or nano-crystalline phases. The main
546 R. Luneng et al.

Table 3 The dimensions, Material H (mm) W (mm) L (mm) m (g) Density (kg/m3) Diff. mass
weight, density, and mass (wt%)
difference observed for the
materials before and after the SUPRA pristine 50.2 50.0 149.5 295.6 787.8 N/A
sodium test, as well as before and SUPRA thermal ref. 50.0 49.9 149.0 293.6 789.8 −0.7
after the thermal reference test
SUPRA pristine 50.2 48.7 149.6 285.8 781.4 N/A
SUPRA sodium test 49.6 48.0 147.8* 279.6* 794.6* −2.2*
SUPER-1100 E pristine 60.0 51.1 180.4 142.1 256.9 N/A
SUPER-1100 E thermal ref. 59.3 50.5 179.4 126.3 235.1 −11.1
SUPER-1100 E pristine 60.2 50.8 181.3 142.8 257.6 N/A
SUPER-1100 E sodium test N/A** N/A** N/A** 132.6 N/A** −7.1
V-1100 (475) pristine 60.4 50.7 179.9 277.8 504.3 N/A
V-1100 (475) thermal ref. 59.5 50.5 177.7 260.8 488.4 −6.1
V-1100 (475) pristine 60.4 51.1 179.6 255.5 460.9 N/A
V-1100 (475) sodium test 58.4 49.0 176.5 245.7 486.5 −3.8
*The bottom part of the sample was stuck to the steel box, giving errors in these values
**Unable to measure due to material deformation, as seen in Fig. 2

Fig. 3 XRD diffractograms of the Moler material as pristine sample Fig. 4 XRD diffractograms of the calcium silicate material as pristine
(upper black graph), thermal reference sample (middle red graph), and sample (upper black graph), thermal reference sample (middle red
sodium exposed sample (lower blue graph). The most important phase graph), and sodium exposed sample (lower blue graph). The most
peaks are also marked (Color figure online) important phase peaks are also marked (Color figure online)

phases in the pristine and thermal reference materials are
SiO2, and Fe2O3. After sodium exposure, SiO2 is still present,
while Fe2O3 has disappeared. A new phase, Mg2Al4Si5O18,
seems to be formed. However, the amount of amorphous
phases in the Moler material is substantial when compared to
the amount of crystalline phases.
The XRD pattern of the pristine calcium silicate material
(Fig. 4) show that xonotlite, Ca6Si6O17(OH)2, is present.
However, after thermal treatment the main phase is identified
as wollastonite, CaSiO3. The X-ray pattern of the sodium
exposed sample demonstrates that the main phase after
sodium exposure is Na2Ca2Si2O7, a sodium calcium silicate.
Combeite, Na2Ca2Si3O9, was also found in the exposed
material.
The XRD measurements of the vermiculite material are
shown in Fig. 5. The X-ray pattern of the pristine vermi-
culite sample show the main phase to be vermiculite, (Mg,
Fe+2, Fe+3)3[(Al, Si)4O10](OH)2
4H2O, a hydrated magne-
sium aluminium silicate mineral. After the heat treatment,
forsterite, Mg2SiO4, and leucite, KAlSi2O6, phases were also
Chemical Stability of Thermal Insulating Materials …
Fig. 5 XRD diffractograms of the vermiculite material as pristine
sample (upper black graph), thermal reference sample (middle red
graph), and sodium exposed sample (lower blue graph). The most
important phase peaks are also marked (Color figure online)
observed. Forsterite is identified in the sodium exposed
sample, together with a sodium aluminium silicate oxide,
NaAlSiO4, and KAlSiO4, as the main phases.
Scanning Electron Microscopy
The microstructure of the pristine materials are compared
with the microstructure of the exposed materials, shown in
Fig. 6. The porous nature of the three pristine materials are
evident by the SEM images to the left. The mechanisms for
obtaining high porosity in the three materials are in principle
different and the microstructures are quite different, but all
three are highly porous.
The image of the sodium exposed Moler material (upper
pictures in Fig. 6) revealed a thin glassy layer on the side
facing the carbon crucible during the test. Although not
continuous, it covers the surface quite well, as seen from the
top down view. The calcium silicate material is still highly
porous, but the microstructure has coarsened during the
sodium test, reflecting the macroscopic change in shape due
to creep. The pristine vermiculite material is mostly exfoli-
ated vermiculite grains pressed together with a water glass
binder. The sheet structure of the grains in the pristine
material is clearly seen by SEM imaging. After sodium
exposure, this characteristic microstructure is not observed,
reflecting that the reaction with sodium leads to significant
coarsening of the grains and removal of the fine porous
microstructure.
547
Discussion
From the XRD data, the following phase changes are pro-
posed for the Moler material. The pristine sample and the
thermal reference sample have the same phase compositions
since the Moler material is burned at high temperatures
during manufacturing. After sodium exposure the iron oxide,
Fe2O3, has disappeared due to the reactions and is likely
reduced to a different phase with Fe2+. A glassy phase is
formed on the side facing the carbon crucible, which is also
observed by SEM. The SiO2, and Mg2Al4Si5O18 phases are
still present, while the major part of the material remains
amorphous. From SEM imaging, and preliminary
energy-dispersive X-ray spectroscopy (EDS) measurements
(not reported here), the glassy layer that is formed seems to
be quite thin, but high in sodium content, most likely
forming a viscous sodium aluminosilicate liquid, which
turns into a glass during cooling. The sodium content drops
significantly beyond this layer and further inside the
material.
Recent work on thermodynamic stability of thermal
insulating materials in sodium vapour environment [7] pre-
dicts both SiO2, and Mg2Al4Si5O18 phases to be present in
the Moler material at low sodium content. Albite, NaAl-
Si3O8, is also predicted to increase significantly with
increasing sodium content. Glassy phases (or liquid at ele-
vated temperatures) close to albite, which normally does not
crystallize, have previously been reported to be present in
reacted refractory layers of shut down cells [5]. The bar
shrunk in all three dimensions during the test, but due to a
small part of the bottom being stuck to the steel plate, the
length and weight measurements reported are not accurate.
Thus, no conclusions can be drawn about the macroscopic
difference in wt% compared to the thermal reference sample.
However, based on the sodium content in the outer layer,
some sodium uptake is likely. The attachment of the sample
to the steel plate also points to the formation of a viscous
liquid due to reactions with sodium.
From the XRD data, the following is proposed for the
calcium silicate material. During heat treatment, the calcium
silicate material transforms from xonotlite to wollastonite,
by evaporation of water. When exposed to sodium, the
wollastonite reacts to form both Na2Ca2Si3O9 and Na2Ca2-
Si2O7. By thermodynamic equilibrium calculations,
Na2Ca2Si3O9 is predicted to form by increasing sodium
content, while Na2Ca2Si2O7 is not predicted [7]. The
experimental results therefore point to kinetics being
important for the phase transformations and reaction with
sodium. Elemental silicon is also predicted to form by
thermodynamic calculations [7], but has not been identified
so far and calls for further investigations. However, the black
colour on the sodium exposed calcium silicate material may
548
Fig. 6 SEM images of the pristine materials to the left, and sodium
exposed samples to the right. Note that some images are from
secondary electrons (marked SE) and some are back-scattered electrons
(marked BSE). From top to bottom: Moler SUPRA, SUPER-1100 E
calcium silicate, and V-1100 (475) vermiculite. For the Moler sample, a
thin glassy layer is observed after sodium exposure, as seen in the
upper right pictures. A top down view is also provided, which
R. Luneng et al.
illustrates that the glassy layer is not continuous across the surface. The
organic fibres, seen in the pristine calcium silicate sample, burn off
during the test, and the sodium exposed sample show more of a
dendritic structure and large voids/pores. The exfoliated grains of the
pristine vermiculite can clearly be seen in the lower left pictures, where
the grains open up in parallel sheets. This structure is lost during
sodium exposure, and a more continuous phase is observed
Chemical Stability of Thermal Insulating Materials …
possibly come from the formation of silicon, but this is yet to
be confirmed. The calcium silicate material suffered severe
deformation during the test, as is seen in Fig. 2, with no
external load except the weight of the bar itself. In light of
the SEM images, it is still showing a rather porous structure,
which points to deformation by creep that is, most likely
caused by viscous flow. A coarsening of the microstructure
is also observed. The XRD data also show complete min-
eralogical transformations taking place comparing the pat-
terns of the pristine, the thermal reference, and the sodium
exposed material. This points to an inability of the material
to resist sodium infiltration, as opposed to the Moler material
where a complete phase transformation is not observed, and
a glassy layer is formed. Compared to the thermal reference
sample, the sodium exposed calcium silicate sample had an
approximate 4 wt% increase, pointing to a high uptake of
sodium in the material.
For the vermiculite material, the thermal treatment of the
reference sample leads to formation of forsterite, Mg2SiO4,
and leucite, KAlSi2O6, illustrating that the material is not
thermally stable with respect to phase composition. After
sodium exposure, forsterite is still present, together with
NaAlSiO4, and KAlSiO4, as the main phases. These phases
have also been predicted to coexist by thermodynamic
equilibrium calculations at moderate sodium content [7].
Compared to the thermal reference sample, the sodium
exposed sample had an approximate 2 wt% increase, about
half of what was observed for the calcium silicate material.
SEM imaging revealed a distinct difference between the
macroscopic gradient observed in the lower right picture of
Fig. 1. While the inner part has a structure similar to the
pristine material, with exfoliated vermiculite grains (lower
left pictures of Fig. 6), the porous sheet structure of the
grains is not seen in the outer part (lower right pictures of
Fig. 6). Preliminary EDS measurements (not reported here)
also show high sodium content in the outer part. The
material shrunk in all dimensions, but as opposed to the
calcium silicate material, it did not deform dramatically and
is apparently retaining its structural integrity. By the XRD
and SEM data, the vermiculite material does not create a
glassy barrier layer like the Moler material, nor does it
experience a complete mineralogical transformation like the
calcium silicate material. Instead, the sodium vapour pene-
trates the outer layer and reacts with the material, leaving the
inner layer, more or less, intact.
Lastly, it is worth mentioning that in a typical design of
an aluminium electrolysis cell, the Moler material (SUPRA)
and vermiculite material [V-1100 (475)] are usually located
in the upper part of the insulation layer, thus being closest to
549
the refractory layer and the cathode. The calcium silicate
material (SUPER-1100 E) is used as back-up insulation, in
the bottom part of the insulation layer. In light of the results,
this placement is most beneficial, as the Moler and vermi-
culite materials are seen to tolerate higher sodium vapour
exposure much better than the calcium silicate material.
Conclusion
A laboratory scale test was set up to expose three common
thermal insulating materials to sodium vapour, which is
likely the first volatile specie to diffuse through the refractory
layer of aluminium electrolysis cells. Phase transformations
during a reference heat treatment were observed in the cal-
cium silicate and vermiculite materials, but not in the Moler
material. When exposed to sodium vapour in the test, the
Moler material reacted to form a glassy layer, which limits
further penetration of sodium. A complete phase transfor-
mation occurred in the calcium silicate material, and severe
deformation by creep was observed. The vermiculite mate-
rial maintained its structural integrity, but sodium penetrated
deeper inside the material than in the case of the Moler
material.
Acknowledgements Financial support from the Norwegian Research
Council and Hydro Aluminium, Alcoa Norway, Elkem Carbon, and
Skamol A/S, through the project CaRMa - Reactivity of Carbon and
Refractory Materials used in Metal Production Technology, is grate-
fully acknowledged.
References
1. A. Seltveit, Ildfaste materialer (Tapir, Trondheim, 1992)
2. E. Skybakmoen, A.P. Ratvik, A. Solheim, S. Rolseth, H. Gud-
brandsen, Laboratory test methods for determining the cathode wear
mechanism in aluminium cells. Light Metals, 815–820 (2007)
3. K. Tschöpe, A. Store, S. Rorvik, A. Solheim, E. Skybakmoen,
T. Grande, A.P. Ratvik, Investigation of the cathode wear
mechanism in a laboratory test cell. Light Metals, 1349–1354
(2012)
4. K. Tschöpe, C. Schøning, J. Rutlin, T. Grande, Chemical degra-
dation of cathode linings in Hall-Héroult Cells—an autopsy study of
three spent pot linings. Met. Trans. B 43, 290–301 (2012)
5. K. Tschöpe, J. Rutlin, T. Grande, Chemical degradation map for
sodium attack in refractory linings. Light Metals, 871–876 (2010)
6. C. Allaire, R. Pelletier, O.-J. Siljan, A. Tabereaux, An improved
corrosion test for potlining refractories. Light Metals, 245 (2001)
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namic stability of thermal insulating materials in aluminium
electrolysis cells. in Proceedings of 34th International conference
ICSOBA (2016), pp. 1–10
 Aging of Insulating Linings in Aluminium
Electrolysis Cells

Ove Paulsen, Christian Schøning, Ove Darell, and Arne Petter Ratvik

Abstract
Dimensional stability of materials used in aluminium electrolysis cells are important for
stable cell operation. The observed compression of insulating linings from autopsies of
industrial cells are in many cases much higher than would be expected from laboratory
creep tests of the corresponding materials. Creep in compression of three commercial
insulating materials for aluminium electrolysis cells, produced from diatomite, perlite and
calcium silicate, respectively, has been studied. The creep rates were measured versus
temperature and load on as received materials, after additional heat treatment, and materials
contaminated with KF and NaF. Refiring the as received materials resulted in a substantial
decrease in the creep rate.

Keywords
Insulation Aluminium Lining Creep

Introduction
The creep mechanism for refractory materials can be com-
plex due to contributions from many factors. The presence of
different phases, including glass, incompletely reacted pha-
ses, and a wide grain size (and shape) distribution, makes
creep behaviour difficult to analyse. Autopsies of cells taken
out of service often show a reduced thickness of the insu-
lation lining in the range of 20–30 mm. This is substantial
compared to the typically 130–180 mm thickness of a new
lining. In linings composed of two layers of insulating
material it is in most cases observed that only the bottom
layer has been compressed while the top layer that has been
exposed to higher temperatures, is unaffected.
Glassy phases can play an important role in creep beha-
viour. If the glassy phase is abundant and wets grain
boundaries, the creep rate will depend on the glass viscosity.
If the glassy phase does not cover the grains, stabilisation
due to grain-to-grain contact decrease the deformation rate.
O. Paulsen (&)
C. Schøning
O. Darell
A.P. Ratvik
SINTEF Materials and Chemistry, Trondheim, NO-7465, Norway
e-mail: ove.paulsen@sintef.no
Hence, the negative effect of the glassy phase can be reduced
by lowering the amount of the phase, either by crystallisation
or by changes in the material composition.
Due to the microstructural complexity of most insulation
materials, they are seldom fired to chemical equilibrium in
the as received state. Further heat treatment, at the same or
higher temperature than the original firing temperature, will
normally lead to changes in the crystalline structure that
effect the creep behaviour. Generally, no insulating lining
material should be applied at higher temperatures than the
firing temperature.
A schematic description of a typical bottom lining is
shown in Fig. 1. The top lining consists of the cathode
carbon blocks with current collector bars. The carbon is
resting on a levelling floor of alumina or powdered fireclay
above the refractory bricks, normally alumina silicate bricks.
The purpose of the refractory bricks is to provide protection
of the underneath insulation bricks from sodium and bath
that penetrates the carbon blocks. A typical temperature
profile through the bottom lining is also shown in Fig. 1.
The calculated profile is for virgin materials, assuming
constant thermal conductivities within each phase. The
temperature drop through the carbon is small due to high

© The Minerals, Metals & Materials Society 2017 551

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_69
552
thermal conductivity. The lower refractory layer reach a
temperature of around 800 °C, while most of the tempera-
ture drop between the metal and the surroundings is con-
trolled by the insulation.
Creep in Compression
The creep rate is defined as de/dt, where de is the strain
change DL/Lo measured during the time interval dt. The
creep rate can generally be expressed in a simplified form
as [2]:
de
e_ = = Arn eðDH=RT Þ
dt
A is a material dependant constant. n is a stress exponent
which depends on the creep mechanism. For diffusion creep,
n = 1, and for dislocation creep, n = 3 [3, 4]. DH is the
apparent activation energy. Creep tests of the same specimen
at different temperatures and loads should yield a linear
relationship between the natural logarithm of the creep rate
and the inverse temperature with a slope equal to −DH/R as
shown in Eq. 2.
DH 1
ln e_ = ln A + n ln r 
R T
Experimental
Three commercial insulating materials based on diatomite
bricks (D), perlite boards (P) and calcium silicate boards
(CS), respectively, were tested. Diatomite and perlite were
both fired products, while the calcium silicate material was
not.
Fig. 1 Schematic cross-section through a bottom lining. The calcu-
lated temperature gradients in the lining are based on thermal
conductivity data for virgin materials [1]
O. Paulsen et al.
The material properties given by the producers are listed in
Table 1. Cylindrical samples, 50 mm diameter and 50 mm
high, with a centre hole with diameter 12 mm were prepared.
Samples were characterized with respect to Young’s
modulus, density, porosity, thermal expansion and mineral
composition to ensure that the test samples of the respective
materials were as equal as possible.
Dynamic Young’s Modulus was measured according to
ASTM C1198-91, using a Charge Amplifier 2635 and
Accelerometer 4375 from Brüel & Kier and a Panasonic
VS-3310P FFT analyser for frequency measurements.
Bulk Density was measured by the Archimedes method
ð1Þ according to ISO 5017 using water as liquid.
Mineral Composition of as received samples and after
refiring (RF) was measured by powder X-ray diffraction with
a Brooker Focus D8 diffractometer. The materials were
milled in a RETSCH mixermill followed by sieving through
a 45 µm sieve.
Thermal Expansion of as received materials was mea-
sured in the temperature range 20–1000 °C using a
NETSCH 402E push-rod dilatometer. The heating rate was
2 °C/min in ambient air.
Fluoride Salt Impregnation was achieved by dipping a
series of the diatomite samples in an aqueous solution with 1
ð2Þ
wt% NaF + 1 wt% KF for 1 min followed by drying in a
vacuum closet. The amount of salt in each sample was ca.
0.02 g/cm3.
Creep Tests Apparatus, shown in Fig. 2, was built at
SINTEF according to ISO 3187, using a vertical tube fur-
nace with a mullite working tube with inner diameter 63 mm
and an alumina tube load piston. Weights up to 700 N could
be applied, giving a maximum load pressure of 3.5 MPa on
a 50 mmØ sample. The measuring system was placed inside
the support tube. The relative positional change between the
top and the bottom of the test sample was measured directly.
The only necessary correction is to compensate for the
thermal expansion of the alumina tube in the centre of
the sample, and the expansion of the alumina support plate.
The temperature was controlled by a Eurotherm 903P pro-
cess controller with a type S thermocouple (TC) placed
1–2 mm outside the sample and 25 mm from the sample
bottom. Another TC was placed in the centre of the sample.
The temperature gradient in the space occupied by the
sample was ±3 °C in the vertical direction. The temperature
difference between the outer and inner TC was *20 °C at
750 °C and *5 °C at 850–875 °C. The temperature gradi-
ent within the sample was considered to be less. An Agilent
34970A was used for data acquisition from TCs and
dimensional changes, measured by an inductive position
transducer with resolution 1 µm.
Creep tests were performed according to ISO 3187. By
measuring the sample height L as function of time t, the
creep rate de/dt could be calculated for each holding
Aging of Insulating Linings in Aluminium Electrolysis Cells 553

Table 1 Chemical and physical Property Unit Diatomite (D) Calcium silicate (CS) Perlite (P)
data of the insulating materials
Maximum service temperature °C 900 1100 900
Bulk density g/cm3 0.55 0.29 0.45
Total porosity % 77 89 82
Compressive strength (EN1094-5:1995) MPa 1.4 2.8 1.28
Thermal conductivity, 600 °C W/mK 0.113 0.1 0.14
Chemical analysis, typical, wt% Oxide
SiO2 77 46 65.0
Al2O3 9 0.3 15.0
Fe2O3 7 0.3 4.0
Na2O 0.55 0.1 1.1
K2O 1.46 0.1 5.0
MgO 1.3 0.6 1.3
CaO 0.8 45 7.0
SO3 1.18
TiO2 0.7 0.5
L.O.I 1.5 7 0.5

complete heating cycle. Sufficient time to reach constant

creep rate was found to be in the range of 15–30 h. For the
following experiments, the hold time at each temperature
Lead weights
(Max 70 kg) was 20–30 h, using the last 5–10 h of the creep data to
calculate the creep rate. The creep rate increased with
Control TC increasing temperature as demonstrated in Fig. 3, where the
thermal expansion for calcium silicate is shown. During
Load column heating from one hold temperature to the next, the materials
Alumina
expanded, but as soon as the temperature was stabilised the
Tube furnace
samples started to creep. The creep rate was high in the
Centre TC beginning and decreased gradually for the next 10–12 h
Sample before it became almost constant.
To see the effect on creep by heat treating the materials,
the diatomite specimens were fired at 850 °C for 96 h or at
Support column 900 °C for 50 h. The perlite and calcium silicate samples
(alumina) were fired at 900 °C for 336 h (two weeks).

Position
measurement 0.4
system
CALCIUM SILICATE
Thermal expansion (%)

0.2

-0.2 750 800 850 900

Fig. 2 A simplified sketch of the creep test equipment, consisting of
the tube furnace that was movable in the vertical direction, the loading -0.4
system and the position measurement system
-0.6

-0.8
temperature of 750, 800, 850 and 875 °C, respectively. The 0 20 40 60 80 100
Time (h)
load was 0.20 MPa for most of the tests, but some samples
were also tested at 0.30 MPa. Fig. 3 Typical thermal expansion versus time curve during creep test,
The samples were heated at a rate of 300 °C/h up to the illustrated by a creep test with calcium silicate. The creep temperatures
first temperature level. The load was activated during the in °C are listed inside the Figure
554 O. Paulsen et al.

Results phase was wollastonite, representing a substantial change in

The measured bulk density and dynamic Young’s modulus
showed that the diatomite bricks could be divided in two
distinct groups; one with E-modulus below 0.373 GPa and
one above 0.391 GPa. For the creep test samples, bricks
with density range 0.55–0.56 and E-modulus range 0.367–
0.373 GPa were used.
Thermal expansion of diatomite and calcium silicate is
shown in Fig. 4. Diatomite starts to creep at *800 °C and
shows a considerable shrinkage at 900 °C. The calcium
silicate material showed two creep steps: one at *700 °C
and one at *900 °C. Hence, none of these materials was
dimensionally stable at 900 °C.
XRD Analysis of the diatomite and calcium silicate
showed that the crystalline structure of both materials chan-
ged substantially after refiring (RF) at 900 °C. In diatomite,
some of the quartz transformed to cristobalite during firing
at 900 °C (see Fig. 5). In this sample, also hematite was
identified. The hematite peaks had increased in height indi-
cating that the crystalline hematite phase developed during
firing. The as received calcium silicate, (Fig. 6), con-
tained calcium-silicate-hydrate, probably Ca6Si6O17(OH)2 in
addition to wollastonite. After firing at 900 °C the main
0.20
0.10
Thernmal expansion (%)
the mineral structure. Changes in the crystalline structure are
also seen in the perlite material, but in this case the changes
are modest, Fig. 7.
The main phase in the perlite material was quartz and the
amounts seemed to be approximately the same in the fired
sample as in the as received sample. The other crystalline
phases in this material have not been identified, but the
X-ray patterns show that the peaks between 27° and 32° (2h)
have changed after firing. In addition, other minor changes
are observed which can influence the creep behaviour.
Changes taken place during firing can be localised at
2h = 22°, which can be cristobalite. Other peaks that have
changed is localized at 2h–27.7° and 2h–30°.
Creep versus Temperature and Load
Average creep rates in µm pr. mm lining thickness pr. day
(d) based on two parallels of the insulating materials versus
temperature and load are shown in Table 2 and in Fig. 8.
The left diagram in Fig. 8 represents the as received mate-
rials and the right diagram the same materials after refiring.
The diatomite and the calcium silicate were the only mate-
rials tested at two different loads; 0.20 MPa and 0.30 MPa,
respectively. Common for all materials was that the creep
rate increased with increasing temperature in the whole
temperature range investigated. Regarding diatomite, the
increase in creep rate was substantially reduced above
850 °C, indicating a change in the creep mechanism or the

0.00 microstructure. As shown in Fig. 8 (filled symbols) the creep

-0.10 rate with 0.30 MPa load is higher than for 0.20 MPa by a
-0.20 factor decreasing from *2.7 at 750 °C to 1.1 at 875 °C.
-0.30 Diatomite had the highest creep rate and calcium silicate the
lowest in the temperature range 750–800 °C.
-0.40
Calcium silicate
-0.50 Diatomite Effect of Refiring on the Creep Rates
-0.60 Refiring of the materials was expected to result in a
0 200 400 600 800 1000 reduction in the creep rate, which also turned out to be the
Temperature (°C) case as shown in Fig. 8 (right diagram). Refiring resulted in
Fig. 4 Thermal expansion of calcium silicate and diatomite samples in
a dramatic reduction in the creep rates. The shape of the
the as received state creep curves was similar for all three materials, following an

Fig. 5 XRD pattern of diatomite

as received (black) and re-fired at
900 °C for 50 h (blue). The
refired material is much more
crystalline compared to the as
received material (Color figure
online)
Aging of Insulating Linings in Aluminium Electrolysis Cells 555

The relative change in creep rate from the as received

CALCIUM SILICATE Wollastonite, CaSiO3 materials to the refired materials is given in Table 3. For the
Xonotlite, Ca6Si6O17(OH)2 diatomite material the creep rates decreased by a factor of
8000 *2–8 after re-firing. For the calcium silicate the decrease
was in the range 1.3–5 times. For perlite the decrease was
Lin (Counts)

6000
tremendous, ranging from a factor of 17 for the creep rate at
4000
900 °C/336h 750 °C to 570 for the creep rate at 850 °C.

2000
Effect of Fluoride Contamination on the Creep Rates
As received
Diatomite samples impregnated with NaF and KF showed
0 an increased creep rate compared with the as received
20 30
samples as demonstrated in Fig. 9. The squares represent the
2-Theta - Scale
contaminated materials while the triangles represent the as
Fig. 6 XRD patterns of calcium silicate as received (black) and after received materials. The open symbols are mean values of
refiring 336 h at 900 °C (red) (Color figure online) two parallels tested at 0.20 MPa load and the filled symbols
are mean values of two parallels tested at 0.30 MPa load.
For the contaminated diatomite material tested with
0.20 MPa load the creep rates increased by a factor of 1.3
above 800 °C. At 0.30 MPa load, the relative increase was
slightly higher, ranging from 1.3 to 1.8 in the same tem-
perature range. The tendency of reduced creep rate above
850 °C observed for the as received materials was also
observed for the contaminated materials.

Activation Energy DH for Creep

Fig. 7 XRD-patterns of MSB450. As received material (black) and
re-fired 336 h at 900 °C (red) (Color figure online)
exponential increase in the creep rate with temperature. The
fast reduction in creep rate above 850 °C observed for as
received diatomite, was not observed after refiring.
Based on Eq. 2 the apparent activation energy DH for
creep has been calculated from linear regression of Arrhe-
nius plots of the creep curves of the as received and refired
materials. The results, based on two parallels, are given in
Table 4. It should be noted that the DH values extracted by
this method, are apparent since several of the factors hidden
in A are temperature dependent [3, 4]. DH values for the as
received diatomite samples are based on the creep results in
the temperature range 750–850 °C, while for calcium

Table 2 Creep results versus Material/treatment Load (MPa) Comment Creep rate (µm mm−1d−1) [d = 24 h]
temperature
750 °C 800 °C 850 °C 875 °C
D/AR 0.20 As received 0.71 4.05 13.70 14.77
D/AR 0.30 As received 1.92 6.65 15.71 16.09
D/RF 0.20 850 °C/96 h 0.36 1.18 4.33 5.65
D/RF 0.20 900 °C/50 h 0.35 0.61 1.76 3.64
D/RF 0.30 900 °C/50 h 0.54 1.11 2.99 3.99
D/AR-IMP 0.20 1%NaF + 1%KF 2.52 5.17 18.25 19.91
D/AR-IMP 0.30 1%NaF + 1%KF 2.08 8.62 28.54 28.14
CS/AR 0.20 As Received 0.17 0.17 0.35 0.55
CS/AR 0.30 As received 0.17 0.44 0.90 1.30
CS/RF 0.20 900 °C/336 h 0.03 0.11 0.28 0.41
P/AR 0.20 As received 0.02 0.23 2.42 0.00
P/RF 0.20 900 °C/336 h 0.001 0.002 0.004 0.005
D diatomite, CS calcium silicate, P perlite, AR as received, RF after refiring, IMP impregnated
556 O. Paulsen et al.

18.0
materials become more crystalline resulting in an increase in
As received Refired
16.0 viscosity due to reduced content of glassy phase.
D/AR 0.2 D/RF 0.2 850 °C/96 h
D/AR 0.3
D/RF 0.3 900 °C/50 h
D/RF 0.201 900 °C/50 h
The choice of 900 °C as the refiring temperature was
14.0
P/AR 0.2 P/RF 0.2 900 °C/336h
CS/AR 0.2 CS/RF 0.2 900 °C/336h done because the insulating materials in question are made
Creep rate (μm·mm-1d-1)

12.0
10.0
8.0
6.0
4.0
2.0
0.0
700 750 800 850
Temperature (°C)
Fig. 8 Creep rates for as received materials and re-fired materials,
under creep loads of 0.20 and 0.30 MPa
silicate and perlite the linear regression is based on the
complete temperature range 750–875 °C. The general pic-
ture is that DH seems lower for the refired materials com-
pared to the as received materials. The biggest drop in DH
was observed for the perlite material, which changed from
476 kJ/mol for the as received sample to 134 kJ/mol for the
material refired 336 h at 900 °C.
Discussion
The observed creep rates of the insulating materials are
influenced by many factors making the interpretation of the
creep results difficult. The general trend of increasing creep
rate with increasing temperature, is expected and in line with
theory. The calculated DH values are also reasonable in spite
of the scarce data the calculations are based on, and in line
with values calculated for refractory firebricks reported by
Hulse and Pask [5].
It is not obvious that refiring should result in reduced
creep rates, but this is the case for all materials. The general
reduction was in the range 1.3–8 times compared to the as
received materials, except for the perlite material where the
reduction in creep rate was by a factor of 17 at 750 °C to 570
at 850 °C. The effect of refiring is probably that the original
for this lower temperature range (900–1100 °C) and that
900 °C is above the expected maximum temperature in the
insulating bottom lining of an electrolysis cell. However, as
the creep data shows, even refiring at 850 °C (diatomite)
reduced the creep rate with a factor of three.
The creep curves for the as received material of diatomite
showed a decrease in the creep rate at temperatures above
850 °C. This is an indication of structural changes above
900 700 750 800 850 900 850 °C. The XRD analysis revealed that the sample refired
Temperature (°C) at 850 °C had a more developed crystal structure compared
to the original material and this can explain the s-shape of
the creep curves of the as received samples.
After refiring the creep curves followed an exponential
trend as expected from creep theory (Eq. 1). In principle, it
should be possible to calculate the stress exponent n of the
rn term in Eq. 1 for the samples tested under different loads.
This implies evaluation of the term A ∙ rn, assuming that A
is constant for each material. The only sample that gave a
reasonable value for n was the as received calcium silicate
material resulting in an n of 2.2. This value is between the
expected n for diffusion creep which is 1 and the exponent
for dislocation creep which is in the range 3–10. A com-
prehensive review of creep mechanisms is given by Cannon
and Langdon [3, 4].
By comparing creep rates for the as received and refired
materials at 800 °C and 0.20 MPa (Table 4), the as received
calcium silicate material had the lowest creep rate, about
20% lower than perlite. On the other end of the scale was the
diatomite with a creep rate *18 times higher than the per-
lite. For the refired materials, perlite had the lowest creep
rate. In this case, the calcium silicate had a creep rate 48
times higher than perlite.
Results for the activation energy DH for creep showed that
the activation energy decreased as the firing temperature
increased. It is reasonable to believe that the main creep
mechanism is caused by amorphous phases on the grain
boundaries. The creep rate will depend on both the chemical
composition and the amount of glassy phase. In the as received
materials, the amorphous phases are rich in silica. As silica

Table 3 Relative change in Sample ID Load (MPa) Refiring temp/time Relative creep rates (as received/re-fired)
creep rate for refired materials
compared to the as received 750 °C 800 °C 850 °C 875 °C
materials Diatomite 0.20 850 °C/96 h 2.0 3.4 3.2 2.6
Diatomite 0.20 900 °C/50 h 2.0 6.7 7.8 4.1
Diatomite 0.30 900 °C/50 h 3.5 6.0 5.3 4.0
Calcium Silicate 0.20 900 °C/336 h 5.0 1.5 1.3 1.3
Perlite 0.20 900 °C/336 h 17.0 96.8 570.6
Aging of Insulating Linings in Aluminium Electrolysis Cells 557

30.0 much lower than 0.20 MPa. If all materials in an electrolysis

D/AR-IMP 0.30 MPa
D/AR-IMP 0.20 MPa
25.0
D/AR 0.30 MPa
D/AR 0.20 MPa
Creep rate (μm·mm-1d-1)
20.0
15.0
10.0
5.0
0.0
700 750 800
Temperature (°C)
Fig. 9 Creep rates of as received diatomite before and after impreg-
nation with NaF + KF at creep stress 0.20 and 0.30 MPa, respectively
crystallises to cristobalite or wollastonite, the glass phase
becomes depleted in silica and hence less viscous. The
resulting glassy phase will start to flow at a lower temperature,
but less amount of glassy phase and an increased amount of
crystalline phases results in an overall lower creep rate.
For insulating materials to be used in electrolysis cells, a
tolerable creep is expected to be in the range of 10–30 mm
during the operational period of 5 years. With two shifts of
insulating material the thickness of the insulating layer is
typically 130 mm. Based on this thickness the maximum
tolerable creep rate would be 1.8–5.3  10−6 mm mm−1 h−1.
The calculated maximum lining temperatures to fulfil these
requirements for as received materials are indicated in
Table 5.
For all materials the temperature should be below 800 °C
at a load of 0.20 MPa. The real creep will probably be lower
since the real load on the insulating lining in most cases is
cell are allowed to move freely in the vertical direction the
load on the insulating lining is only caused by the weight of
the materials above. This weight represents a pressure of
*0.02 MPa, which is only 1/10 of the maximum load used
in the creep tests. However, during the years of cell opera-
tion, a “lens” of material builds up below the cathode. This
causes the cathode to bend upwards and will also result in a
substantial pressure downwards that probably is much
higher than the theoretical value.
The temperature in the bottom lining during operation is
also a matter of uncertainty. In a normal cell, the mean
temperature is probably not higher than 400–500 °C
(Fig. 1). By using the creep results for a load of 0.20 MPa
850 900 the expected creep during 5 years for a 100 mm insulating
lining of uncontaminated material has been calculated
(Table 6). For a lining temperature of 500 °C none of the
tested insulating materials will creep more than 0.05 mm. At
600 °C the maximum creep will be 1.3 mm. At 700 °C the
spread is larger showing creep up to 25.7 mm for uncon-
taminated samples and the double (53 mm) for the diatomite
samples infiltrated with NaF and KF. Contamination with
1% NaF + 1% KF resulted in a mean increase in creep rate of
70% (Table 2) in the temperature range 750–875 °C.
An example from an autopsy of a bottom lining consisting
of two shifts of diatomite insulation bricks has been reported
[6]. It was observed that the shift closest to the bottom was
depressed 30 mm, while the upper shift had the original
thickness. X-ray diffraction analysis of the two shifts showed
that the upper shift was far more crystalline than the lower.
This indicates that even at moderate temperatures diatomite
materials crystallises and become creep resistant. To avoid
reduction in thickness of the insulation lining, the shift
closest to the bottom should be fired at higher temperatures or
fired for longer time compared to common practice, before
the material is installed in the electrolysis cell.

Table 4 Activation energy for Sample ID Load (MPa) Comment DH (kJ/mol) Constant A
rn
creep for as received, refired and
impregnated samples D/AR 0.2 As received 284 9.7E+09
D/AR 0.3 As received 201 1.6E+06
D/RF 0.2 850 °C/96 h 224 4.0E+06
D/RF 0.2 900 °C/50 h 118 2.0E+04
D/RF 0.3 900 °C/50 h 161 3.3E+03
D/AR IMP 0.2 1%NaF + 1%KF 253 4.4E+08
D/AR IMP 0.3 1%NaF + 1%KF 251 4.9E+08
CS/AR 0.2 As received 156 3.0E+02
CS/AR 0.3 As received 156 7.4E+02
CS/RF 0.2 900 °C/336 h 193 1.1E+04
P/AR 0.2 As received 476 1.3E+18
P/RF 0.2 900 °C/336 h 134 3.0E−01
558 O. Paulsen et al.

Table 5 Calculated maximum Material Load (MPa) 10 mm/5 year, Tmax, °C 30 mm/5 year, Tmax, °C
lining temperature for 10 and
30 mm total creep in 5 years for D/AR 0.20 668 697
the three tested materials in the as D/AR 0.30 606 642
received condition
CS/AR 0.20 719 780
CS/AR 0.30 674 730
P/AR 0.20 770 791

Table 6 Calculated total creep Material Load Comment Creep in mm pr. 100 mm lining/5 years
in mm after 5 years in a 100 mm
thick insulating lining versus (MPa) 500 °C 600 °C 700 °C
lining temperature for the three D/AR 0.20 As received 0.00 0.46 25.70
studied materials
CS/AR 0.20 As received 0.04 0.58 5.32
P/AR 0.20 As received 0.00 0.00 0.15
P/AR 0.20 As received 0.00 0.16 12.94
D/RF 0.20 850 °C/96 h 0.01 0.73 17.22
D/RF 0.20 900 °C/50 h 0.05 1.36 17.53
CS/RF 0.20 900 °C/336 h 0.00 0.14 2.14
P/RF 0.20 900 °C/336 h 0.00 0.01 0.09
D/AR IMP 0.20 1%NaF + 1%KF 0.02 1.48 52.96

Conclusion diatomite was 260 times higher. Compared to

The creep in compression of three commonly used insulating
materials, based on diatomite, calcium silicate and perlite,
have been examined at loads of 0.20 and 0.30 MPa in the
temperature range 750–875 °C. For all materials in the as
received state, the creep rate increased with increasing
temperature and increasing load. At 800 °C and 0.20 MPa
load the creep rates were ranged in the following order:
calcium silicate \perlite \diatomite
Except for diatomite, which showed a decrease in creep
rate above 850 °C, the materials showed an exponential
increase in creep rate versus temperature. After refiring the
materials at 900 °C the exponential law was followed for all
materials.
XRD diffraction analyses showed that the crystalline
structure became more developed after firing compared to
the as received materials. The firing resulted in a substantial
decrease in the creep rates for all materials. Especially the
creep rate of the perlite material changed dramatically,
demonstrating that refiring this material makes it extremely
stable compared to the others. At 800 °C the creep rate of
fired perlite bricks was only *1/100 of the as received
material. At 800 °C and 0.20 MPa load the creep rates for
the refired materials were ranged in the following order:
perlite \calcium silicate \diatomite
Relative to the perlite material, the creep rate of calcium
silicate was 48 times higher and the creep rate of the
un-contaminated diatomite, contamination with 1 wt% NaF
+ 1 wt% KF, resulted in 70% increased creep rate in mean,
for the temperature range 750–875 °C. This observation
demonstrates that fluoride contamination results in a sub-
stantial increase in the creep rate of the diatomite. It is
believed that this kind of contamination will have a similar
effect also on the perlite and calcium silicate materials.
Regarding use as insulating material in the bottom lining
of aluminium electrolysis cells, all materials tested in this
work are applicable. Both temperature and pressure is nor-
mally much lower in a real electrolysis cell compared to the
creep test conditions used in the present work. Based on the
creep results an insulating lining with thickness 100 mm and
temperature 600 °C made of the examined materials, will be
compressed less than *0.5 mm in 5 years. The creep can be
substantially reduced by firing all materials at 900 °C before
installation.
Acknowledgments We would like to acknowledge the Research
Council of Norway Hydro Aluminium A/S for partial funding of this
work.
References
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aluminium reduction cells. Part I: Equilibria at 1100 K, XIV
International Aluminium of Siberia Conference, Krasnoyarsk,
Russia, 69–75 (2008)
2. W.D. Kingery, H.K. Bowen, D.R. Uhlmann, Introduction to
ceramics (Wiley, 1975)
Aging of Insulating Linings in Aluminium Electrolysis Cells 559

3. W.R. Cannon, T.G. Langdon, Review: creep of ceramics—part 1: 5. C.O. Hulse, J.A. Pask, Analysis of deformation of a fireclay
mechanical characteristics. J. Mater. Sci. 18, 1–50 (1983) refractory. J. Am. Ceram. Soc. 49, 312–318 (1966)
4. W.R. Cannon, T.G. Langdon, Review: Creep of ceramics—part 2: 6. Schøning, C. Compression of insulation bricks in electrolysis cells.
an examination of flow mechanisms. J. Mater. Sci. 23, 1–20 (1988) Internal communication in ALILAB (2012.09.14)
 Cathode Wear Based on Autopsy
of a Shutdown Aluminium Electrolysis Cell

Samuel Senanu, Christian Schøning, Stein Rørvik, Zhaohui Wang,

Arne Petter Ratvik, and Tor Grande

Abstract
To investigate cathode wear, an autopsy of a shutdown aluminium electrolysis cell was
conducted. The original lining consisted of a fully impregnated and graphitized carbon
block and the cell was shut down after 2461 days operation. The cell was cleaned down to
the surface of the carbon cathode, revealing the profile of the cathode wear. Generally, the
cathode wear was uneven across the cell with typical potholes. At a finer length scale, the
wear was characterized by small “pitholes” resembling wide shallow pitting corrosion.
Samples of the cell lining were obtained by drilling cylindrical samples at different
locations in the cell. These samples were analysed with respect to phase composition and
microstructure by a combination of X-ray computed tomography, optical and electron
microscopy. The findings are discussed in relation to the current understanding of the
underlying mechanism(s) for cathode wear.

Keywords
Potholes formation Cathode erosion Carbon cathode Aluminium reduction cell

Introduction laboratory tests show that graphitized blocks are inferior to

Cathode wear is one of the most important factors in
determining the cathode life of an aluminium reduction cell
[1]. Factors such as carbon type, amperage levels, bath
chemistry, and cathode design as well as other factors play
an important role in cathode wear [1], making cathode wear
a complex phenomenon. Introduction of the more graphi-
tized cathode bottom blocks coupled with higher amperage
levels and more acidic baths in the aluminium industry
seems to have accelerated cathode wear [1, 2]. Even though
S. Senanu (&)
T. Grande
Department of Material Science and Engineering, NTNU -
Norwegian University of Science and Technology, 7491
Trondheim, Norway
e-mail: samuel.senanu@ntnu.no
T. Grande
e-mail: tor.grande@ntnu.no
C. Schøning
S. Rørvik
Z. Wang
A.P. Ratvik
SINTEF Materials and Chemistry, 7465 Trondheim, Norway
e-mail: arne.p.ratvik@sintef.no
their more amorphic counterparts in terms of mechanical
wear [3], its usage in the aluminium industry is on the rise
[2]. This is largely because of their properties such as low
sodium expansion and high electrical and thermal conduc-
tivity, which contributes to increased productivity and
energy efficiency [4]. Despite the beneficial attributes, it is
observed that cathode life is reduced in line with the intro-
duction of graphitized blocks [1]. The reduction in cathode
life is attributed to the higher degree of uneven cathode
erosion observed on graphitized blocks. The observed wear
rate in industrial cells can be ranked as: graphi-
tized > graphitic > anthracitic carbon [1].
Measurements by Tabereaux et al. [5] showed that the
highest cathode block erosion was located under the anodes
towards the sidewall of the cell, and that the wear under
some anodes was deeper than under others. They also found
almost no erosion in the centre of the cell. This uneven form
of cathode erosion leads to the most common erosion pattern
observed in modern high-amperage prebaked anode cells
called the W or WW wear pattern [1, 4, 6]. Another

© The Minerals, Metals & Materials Society 2017 561

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_70
562
detrimental form of uneven cathode erosion observed in
industrial cells is formation of single potholes or tunnelling
potholes [1, 7, 8], often leading to early pot failure or failure
by tap out [1].
Replacing potlinings and disposing off the spent potlin-
ings (SPL) imposes extra costs for smelters [1]. All attempts
to understand the mechanisms behind cathode wear so as to
implement the necessary actions to improve cathode life, is
therefore of great importance.
Autopsy of spent potlinings have been an important tool
for understanding the mechanisms behind cathode erosion
on both macro and micro scales over the past years [9–11].
The autopsy process involves a combination of various
activities including visual inspection, cavity measurements,
imaging and samples collection from different locations of
interest on the spent potlining and analysing these samples
using different microscopic and X-ray techniques, amongst
others. Øye and Sørlie [1] have given a detailed outline of a
procedure for an autopsy.
In this paper we present an autopsy of an impregnated
and graphitized carbon bottom lining obtained from a cell of
a prebaked technology and side-by-side configuration that
was shut down after 2461 days in operation. Beside visual
observations and measurements of wear, samples from the
autopsy were analysed by a combination of light and scan-
ning electron microscopy and X-ray computed tomography.
Experimental
Autopsy and Sample Preparation
The autopsy was conducted on a spent potlining (D068)
from one of Hydro’s SU4 cathode technologies [12, 13]. The
autopsied pot was about 4 meters wide and 15 meters long with
a cavity of about 53 cm. The bottom lining comprised 19 fully
impregnated and graphitized carbon blocks (TG2). The cell
was operated on an amperage of 313 kA for 2461 days. Six of
the collector bars had been cut prior to the planned shutdown
to prevent iron contamination or tap out from the cell. Before
the autopsy was conducted, the pot was allowed to cool over a
couple of days in an enclosed and dry area, thereby avoiding
any contact with water. Bath and metal were carefully
removed from the spent potlining leaving the exposed surface
of the carbon cathode. The surface was then vacuum cleaned to
reveal all the details such as cracks, potholes, metal plugs,
sludge (muck), etc. The individual cathode blocks were also
numbered with a marker for easy documentation.
Locations of interest all over the cathode bottom block
were photographed. The locations of interest for this autopsy
were the locations with excessive wear on the cathode
blocks, such as near the ends of the cathode blocks, potholes,
wide shallow pittings and other abnormal observations.
S. Senanu et al.
Fig. 1 Illustration of the measurement of the wear profile of the spent
potlining. The blocks are numbered with yellow markings
To obtain the wear pattern on the cathode bottom block, a
laser, an aluminium bar and a ruler were used. Each of the
individual cathode blocks were measured from one end to
the other at regular intervals of 40 cm. The potholes that
were observed were also measured to determine their depths
and diameters. The data obtained were used to characterize
the appearance of potholes on each of the cathode blocks.
Figure 1 is a picture of the measurement setup on the
cleaned spent potlining.
The samples from the spent cathode were obtained by
drilling into the lining at different locations of interest using an
electrical drilling machine. The drilling machine could drill
core samples up to a depth of 10 cm and a diameter of 5 cm.
Before the drilling commenced, all the sample locations were
marked with a yellow marker. All the autopsy samples were
vacuum packed and sealed after the drilling to avoid reactions
with moisture. During sample preparations, a thin bath film
detached from the surface of two samples and the thickness of
the films were measured using a dial indicator.
Laboratory Analysis
The cathode samples were analysed using X-ray com-
puted tomography (CT scan). The CT data was acquired by a
Nikon XTH225ST instrument (cone beam volume CT).
A tungsten reflection target was used with an acceleration
voltage of 140 kV and a current of 135 lA. The imaging
was done with an integration time of 1 s, amplification of
18 dB, with 3142 projections per 360º. The distance from
source to sample was 226.7 mm, distance from source to
detector was 1124.8 mm, detector size 400  400 mm,
resulting in a voxel size of 40.2 lm. The images were
exported as 16-bit TIFF and processed in the public domain
software ImageJ. The autopsy samples were used without
any particular preparation apart from inserting it into a
plastic container to provide stability while in the chamber of
the CT scanner.
For the microstructural and chemical analysis, the
autopsy samples had to be cut into smaller samples,
Cathode Wear Based on Autopsy of a Shutdown Aluminium …
imbedded into epoxy overnight and mechanically polished
to obtain a smooth surface. Optical microscopy was per-
formed using the REICHERT MeF3A optical microscope
whilst Electron microscopy was carried out using the Hitachi
S-3400 N Scanning Electron Microscope. EDS (Energy
Dispersive X-ray Spectroscopy) mapping with AZtec was
used to analyse the elements present.
Results
Visual and Macroscopic Observations
A picture of the spent potlining showing the wear pattern
and the location of the two pothole samples used for the CT
scanning is shown in Fig. 2. A 3D plot of the measurements
of the cavity gave an indication of the wear pattern, this was
similar to the laser scan wear profile observed by Skybak-
moen et al. [13]. The 3D plot is shown in Fig. 3.
Generally, a non-uniform wear was observed all over the
cathode surface and the cathode blocks were observed to be
more worn than the ramming joints between them. The most
severe wear was near the outer ends of the cathode blocks on
both sides (upstream and downstream) of the cell. The wear
towards the centre of the cell was generally less pronounced,
however, moving away from the centre, another area of rel-
atively high wear on both sides of the centre of the cell was
observed. This wear was, however, less than the one observed
near the ends of the cathode blocks. This very high–low–
high-very low–high–low-very high wear pattern of cathode
erosion observed across the cathode block from side to side is
the WW wear pattern. Some of the wear near the ends of the
cathode block were deep and could be described as large
potholes. These large potholes measured up to about 50 cm in
Fig. 2 Picture of the spent potlining showing wear profile and locations
of the pothole samples used in the CT scanning reaction front analysis
563
diameter and about 7–10 cm in depth. A closer examination
revealed a high degree of wide shallow pitting at the surface
within each pothole. A picture of the wear near the ends of the
cathode blocks showing the high number of wide shallow
pitting within the large potholes is displayed in Fig. 4.
Two patterns of erosion, all showing high levels of wide
shallow pitting corrosion, were observed near the ends of the
cathode blocks. It was observed in most instances that the
erosion continued to a certain depth and then stopped before
getting to the collector bars whilst in a few instances it was
observed that the erosion continued all the way to the col-
lector bars with just millimetres of carbon material remain-
ing. Another observation was the relatively high wear
pattern towards the tapping position as compared to the
suction position and the considerably high level of bottom
ledge and sludge at the suction position. The centre canal
towards the suction position had the least cathode wear.
Wide shallow pitting with varying diameter (2–5 cm) and
depth (1–2 cm) were observed on most of the surface of the
cathode blocks. At some locations, typically close to the
sidewall, one could observe a cluster of these pittings that
had joined to form a pothole with diameters of up to 12 cm
and depth of 6–7 cm. A pothole showing the relatively
smaller pittings within is shown in Fig. 5.
A thin layer of bath was observed covering the whole
cathode surface. A picture showing this thin layer of bath
that was detached from the autopsy samples is shown in
Fig. 6. Six different measurements of the thickness of this
thin layer gave an average thickness of 636 ± 200 µm.
Yellowish aluminium carbide was also observed, especially
at locations towards the ends of the cathode blocks where the
erosion was highest and between the ramming joints and the
cathode blocks. Aluminium carbide was clearly visible on
the carbon cathode blocks as shown in Fig. 6.
Laboratory analysis
CT scanning analysis, making use of a computer-processed
combination of several X-ray images obtained from different
angles to produce tomographical images of specific areas of a
scanned object, was used to investigate the distribution of
different phases present in the cathode. The phases were
identified as different shades of greys. For the cathode samples
analysed, the bath component corresponds to the white areas
while the carbon components are reflected in different forms
of grey. Analysis from the CT scanning demonstrated that the
porosity of all the autopsy samples were fully impregnated
with bath. The CT scan point to a relatively higher amount of
bath within the ramming joints than the fully impregnated and
graphitized blocks, probably due to the higher porosity in the
ramming joints. CT scanning image showing bath impreg-
nation is displayed in Fig. 7.
564
Fig. 3 Top view of the wear pattern of the autopsied cell. The yellow dotted rectangles show the sample positions (Colour figure online)
Fig. 4 Cathode wear along the ends of the cathode blocks showing
wide shallow pitting corrosion within. One can also see the less worn
out ramming joint between the more worn out blocks
S. Senanu et al.
Fig. 5 A pothole showing the smaller pittings that joined to form it.
The diameter and depth are also shown
The CT scanning technique was also used to investigate
the reaction front along the edges of the carbon/aluminium
carbide interface in two of the pothole samples prepared by
drilling. It was observed from the CT scanning images that
the cathode block pothole sample had a rougher reaction
front than the sidewall pothole sample. Figures 8 and 9
shows the CT scan at the cathode surface for these two
pothole samples.
Optical microscopy was combined with scanning electron
microscopy and EDS to investigate the microstructure and
phases present in the bath film and near the cathode surface.
Cathode Wear Based on Autopsy of a Shutdown Aluminium …
Fig. 6 Autopsy samples showing the detached thin bath film. The yellow colour at the surface is aluminium carbide. Aluminium carbide could be
observed under the detached thin bath layer on the sample to the left (Colour figure online)
Fig. 7 CT scanning image showing bath impregnation within the
ramming joints and the fully impregnated and graphitized block. The
white is bath and the greys are carbon components
An observation that was made from the different cathode
samples analysed was the absence of aluminium in direct
contact with carbon. Where aluminium was observed, it was
seen as floating fragments, see Fig. 10. The aluminium
carbide layer was also observed in its hydrated form as a
distinct layer rich in oxygen on the EDS mapping images
(Fig. 11).
Discussion
In line with other autopsy investigations [1, 4, 5, 10, 11, 13]
the typical WW pattern was also observed in this study.
Cathode erosion mechanisms are proposed by many authors
[1, 5, 14–21] to be controlled mainly by the formation,
dissolution and transport of aluminium carbide.
Evidence of the limited wettability of aluminium on the
carbon cathode as observed from the cathode samples and
the role of wide shallow pitting corrosion as a precursor for
565
pothole formation are important experimental observations
in the present autopsy. The presence of a thin layer of bath
all over the cathode surface and the high level of bath
impregnation by both the fully graphitized and
non-graphitized parts of the bottom lining, as observed from
the CT scanning images, suggests that the molten electrolyte
wets the carbon cathode block well. Bath impregnation,
which follows the wetting of carbon cathode by the bath, is
assumed to occur fast after the cell has been put online due
to the sodium activity [1, 15].
Aluminium has been assumed to wet carbon in the
presence of molten electrolyte when current is applied to the
cell and the electrochemical cathode reactions are initiated
[1, 22, 23]. However, the almost total absence of aluminium
in contact with the carbon cathode, as observed by micro-
scopy, seems to question the extent to which aluminium
wets the carbon cathode at all during electrolysis. In the
present study, there were no observations of carbon in direct
contact with aluminium on any appreciable level, indicating
that aluminium wets the carbon significantly less than the
molten bath. It can be argued that direct contact between
carbon and aluminium should result in carbide formation
due to the favourable conditions for the carbide forming
reaction (Gibbs energy of −147 kJ at 970 °C) [1],
Reaction 1.
Al(l) þ C(s) ¼ Al4 C3 ðsÞ ð1Þ
If this is an important wear mechanism, aluminium
should have been observed on top of the carbon and the
carbide layer, which was not observed. In the present
autopsy, a thin bath film on top of both the carbon cathode
and the carbide layer was observed. Most likely a thin bath
film may have been present all the time from the start-up of
the pot with bath [1]. If this is indeed the case, the alu-
minium metal will have reduced chances to wet the carbon
cathode, making direct carbide formation a less likely
scenario.
566 S. Senanu et al.

Fig. 8 CT scan of pothole sample taken on the fully impregnated and graphitized cathode block showing reaction front along the edge within the
pothole

Electrochemical wear leading to possible dissolution of
carbon may explain the pothole formation mechanism
observed in the two pothole samples used in the CT scanning
analysis. The wide shallow pitting corrosion seems to have
different formation rates in different parts of the cell. The high
degree of wide shallow pitting corrosion observed within the
locations of relative high erosion near the ends of the cathode
blocks, as shown in Fig. 4, as well as other parts of the cell,
may suggest that wide shallow pitting corrosion is the most
dominant cause of cathode erosion. It can also be assumed
that the mechanism is electrochemical in nature due to the
high current densities at the locations with highest wear.
Cathode Wear Based on Autopsy of a Shutdown Aluminium … 567

Fig. 9 CT scan of pothole sample taken 50 cm from the sidewall showing the reaction front along the edge within the pothole
568
Fig. 10 Light microscopy picture of an interface between carbon, bath
and aluminium showing fragments of aluminium and a defined layer of
hydrolysed aluminium carbide
The absence of carbon particles in the samples analysed
may suggest that wide shallow pitting of cathode blocks
arises from electrochemical induced wear resulting in dis-
solution of the carbon cathode without particle detachment.
This may be because both the binder and the aggregate phase
are fully graphitized and there is no preferential binder phase
dissolution leading to particle detachment as proposed for
cathode blocks with amorphic binder phases [1].
As most of the wide shallow pitting corrosion seems to
be both restricted in width and depth, it is a good indication
that this initiating pitting stops or slows down at some
depth. The real cause for this is presently not determined,
but a plausible explanation may be that bath components
are involved in both the initiation and the slow down.
A possible mechanism is that bath is slowly depleted of
aluminium, resulting in two slow down mechanism. One is
that the wear is less in more basic bath (lower activity of
aluminium for the formation of aluminium carbide) and,
secondly, the fact that more basic bath may freeze out due
to a higher melting temperature. When neighbouring wide
shallow pits reduce the depth of the first pit, the process
may start over again, creating new shallow pits within the
original pit.
The presence of smaller pittings within the larger
potholes, as shown in Fig. 5, supports that this is a central
mechanism for pothole formations. Figure 5 shows that
potholes seem to form from individual pittings joining under
the right conditions. This kind of pothole formation is dif-
ferent from a single pothole formed as a result of chunks
breaking off due to weaknesses or defects in the carbon
lining [1]. The smaller wide shallow pitting seems to form as
a result of electrochemical induced mechanisms. The cir-
cular nature of these pittings may suggest that convective
patterns set by metal pad movement, or whirlpool effect on
S. Senanu et al.
the metal pad close to the carbon surface, due to high current
densities, play a part in their formation [1, 7].
The convective patterns set up by the metal pad move-
ment during metal tapping may also play a part in cathode
erosion. This may contribute to the relatively high erosion
towards the tapping position as compared to the suction
position. Higher velocities within the metal pad movements
during metal tapping will induce convective movements
within the bulk of the bath. This may in turn introduce fresh
bath to the locations with carbide leading to increased car-
bide dissolution and transport, which is suggested to be a
prerequisite for cathode erosion [1, 16, 21]. The consider-
ably high levels of bottom ledge and sludge observed at the
suction position may explain the relatively low erosion rates
observed there. The extensive bottom ledge and sludge that
is accumulated may also be a result of a colder zone or a
more stagnant flow at this location [12]. The high level of
bottom ledge or sludge may protect the carbon cathode block
from erosion by reducing the access of fresh bath that
enhances the dissolution of the carbide layer at this location.
A frozen bottom ledge or sludge may also prevent the
transport of the formed carbide to the bulk bath, thereby
creating a saturation zone for aluminium carbide and thus
reduce its formation.
The high magneto-hydro-dynamic (MHD) forces caused
by the high current densities near the ends of the cathode
blocks, and the close proximity of bath being transported
along the side ledge, may also explain the higher wear
observed near the ends of the cathode blocks. The higher
MHD forces will induce local flow patterns and the close
proximity of bath being transported along the side ledge will
ensure presence of fresh bath that will enhance carbide dis-
solution and transport. Enhanced formation, dissolution and
transport of aluminium carbide at these locations may
enhance the formation of individual wide shallow pits,
which may merge faster with neighbouring pits, collectively
creating the larger potholes.
Some of the earlier proposed theories for cathode wear
may explain the W wear pattern [6]. However, the WW wear
pattern, also observed during the present autopsy, is not
easily explained by many of the prevailing theories. This is
especially true for the W wear pattern close to the centre of
the cell. A mechanism related to the anodes may contribute
to the centre W wear pattern. Gas released from under the
anodes will create additional bubble-induced flow. This
bubble-induced flow may cause more turbulence at the
bath/metal interface in the centre of the cell with the possi-
bility of more bath entrainment and transport to the cathode
surface. In addition, the centre space between the anodes, to
allow room for centre feeders, may cause a different metal
flow pattern compared to cells without centre feeders and no
centre canal. In addition, the additional edge current along
this centre canal may contribute to higher current densities in
Cathode Wear Based on Autopsy of a Shutdown Aluminium … 569

Fig. 11 a, b EDS mapping of the interface described in Fig. 10 showing the individual elements present
570
this area. These mechanisms will be investigated using CFD
(computational fluid dynamics) and MHD models in the
future.
Conclusion
CT scanning images demonstrated that the porous ramming
joint contained higher amount of bath than the graphitized
and fully impregnated cathode blocks. However, both were
completely infiltrated by molten bath. The absence of any
appreciable amounts of aluminium in direct contact with the
carbon cathode suggests that electrochemical induced wear
is the main mechanism behind cathode wear in industrial
cells. The high level of wide shallow pitting at locations with
high erosion rates further suggests that fully impregnated
and graphitized blocks tend to wear by the formation of
these shallow cavities. A possible mechanism for the W
wear pattern towards the centre of the cell is suggested. The
mechanism involves a bubble-induced flow caused by gas
release under the anode leading to turbulence at the
bath/metal interface in the centre of the cell and/or a flow
pattern at the bottom of the cell caused by the two anode
rows being arranged with a space between to accommodate
the centre point feeders.
Acknowledgments Financial support from the Norwegian Research
Council and the industrial partners Hydro, Alcoa, Elkem Carbon and
Skamol through the project “CARMA—Reactivity of Carbon and
Refractory Materials used in Metal Production Technology” is
acknowledged. Special thanks go to the Hydro Sunndal team for the
help with the autopsy.
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 SPL Recycling and Re-processing

Victor Mann, Vitaliy Pingin, Aleksey Zherdev, Yuriy Bogdanov,

Sergey Pavlov, and Vladimir Somov

Abstract
Aluminum smelters generate a considerable amount of spent potlining (SPL), which results
from the chemical and mechanical degradation of carbon, refractory and insulating
materials used to isolate them from a high-temperature and chemically aggressive process
of electrolysis. The specific amount of generated SPL is 18–40 kg/t Al, and it depends on
the life of the cell, which varies from 5 to 7+ years. Besides considerable expenses for cell
relining, SPL has a negative impact on the environment due to fluorine compounds and
cyanides, and for this reason it is classified as a hazardous waste. There are two most
evident ways of minimizing the above negative impact from SPL: a decrease in the amount
of SPL, and SPL re-processing, including SPL neutralization and the production of
sub-products such as fluorine, carbon and aluminosilicates. These materials can either be
used in-house or sold to third parties. This paper covers RUSAL’s efforts aimed at
developing and implementing a technology to recycle and re-process SPL.

Keywords
Spent pot lining Re-processing Recycling

Introduction is that the problem has become acute in Russia. A solution

SPL has the potential to be a future-proof feedstock to
extract essential constituents from it for the conversion into
products to be used in aluminium smelters as well as at the
other industries. Several technical solutions for the precipi-
tator’s dust, scrubber’s slurry leaching, flotation tailing,
spent pot lining recycling and recovery are available at the
moment. Of those a substantial number of the technical
solutions and projects are found to be cost intensive tech-
nologies [1, 2].
Environment friendly and cost efficient waste recycling is
an issue that concerns all the smelters, but what has changed
V. Mann
RUSAL Global Management B.V., 13/1 Nikoloyamskaya Str.,
Moscow, 109240, Russian Federation
V. Pingin
A. Zherdev
Y. Bogdanov (&)
S. Pavlov
V. Somov
RUSAL ETC LLC, 37/1 Pogranichnikov Str., Krasnoyarsk,
660111, Russian Federation
e-mail: Yuriy.Bogdanov@rusal.com
must be found soon.
One of the first large scale SPL processing plants in the
world is that of Alcoa located in Gums Springs, Arkansas,
USA. A mixture of pre-grinded spent pot lining, lime and
anticaking agent (calcium silicate) is loaded into a rotary kiln
75 m long and with a diameter of 2.7 m and is treated at
650–815 °C. The main goal of this process is detoxification
of SPL with the aim of producing a byproduct that is stored
in a special landfill.
In 2008 Rio Tinto Alcan put into operation the integrated
spent pot lining recycling plant in Québec with capacity of
80,000 ton per year at an estimated capital cost $226.8 mln.
Recycling is based on a hydrometallurgical route of
low-caustic leaching and liming process (LCLL process). The
plant produces mainly chemicals (NaOH, CaF2, NaF) and
pure carbon materials. As per the method the pot lining is
delivered in specially designed water-proof and well venti-
lated containers. At the first stage the material is sorted out and
metal inclusions (aluminium and iron) are separated. The SPL

© The Minerals, Metals & Materials Society 2017 571

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_71
572 V. Mann et al.

is then sized in a grinding mill. After grinding the material SPL Recycling Technology
undergoes a two-stage leaching process by water and soda
liquor where fluorides and cyanides from the spent pot lining Laboratory Investigation Stage
are dissolved. The mixture is filtered and the filtrate goes to a
flash tank and the residue is sent to a washing stage. The First cut of SPL recycling technology was developed within
filtrate goes to the crystallizer where the water is evaporated the scope of RUSAL environmental policy. Analytical
and sodium fluoride contained in the solution is crystallized. research was performed at the initial stage of the develop-
According to the market requirements the method provides ment based on the investigation of the main physicochemical
for CaF2 and NaOH production with the introduction of lime properties of SPL.
into the NaF solution. The downside of the method is a large The following reactions are essential in alkaline leaching
recycling flow of water, emission of toxic and explosive of SPL:
gases, a large volume of aggregates in the process and its
requirement to be attached to the alumina refinery because of NaFðsolidÞ þ H2 O þ Na2 O ! NaFðliquidÞ þ H2 O þ Na2 O
the large amount of the alkali that is produced. ð1Þ
Secondary cryolite production from a pot lining produc-
tion facility in Russia was designed and put into operation in Na3 AlF6 þ 2Na2 O þ H2 O ! 6NaF þ NaAlO2 þ H2 ð2Þ
1972 at Achinsk Alumina Refinery basing on the techno-
Na5 Al3 F14 þ6Na2 OþH2 O ! 14NaFþ3NaAlO + H2 O
logical process developed by Klimenko V.P. (fluorides lab).
The technology and the project were developed by the ð3Þ
Irkutsk branch of VAMI (Russian Aluminium and Magne-
AlF3 þ 2Na2 O þ H2 O ! 3NaF þ NaAlO2 þ H2 O ð4Þ
sium Institute). Ground pot lining material with a grain size
<0.2 mm was treated after mixing with a caustic soda
Na2 SO4ðsolidÞ þH2 OþNa2 O
solution at 80 °C in a stirred tank reactor. The solution after
! Na2 SO4ðliquidÞ þH2 OþNa2 O
filtration was sent to the carbonization to extract fluorides as
cryolite. For several years the facility had been recycling and ð5Þ
treating pot lining of the smelters located in Siberia.
2Al þ Na2 O þ 3H2 O ! 2NaAlO2 þ 3H2" ð6Þ
The leaching technology was surpassed by another pro-
cess involving the application of spent potlining in steel- Al4 C3 þ 2Na2 O þ 6H2 O ! 4NaAlO2 þ 3CH4" ð7Þ
making as a replacement for fluorspar: in 1989 IF VAMI
together with UralNIIChM conducted the research program Al4 C3 þ 6 H2 O ! 3CH4" þ 2Al2 O3 ð8Þ
“Fluoride carbon waste of aluminium cell application in
steelmaking”. Based on the developed technology the Al2 O3 þ Na2 O þ H2 O ! 2NaAlO2 þ H2 O ð9Þ
smelters introduced grinding of first cut spent lining (carbon
only), grading and delivery to ZapSIB (West-Siberian CaF2 þ Na2 O þ H2 O ! 2NaF þ CaðOHÞ2 # ð10Þ
Metallurgical Plant) starting from 1993.
MgF2 þ Na2 O þ H2 O ! 2NaF þ MgðOHÞ2 # ð11Þ
UC RUSAL is deeply concerned by environmental issues
in general, and aims to minimize impact of the facilities SiO2 þ Na2 O þ H2 O ! Na2 SiO3 þ H2 O; ð12Þ
certified according to ISO 14001 (environmental manage-
ment system) on the environment. 2Na2 SiO3 þ2NaAlO2 ! Na2 O
Al2 O3
2SiO2 þ2 Na2 O
Environmental policy of UC RUSAL approved by Act ð13Þ
NRGM-11-P029 dd. 26.10.2011 involves all Company
divisions. As per the above policy the environmental activity Al4 C3 þ 12H2 O ! 3CH4" + 4AIðOHÞ3 ð14Þ
of the Company is aimed to the consistent environmental
parameters improvement engaging the best available tech- AIðOHÞ3 þ 3 NaF ! AlF3 þ 3NaðOHÞ ð15Þ
niques and methods to increase waste recycling and recovery
as well as their safe storage [3]. AlF3 þ 3NaF ! Na3 AlF6 ð16Þ
SPL Recycling and Re-processing 573

Table 1 Thermodynamic Reaction № DH298 kJ/mol DS298 DGT kJ/mol

J/molК
parameters for the reactions
proceeding at alkali leaching of 1 −29.18 −22.25 −22.55
the cathode blocks of the carbon 2 −865.22 −21.92 −865.69
part of the lining
3 −1365.63 −5.43 −1364.01
4 −1025.92 14.86 −1030.35
5 −242.07 −65.35 −222.59
6 −990.9 190.46 −1047.68
7 −1989.97 180.90 −2043.88
8 −1524.27 184.02 −1589.1
9 −227.85 −1.56 −227.39
10 28.13 8.18 2.409
11 −247.37 −36.69 −236.44
12 −248.61 9.14 −245.89
13 No data
14 −936.71 1203.78 −1315.44
15 −159.37 −195.29 −101.174
16 −80.35 18.39 −85.83

The probability of the reactions and exothermic proper-

ties are determined by thermodynamic calculations specified
in Table 1.
Calculations were performed as per the standard methods.
Gibbs thermodynamic potential change (ΔGT) was calcu-
lated according to the first approximation equation of Ulich
[4]. WebBook Nist [5] reference data were used for the
calculation. The calculations were performed for the refer-
ence temperature and the research temperature of 363 K
(900 °C) is not believed to influence the results substantially.
It is generally accepted to designate heat of process as ΔH; if
ΔH > 0 the process is endothermic, if ΔH < 0 the process is
exothermic. ΔS is entropy change, ΔG is Gibbs thermody-
namic potential that is in charge of the process spontaneity: Fig. 1 Cell switched off for re-lining
if ΔG < 0 the process is executable, if ΔG > 0 the reaction is
not executable.
Samples for the test were taken from the carbon layer of Main parameters of the of the SPL carbon layer recycling
the spent pot lining of the cell bottom, cell type C8BM process technology are provided below. The lining is cru-
installed at the Krasnoyarsk smelter with a cell lifetime of shed followed by milling to a grain size <200 µm. This to
68 months (Fig. 1). Test results were processed by modern increase the specific surface and thus the reactive power of
methods of analysis: X-ray fluorescence analysis, X-ray the processed material to provide for its further separation
diffraction analysis, SEM, crystal optic analysis was applied from solution phase on industrial suction-type filters or
in part. centrifuges. In case of insufficient milling (grain size bigger
The samples were taken from the cell bottom by core than 200 µm) effective constituents are recovered only in
drilling whereby the bottom area was fully included as per the part and the overall process efficiency decreases. At fine
total bottom block thickness (12 drill samples with dia. milling (less than 50 µm) the required efficiency increase is
30 mm). Drill samples were crushed to a grain size <0.2 mm, not yet reached but power consumption for milling expo-
then mixed and after that average sample was made for the nentially grows in the meantime. First cut spent pot lining is
test samples to be taken from. The sample were taken after milled in aquatic medium at temperature up to 60 °C and
wet cell de-lining i.e. after cathode filling with water. pH 6–8 to prevent dusting of the milled material and
574
premature start of the abovementioned reactions of hydro-
gen (6) and methane release (6) as well as to provide for the
process safety. The pulp is later treated by caustic soda
solution at Na2Ocaustic = 17.5 g/dm3 at temp 80–90 °C
within 120 min. At these process data the solution is
desilicated and the maximum fluoride extraction efficiency
is obtained.
In the course of the lab tests cyanide containing com-
pounds that were accumulated in the pot lining during
operation were studied. The data show that:
– The amount of cyanides and rhodanites in the refractory
lining is low (CN− + CNS− = 0.002% mass);
– In the side wall point sample of the lining it is high
(CN− + CNS− = 0.11–0.14% by mass);
– In the representative sample without chamotte it is
extremely high (CN− + CNS− = 0.14–0.16% mass);
– In the representative lining sample with chamotte content
20% (CN− + CNS− = 0.12% by mass).
Approximately 95% of the cyanide and rhodanite trans-
fers into the solution during leaching. So their content in the
carbon material is extremely small (CN− + CNS− = 0.002–
0.003% mass).
Cyanides and rhodanites transferred into liquor in the
course of cryolite precipitation stay in the liquor to be
used for soda liquor preparation and they are transferred to
the wet scrubber gas treatment system where they are
mixed with the rest of soda liquor flow and undergo
multiple dilutions. Cyanides are not volatile in alkaline
medium.
After alkaline leaching of two tonnes per hour of SPL
produced 15.5 m3/h of solution that contains 42  55 mg/l
of CN-ion. The mass balance calculations show that taking
into account the obtained soda solution mixing with the
general flow supplied to gas treatment center (*450 m3/h),
that the actual solution supplied to the wet scrubbers con-
tains CN-ion ((42  55) * 15.5)/450 = 1.45  1.89 mg/l.
Mud water volume at Krasnoyarsk smelter is 190 thousand
m3 so cyanide dilution and partial oxidizing by air oxygen
will take place on mud storage area. So the residual cyanide
concentration ((1.45  1.89) * 450)/190,000 = 0.0034 
0.0045 mg/l in the mud water will be lower than the per-
missible concentration limit for portable water. Also, in case
of increasing concentration in the mud water there are fol-
lowing ways for detoxing cyanides: thermal hydrolyze,
transformation CN-ion to non-toxic SCN-ion using ele-
mentary sulfur and oxidation using hydric dioxide or per-
oxosulfuric acids in alkaline medium.
As per the results of the lab tests performed the recovery
of three useful compounds as follows:
V. Mann et al.
1. Fluoride (F): 82–84% (of lining content). Non-recoverable
fluoride loss is due to the presence of calcium oxide
4.3 ± 0.3% mass in fluoride form in the lining. Fluorine
recovery reduction can be caused by solution concentration
drop as per Na2Ocaustic lower than 10 g/dm3, leaching by
high alumina concentration solutions and by high sulfates
concentration solutions;
2. Sodium (Na): 88–90% (of lining content). Non-recoverable
sodium loss is due to the presence of two sodium-containing
phases: b-Na2O  11Al2O3 and NaAlSiO4 that are not
released in the atmospheric leaching environment by weak
liquors;
3. Aluminium (Al): 48–52% (of lining content).
Non-recoverable aluminium loss is due to the presence of
two Al-containing phases: b-Na2O  11Al2O3 and
NaAlSiO4 that are not decomposed at out-of-autoclave
leaching by weak liquors (Fig. 2).
The solutions obtained after leaching contain fluorine at
levels of 10–16 g/dm3 or in terms of NaF 22–36 g/dm3,
1–2 g/dm3 Na2SO4, less 0.1 g/dm3 SiO2 and 4–6 g/dm3
Al2O3. Such type of solution allows for secondary cryolite
recovery with an acceptable quality. Carbon material
obtained after leaching and filtration can be used as a flux for
cement production, as it contains 68–71% mass carbon and
2.8–3.5% mass fluoride.
Process Development
As per the lab test results process flow diagram for spent pot
lining recovery was developed (Fig. 3).
The process flow diagram that is developed requires that
the existing hydrate storage area and Fluorides Production
Shop equipment need to reconstructed on Krasnoyarsk
Smelter site (on Fig. 3 this equipment is colored red), as well
as for refurbishing some other equipment (colored green).
The refurbished equipment belongs to the suspended
production line for recovered cryolite production. Only a
flotation type cryolite is now produced at Krasnoyarsk
smelter by froth treatment.
Using existing systems and equipment allows us to
implement the process flow diagram on site at the Fluorides
Production Shop with the installation of some new equip-
ment such as pumps, valves, flow sensors, level sensors and
temperature sensors.
Pilot Testing
The goal of the pilot testing was to prove the data obtained
from our research and laboratory tests. 120 ton of sodium
SPL Recycling and Re-processing 575

Fig. 2 XRD—pattern of the

average pot lining sample

Fig. 3 Process flow diagram

(Color figure online)

hydrate, 30 ton of aluminium trihydrate were delivered and
300 ton of carbon lining with refractory inclusions were
crushed and milled to specification for testing (Fig. 4).
Pilot testing was performed according to the developed
schedule.
Pilot testing of the carbon pot lining recovery technology
for cryolite and carbon material production included the
following stages:
– Grading, crushing and piling at crushing shop 300–350 t
of carbon lining;
– Carbon pot lining transportation to Fluorides Production
Shop;
– Alkali and aluminate liquor solutions preparation at
hydrate storage area of Fluorides Production Shop;
– Start-up and commissioning of pot lining recovery
equipment for Cryolite and carbon material production;
576 V. Mann et al.

Fig. 4 Work station at automatic

process control system
visualization

Table 2 Testing parameters
Solution input parameter for recovery
T = 80  95 °C
Leaching time = 120 min
Leaching solution concentration as per
Na2Ocaustic = 15.5  19.4 g/dm3
Liquid to solid ratio = 6  8 to 1
Recovery process
Process temperature set to 80.5 °C
Specified amount of fresh aluminate liquor in stoichiometric
amount was added to with agitated mixing necessary for
cryolite formation
Mud water was added into solutions mixture to neutralize
and precipitate cryolite with flow rates of 18  20 m3/h
Process time at specified temperature is 120 min
The obtained cryolite pulp was filtered at suction-type filter
The product was packed into Big Bags after drying

– Crushing, leaching, digestion, and filtration with the
production parameters adjustment;
– Test lot of cryolite and carbon material production;
– Process technical and economic indexes analysis.
The main production process parameters for pot lining
recovery to produce cryolite and carbon are provided in
Table 2.
Samples are taken from all of the flows during the pilot
testing by laboratory assistants of the Krasnoyarsk smelter
laboratory.
milled carbon pot lining pulp to be leached for the whole
period of time for fluoride extraction as well as the particle
size. As it can be seen from the provided data, well crys-
tallized cryolite with fluorine content *43% by mass and
negligible impurities is produced as a result of pot lining
treatment with weak alkali liquor and further cryolite pro-
duction by aluminate liquor (Figs. 5 and 6).
Re-processing Technology of Refractory
Parts of SPL

Lining materials need to be recycled, otherwise they have to

Results
Pilot tests performed for spent pot lining recovery showed
high fluoride transition into solution. Fluoride losses are
connected with fluorspar presence in the pot lining (CaF2).
The tests revealed the importance of the total amount of the
be disposed of in some other way, such as in a landfill. Rusal
proposed a process that uses highly dispersed shapeless
lining materials, which can be recycled. The process results
in a multi-layered compacted base to support a structure on
top of it made from various types of highly dispersed lining
materials prepared and laid in the cells using special
SPL Recycling and Re-processing 577

a)

Fig. 5 Cryolite produced

b)

Fig. 6 Fluoride mass fraction comparison of the produced cryolite and

cryolite from the other company plants

equipment, such as a mixer, an installer, and a vibration c)

packer (Fig. 7). The process compacts the shapeless lining
materials to such an extent that in terms of their refractory
and heat insulation properties they are just as good as mol-
ded refractory and heat insulation materials. This process is
being introduced at the company’s smelters, enabling them
to reduce the amount of spent materials they have to dispose
of by 70–80%. The process also includes efficient methods
for disposing of those spent materials that cannot be recy-
cled. At the moment, the company has over 100 reduction
cells in operation that have been lined with recycled mate-
rials using this method.
Fig. 7 Recycling of spent pot lining materials: mixer (a), installer (b),
and packer (c)
Conclusions
Rusal is focused on improving its environmental friendliness
and reducing accumulated environmental damage in the
territories where it has its production sites. Taking into
account the experience and efforts the company is directing
at resolving the environmental issues, it is clear that Rusal
578
has great potential when it comes to developing the use and
recycling of production waste. In fact, the company already
views its waste disposal areas as man-made deposits of raw
materials. However, this approach requires the introduction
of best practices for separation and storage of production
waste. The company is investing a portion of its profit every
year to continue to explore projects aimed at improving the
environmental situation and developing new processes for
recycling production waste.
Acknowledgements The authors wish to thank technology depart-
ment of alumina production RUSAL ETC (St. Petersburg) and per-
sonally to Dr. A. Suss which supported us in during laboratory stage of
SPL processing.
V. Mann et al.
References
1. G. Holywell, R. Breault, An overview of useful methods to treat,
recover, or recycle spent potlining. JOM 65(11), 1441–1451 (2013)
2. B.P. Kulikov, S.P. Istomin, Aluminium Smelting Wastes Treatment
and Recovery, 2nd edn. (St Petersburg MANEB, 2004), 480 p
3. http://rusal.ru/development/ecology/
4. A.A. Zhuhovitskiy, L.A. Shvartzman, Physical Chemistry (Metal-
lurgy, Moscow, 1976), 545 p
5. http://webbook.nist.gov/chemistry
 Alternative Applications of SPL: Testing Ideas
Through Experiments and Mathematical
Modeling

Dawei Yu, Vishnuvardhan Mambakkam, Donghui Li,

Kinnor Chattopadhyay, and Lei Gao

Abstract
Spent pot lining (SPL) is a well-known waste product from the aluminium electrolytic cell.
The SPL generation rate is approximately 1–1.5 million tons per annum, and this is a
significant environmental burden to the aluminium industry. Previous reports indicated that
more than half of the total amount of SPL generated is stored in lined/ unlined
sites/buildings, waiting for further treatment. At the University of Toronto, the Process
Metallurgy and Modelling Group (PM2G) is working extensively to understand the
chemistry of SPL and find alternate applications of SPL. Some of the potential applications
of SPL conceptualized at the University of Toronto are: (a) as a flux in the non ferrous
industry, (b) as an alternate to coal in ironmaking blast furnaces. Experimental and
mathematical modeling techniques have been used to test these ideas, and the results are
discussed in detail.

Keywords
Spent pot lining Mathematical modeling Waste management Recovery Recycling

Introduction generally ranged from $400–$1200 per ton in 2009 [3]. As a

SPL is a hazardous solid waste discharged from the aluminum
smelter, and has a capacity of 1–1.5 million tons per annum
[1]. Soluble fluoride and cyanide inside SPL makes this
industrial waste toxic, and difficult for direct recycling [2].
Treatment of SPL is costly, the unit treatment prices of SPL
D. Yu
CANMET MINING, Natural Resources Canada, 555 Booth
Street, Ottawa, ON K1A 0G1, Canada
V. Mambakkam
D. Li
K. Chattopadhyay (&)
Process Metallurgy and Modelling Group, University of Toronto,
184 College Street, Suite 140, Toronto, ON M5S3E4, Canada
e-mail: kinnor.chattopadhyay@utoronto.ca
D. Li
K. Chattopadhyay
Innovative Extractive Technologies Ltd., 145 St. George Street,
Suite 406, Toronto, ON M5R2M1, Canada
L. Gao
State Key Laboratory of Complex Non-Ferrous Metal Resources
Clean Utilization, Kunming University of Science and
Technology, Kunming, 650093, China
result, most SPL is currently stored at the aluminum smelter
sites or placed in landfills. The storage of this hazardous waste
may have environmental impacts as it will contaminate the
earth’s crust and underground water [4, 5]. At the University
of Toronto, Process Metallurgy and Modelling Group
(PM2G) is working extensively to understand the chemistry of
SPL through thermochemical simulations and advanced
characterisation techniques. Additionally, they have devel-
oped potential alternate applications including (a) as an
alternate to coal in ironmaking blast furnaces; (b) as a flux in
the non ferrous industry. Experimental and mathematical
modeling techniques have been used to test these ideas and the
results are discussed in detail.
SPL as an Alternative Fuel in the Blast Furnace
Environmental concerns like global warming presents an
urgency for decreasing the emission of greenhouse gases
(GHG), and ironmaking furnaces are a major contributor to

© The Minerals, Metals & Materials Society 2017 579

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_72
580 D. Yu et al.

GHGs [6]. In the iron and steel industry, the production of Table 2 Different air components considerations
coke creates excessive emission of greenhouse gases, and Air (wt%) Case1 Case2 Case3 Case4
energy wastage every year. Coke ovens are considered to be N2 0.76 0.74 0.71 0.68
a major source of pollution in the steel plants, and metal-
O2 0.23 0.25 0.28 0.31
lurgical coke is expensive constituting more than 60% of the
Ar 0.01 0.01 0.01 0.01
total burden cost [7]. The market price of coke has varied
from $130 to $800/ton in 2010 [8]. The most promising
trend to reduce greenhouse gas emissions is the replacement
Thermodynamic Predictions
of coke by other carbonaceous materials, which include PCI
(Pulverised Coal Injection), NG (Natural Gas), Hydrogen
The peak flame temperature for the combustions of different
and Oil [9, 10]. Parts of the SPL, namely the first cut, is one
SPL cases are shown in Fig. 1. SPL samples with a mass
of the carbonaceous material as it contains nearly 50% car-
weight of 100 g were combusted under different air weight
bon [11]. The carbon inside SPL is graphitic carbon, which
ratios X. The X was defined as the ratio of the fuel sample
can be recycled as an alternative fuel in the blast furnace.
weight to the air weight. When the fuel sample fully oxi-
Combustion of SPL ensures the destruction of the cyanides
dizes, the air weight ratio is defined as 1. From Fig. 1, the
into Carbon and Nitrogen which reduces the toxicity of this
combustion of SPL samples can achieve a peak adiabatic
industrial waste. Energy released during combustion can be
flame temperature of 2171 °C, and the air weight ratio X is
utilized by the furnace. Moreover, injecting this industrial
between 0.8 and 1.0. On comparing with coal combustion as
waste as an alternative fuel can also reduce coke rates, which
shown in Fig. 2, the peak flame temperature is around
is essential to reduce production costs and green gas emis-
2800 °C, which means that SPL combustion has the
sions during ironmaking.
potential to be used as an alternative fuel of coal in the blast
In this paper the possibility of utilizing SPL as an alter-
furnace. The slightly lower flame temperature for SPL, can
native fuel is demonstrated, and investigated by mathemat-
be compensated by blending SPL with other types of coal or
ical modelling and thermodynamic calculations. The
natural gas during injection. Besides, pre-treatment like
combustion of SPL was predicted by thermodynamic cal-
leaching will increase the graphitic carbon quality of SPL,
culations using FactSage 7.0. The calculation results illus-
which may also increase the flame temperature. This
trated the adiabatic flame temperature, and products of SPL
assumption was predicted by thermodynamic calculation
combustion, and these were compared against the burning of
results of SPL-washed case (Table 3) combustion.
pulverized coal. Chemical reactions between SPL combus-
tion products, and blast furnace slag were also considered in
the simulation. To account for the kinetics and mass transfer
Fluorides Reaction with Slag
aspects of SPL combustion, a CFD model was developed by
ANSYS, and SPL burnout in the tuyere region was pre-
The reactions between the products of combustion from SPL
dicted. The compositions of SPL and Air considered in this
and blast furnace slag are presented in Tables 4 and 5,
study are listed in Tables 1 and 2 respectively.
respectively. The cyanides were decomposed during burn-
ing, and fluorides in the off-gas can reach up to 1.46 (wt%)
Table 1 Different SPL components considerations which is believed to be an environmental concern. However,
SPL (wt%) Case1 Case2 Case3 Case4 Case5 on reaction with blast furnace slag, the fluorides existing as
off-gasses were decreased as shown in Fig. 3a. From
C 40 45 50 55 60
Fig. 3b, it is clear that this decrease is caused by the for-
Na3AlF6 24 17.3 19.8 16.8 15
mation of NaF, CaF2, MgF2 and FeF2 in the slag phase. The
Al2O3 12.3 15 10 6.5 5 capacity of fluoride absorption is proportional to the slag
SiO2 5 6.5 8.5 5 10 input in a considerable range, which means that the effect of
AlF3 7.5 5.5 3.5 10 2 fluorides can be minimized if SPL was mixed with other
NaF 4 1 0 5 2 fuels. Capturing the fluorine in blast furnace slag is an
NaOH 4.5 5 3.5 0 0 innovative way to abate fluoride emissions; however, its
Fe2O3 0 1.5 2.5 0 5 effect on blast furnace slag viscosity, surface tension, liq-
uidus temperature and refractory erosion needs to be
Al 2.5 3 2 1.5 0.8
investigated both experimentally and by thermodynamic
HCN 0.2 0.2 0.2 0.2 0.2
calculations [12–14]. This is outside the scope of this study,
SUM 100 100 100 100 100
and is an ongoing research activity.
Alternative Applications of SPL … 581

2000 PEAK TEMPERATURE= 1944°C 2000 PEAK TEMPERATURE= 1996°C

FLAME TEMPERATURE(°C)

FLAME TEMPERATURE(°C)
1800 1800

1600 1600

1400 AIRCASE1,O 2(23%) 1400 AIRCASE2,O2(25%)

SPLCASE1,C(40%)
1200 SPLCASE1,C(40%)
SPLCASE2,C(45%) 1200 SPLCASE2,C(45%)
SPLCASE3,C(50%)
SPLCASE3,C(50%)
1000 SPLCASE4,C(55%)
1000 SPLCASE4,C(55%)
SPLCASE5,C(60%)
SPLCASE5,C(60%)
800
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 800
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
AIRWEIGHT RATIO,X
when SPL is fully oxidized, X=1 AIRWEIGHT RATIO,X
when SPL is fully oxidized, X=1
(a)
(b)
2200
PEAK TEMPERATURE= 2091°C 2200 PEAK TEMPERATURE= 2171°C
2000
FLAME TEMPERATURE(°C)

2000

FLAME TEMPERATURE(°C)
1800
1800
1600
1600
AIRCASE3,O2(28%)
1400 AIRCASE4,O2(31%)
SPLCASE1,C(40%) 1400
SPLCASE1,C(40%)
1200 SPLCASE2,C(45%)
SPLCASE2,C(45%)
SPLCASE3,C(50%) 1200
SPLCASE4,C(55%) SPLCASE3,C(50%)
1000 SPLCASE4,C(55%)
SPLCASE5,C(60%) 1000
SPLCASE5,C(60%)
800
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 800
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
AIRWEIGHT RATIO,X
when SPL is fully oxidized, X=1 AIRWEIGHT RATIO,X
when SPL is fully oxidized, X=1
(c)
(d)
Fig. 1 Peak flame temperature of SPL combustion, a Aircase 1, b Aircase 2, c Aircase 3, d Aircase 4

Table 3 Analysis of the injection

Injectant High vol coal (wt%) SPL washed (wt%)
Proximate analysis (db)
Volatile 36.86 3.26
FC 55.74 80.39
Residue 7.40 16.35
Ultimate analysis (daf)
C 84.12 93.11
H 5.66 0.24
O 7.57 6.65
N 2.65 0.00
Db dry basis, Daf Dry ash free basis

Fig. 2 Peak flame temperature of coal combustion

582 D. Yu et al.

Table 4 SPL combustion products

Product N2 CO2 CO NaF Ar AlF3 Na FeF3 FeF2 NO
wt% 64.44 19.36 12.62 1.46 0.67 0.24 0.19 0.12 0.11 0.1

Table 5 Blast furnace slag

SiO2 Al2O3 CaO MgO FeO
34.82 12.57 39.75 0.375 0.35
Validation of the CFD Model
The kinetic aspects of the SPL combustion were considered by
the CFD model. Burnout results obtained using the described
model were compared with the experimentally reported burnout
values of a ‘High vol’ coal for a bench scale injection rig. The
injection rig basically is a horizontal cylindrical reactor tube
maintained at 1350 °C temperature where coal is injected at a
rate of 1.2 kg/h using carrier N2 at a flow rate of 0.4 Nm3/h in an
air flow of 10 Nm3/h. The air is preheated to around 800 °C.
Figure 4 shows the burnout comparison at different
oxygen levels [15]. The mathematical predictions were in
close agreement with experimental results, and thus gives
confidence on the ability of the model to predict burnout
results for an actual ‘Tuyere-raceway’ system.
TiO2 Fe2O3 P2O5
Combustion of SPL in the Blast Furnace
0.95 0.765 0.092
The different simulation conditions along with their burnout
values at the end of the domain are compiled in Table 6.
Calculation of burnout was carried out using Eq. 1:
Burnout % ¼ ðmass of combustible in mass of combustibleout Þ
mass of combustiblein  100
ð1Þ
From the computed values for ‘High vol’ coal (Base Case)
and ‘SPL washed’ (Case1), it is clear that ‘SPL washed’ will
leave the raceway practically unburnt (2.89%). With higher
density and heat capacity compared to ‘High vol’ coal, ‘SPL
washed’ particles do not get enough time to get heated in the
short residence period in ‘Tuyere-Raceway’ system. This is
evident from the computed temperature difference shown in
Fig. 5 for ‘Base Case’ of ‘High vol’ coal and ‘Case1’ of
‘SPL washed’.
To promote the heat transfer, a few conditions with dif-
ferent combinations of natural gas with carrier nitrogen, and

102
4.0
101 NaF
100 3.5 CaF2
10-1 MgF2
3.0
10-2
Slag components wt%

FeF2
10-3
Gas products wt%

2.5
10-4
2.0
10-5 N2
CO
10-6 CO2 1.5
10-7 Ar
10-8 NaF 1.0
NaAlF4
10-9 CaF2 0.5
10-10 AlF3
10-11 SiF4 0.0
10-12 0 500 1000 1500 2000
0 500 1000 1500 2000
Reaction Slag (g) Reaction Slag (g)

(a) (b)
Fig. 3 Fluorides in the products: a gas products; b slag components
Alternative Applications of SPL … 583

Burnout ‘SPL washed’ in’Tuyere-Raceway’ system. Further studies

100 are required for estimating the burn out of different types of
High Vol SPL.
90
Modeling Prediction (%)

SPL as Flux for the Non Ferrous Industry

80
In a nickel smelter, a molten matte product typically con-
taining 15–40% Ni, 20–40% Fe, and 20–25% S from electric
70
R2=0.9395 or flash smelting is further converted in a Pierce-Smith
converter [16, 17]. Partial removal of Fe and S is achieved in
60 the converter by injecting air or oxygen-enriched air into the
molten matte to form oxidative products which reports to the
molten silicate slag (FeO) and off gas (SO2). Due to the high
50 oxygen potential, metal losses are high in the converter slag
50 60 70 80 90 100
in the form of entrained matte droplets and dissolved oxides.
Experimental (%)
The predominant form of metal loss is dissolved oxides. It
Fig. 4 Measured burnout versus CFD calculated burnout for ‘High was reported by Toscano and Utigard [18] that as much as
vol’ coal at different oxygen level 76 wt% of nickel in the slag occurred as dissolved nickel
oxide, and 98 wt% cobalt loss in the slag is in the form
dissolved oxides. The converter slag is thus processed in an
2100 SPL washed 1827 electric settling furnace (also called slag-cleaning furnace)
High vol for further metal recovery. By providing enough residence
1700 1427 time for settling (2–4 h [17]) and adding reductant (coke
Paticle Temperature (oC)
Paticle Temperature (K)

[17]) to create an reducing environment, nickel and cobalt

1300
900
500
100
0.0 0.5 1.0 1.5
Distance (m)
Fig. 5 Variation of average particle temperature with distance from
injection point
different oxygen levels were investigated. From Fig. 6, it is
clear that natural gas increases the burnout of ‘SPL washed’,
which is evident from Table 6.
It was also observed that though gas temperature in
raceway increases with higher amount of natural gas injec-
tion in ‘Case5’, the burnout practically remained identical
compared to ‘Case4’. The probable cause is the deficiency of
the presence of oxygen to help the burning process. This is
evident from Fig. 6. Increase in oxygen percentage in
‘Case6’ increases the burnout significantly.
This preliminary study shows that with proper proportion
of natural gas injection along with ‘SPL washed’ and oxygen
enrichment, there is a potential to increase the burnout of
1027 can be recovered in metallic or sulfide forms which settle to
the bottom of the furnace. The aim of this study is to
627
investigate the addition of spent potlining (SPL) as a fluxing
material into the settling furnace in placement of coke as the
reductant for metal recovery.
227
The effect of the addition of SPL first cut was evaluated
by equilibrating varying amounts (0–5 g) of the first cut with
-173
2.0 100 g converter slag at 1200 °C. The mass distribution of
phases at equilibrium is plotted in Fig. 7. Two stages can be
seen from this figure. For SPL first cut addition from 0 to
1.25 wt%, the formation of spinel (Fe3O4) was greatly
reduced to almost nil. This is because the spinel was grad-
ually reduced by the carbon in the SPL first cut forming
FeO, which was then dissolved in the molten slag phase.
This is represented by the reaction (Eq. 2). The second stage
started when more than 1.25 wt% SPL first cut was added. In
this stage, the mass of the molten slag decreased with the
addition of more SPL first cut because the dissolved iron
oxides in the molten slag was gradually reduced by carbon,
which was then absorbed by the matte phase. In fact, the Fe
concentration in the matte phase increased from 20 wt% at
1.25 wt% first cut addition to 67 wt% at 5 wt% first cut
addition. The mass increase of matte in the second stage is
greatly attributed to the reduction of dissolved iron oxides
from the molten slag. A small amount of nepheline (NaAl-
SiO4) was also formed in the second stage.
584 D. Yu et al.

Fig. 6 Variation of ‘SPL washed’ particle burnout at different conditions in a simulated 2D tuyere region

Table 6 Burnout values under different simulation conditions

Injectant Oxygen level (wt%) Burnout %
Case Solid Gaseous
Base High vol X 23 74
Case1 SPL washed X 23 2.89
Case2 SPL washed 25 wt% NG of carrier N2 23 8.78
Case3 SPL washed 50 wt% NG of carrier N2 23 12.36
Case4 SPL washed 50 wt% NG of carrier N2 25 14.39
Case5 SPL washed 75 wt% NG of carrier N2 23 14.52
Case6 SPL washed 75 wt% NG of carrier N2 25 18.17

100 2Fe3 O4 ðs) þ C(s) ¼ 6FeO(l,slag) þ CO2 ðg) ð2Þ

95
Molten slag (g)

90 Compositions of the offgas from the addition of varying

85 amounts of SPL first cut into the converter slag are plotted in
80
75 Fig. 8. As can be seen, CO2 was the major gaseous product
70 in the first stage. There was also formation of SO2 from the
65 30
reaction between the matte and the oxides. These indicate
Molten slag
Matte 25 that the oxygen potential in the first stage was still relatively
Spinel
Nepheline high. The increasing CO/CO2 ratio shows that the oxygen
Gas 20
potential in the system decreased with the further addition
SPL first cut. In the second stage, the formation of CO
Others (g)

15
started to predominate. And this highly reducing environ-
10 ment, introduced by the presence of more carbon from SPL
first cut, resulted in the higher concentrations of Fe in the
5
matte which has been mentioned earlier. There are also
0 minor amounts of HF, H2O, S2 and N2 formed in the offgas.
0 1 2 3 4 5 The formation of N2 is due to the complete decomposition of
Addition of first cut (wt% slag)
cyanide.
Fig. 7 Mass distribution of phases after equilibrating varying amounts With the addition of SPL firs cut, dissolved oxides of Ni
of SPL first cut with 100 g nickel converter slag at 1200 °C and Co in the molten converter slag were gradually reduced
Alternative Applications of SPL … 585

100 2.8
Einstein-Roscoe

CO, CO2 (vol%)

80 2.4 Molten slag

Viscosity (poise)
60 2.0
40 1.6
20 1.2
0 0.8
15 0.4
CO2
CO 0.0
SO2
0 1 2 3 4 5

Others (vol%)
HF
H2O 10 Addition of first cut (wt% slag)
S2
N2
Fig. 10 Effect of the addition of SPL first cut on the viscosity of the
5 molten slag at 1200 °C

0 Toscano and Utigard [23] that the distribution coefficient of

0 1 2 3 4 5
Addition of first cut (wt% slag) Ni (i.e. [wt% Ni]matte/[wt% Ni]slag) is at least one order of
magnitude higher than that of Co under the same conditions.
Fig. 8 Compositions of the offgas after equilibrating varying amounts Viscosity of the converter slag greatly affects the settling
of SPL first cut with 100 g SPL first cut at 1200 °C
efficiency of the matte droplets through the molten converter
slag, which can be expressed by Eq. 3.

V ¼ ðqM  qSÞgr 2 =ð3 lSÞ

Metal recovery from slag (wt%)

100 ð3Þ
80 Ni The viscosities of the molten slag were calculated as a
Co
function of the addition of the SPL first cut and are plotted in
60 Fig. 10. Due to the presence of solid phases (i.e. spinel and
40 nepheline) in the melt, the viscosity became substantially
greater. The viscosity of the melt + crystal system can be
20 calculated with the Einstein-Roscoe equation:

0 gr ¼ g=gm ¼ ð1  u=rÞ2:5 ð4Þ

0 1
Addition of first cut (wt% slag)
Fig. 9 Ni and Co recoveries from the molten converter slag by adding
varying amounts of SPL first cut at 1200 °C
and absorbed in the matte phase, which could be recovered
when the matte droplets settle to the bottom of the electric
settling furnace. Recoveries of Ni and Co from the converter
slag due to reduction of the dissolved oxides are plotted in
Fig. 9. As discussed earlier, the main reaction in the first
stage was the reduction of spinel (Eq. 2). In this stage, the
recovery of Ni reached about 42 wt%. This is because a
substantial amount of Ni was present in the form of spinel
(e.g. FeNi2O4, NiFe2O4). The recovery of Ni in the first
stage was attributed to the reduction of the nickeliferous
spinel. The increase in the recovery of Ni when the addition
of SPL first cut was more than 1.25 wt% is due to the
reduction of the dissolved NiO in the molten silicate slag.
More than 90 wt% of Ni can be recovered by adding 3 wt%
SPL first cut. The recovery of Co is much lower compared
with that of Ni. This can be explained by the findings by
2 3 4 5
The difference between the two curves in Fig. 10 is due to
the presence of those solid phases. As can be seen, the
viscosity of the slag system reduced from 2.6 poise to 0.4
poise in the first stage because: (1) the spinel was reduced by
the carbon in the SPL first cut; and (2) the fluorides dis-
solved in the molten slag which further reduced the viscosity
of the molten slag. In the second stage, the viscosity
increased slightly due to the formation of small amounts of
nepheline (Fig. 7). From the analysis on the viscosity, it can
be expected that the settling of the matte droplets through the
molten converter slag could be greatly accelerated by the
addition small amounts of SPL first cut (>1 wt%).
Conclusions
Through the thermodynamic predictions, SPL was proved to
have the potential to release enough energy during com-
bustion as an alternative fuel. High temperature during
combustion also ensures the destruction of cyanides which
will reduce the toxicity of this industrial waste, and the
586
fluorides inside the products will be absorbed by the met-
allurgical slag. Nevertheless, thermodynamic calculation
was found to have the limitation as it ignores the kinetics of
combustion. Thus, the kinetics were captured by the CFD
model, which was validated against experimental results for
a standard high volatile coal. The combustion of SPL was
found to have some prerequisites like blending with natural
gas. It should be emphasized that the burnout rate of SPL is
encouraged by oxygen enrichment which is required to be
examined in further detail in studies to follow.
The addition of SPL as a flux into the nickel converter
slag for metal recovery was investigated by performing
simulation work with FactSage. Results show that the
addition of SPL first cut was effective in improving metal
recovery by (1) reducing the dissolved oxides of Ni and Co
and (2) greatly reducing the viscosity of the converter slag.
By adding 3 wt% SPL first cut, metal recoveries of 90 wt%
Ni and 50 wt% Co could achieved, and the viscosity could
decrease from 2.6 poise to 0.4 poise.
The process metallurgy and modelling group (PM2G) at
the University of Toronto, looks at SPL as a strategic
material as opposed to a hazardous waste. In the 21st cen-
tury, better waste management procedures are required to
deal with SPL, rather than procedures like landfilling and
seawater leaching. The way forward will be to use SPL in
value added applications, ensuring proper waste handling
and disposal and making the environment cleaner and safer.
References
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Spent potlining (SPL): a myriad of opportunities. Alum. Int. Today
5, 1–4 (2015)
2. T.K. Pong, R.J. Adrien, J. Besida, T.A. O’Donnell, D.G. Wood,
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coal and natural gas in blast furnace. ISIJ Int. 39(3), 229–238
(1999)
10. J. Li, P. Wang, L. Zhou, M. Cheng, The reduction of wustite with
high oxygen enrichment and high injection of hydrogenous fuel.
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possibilities. Waste Manag Res 21(5), 467–473 (2003)
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 Part XIV
Aluminum Reduction Technology: Cell Voltage and
Pot Control
 Clustering Aluminum Smelting Potlines Using
Fuzzy C-Means and K-Means Algorithms

Flávia A.N. de Lima, Alan M.F. de Souza, Fábio M. Soares,

Diego Lisboa Cardoso, and Roberto C.L. de Oliveira

Abstract
Aluminum smelting potlines usually have a big number of cells, producing aluminum in a
continuous and complex process. Analytical monitoring is essential to increase the
industries’ competitive advantage, however, during their operation, some cells share similar
behaviors, therefore forming clusters of cells. These clusters rely on data patterns that are
usually implicit or invisible to operation, but can be found by means data analysis. In this
work we present two clustering techniques (Fuzzy C-Means and K-Means) to find and
cluster the cells that present similar behaviors. The benefits of clustering are mainly in the
simplification of potline analysis, since a large number of cells can be summarized in one
single cluster, which can provide richer but compacted information for control and
modelling.

Keywords
Aluminium smelting potlines Clusters of cells Data patterns Fuzzy C-Means
K-Means

Introduction volume of available data and so on. The analysis of large

In today’s world, especially in the last three decades, it is
natural to have institutions, corporations, companies or
industries with huge databases, the so called big data [1].
This scenario introduces some questions [2]: what to do
with the data stored, how to analyze and use usefully entire
F.A.N. de Lima (&)
A.M.F. de Souza
F.M. Soares
Post-Graduation Program in Electrical Engineering,
Federal University of Pará, Belém, Brazil
e-mail: flavia.ayana@gmail.com
A.M.F. de Souza
e-mail: alanmarcel2@gmail.com
F.M. Soares
e-mail: fms@ufpa.br
D.L. Cardoso
R.C.L. de Oliveira
Faculty of Electrical and Computing Engineering,
Federal University of Pará, Belém, Brazil
e-mail: diego@ufpa.br
R.C.L. de Oliveira
e-mail: limao@ufpa.br
amounts of data by humans is not feasible without the aid of
appropriate computer tools [3]. The data mining area has
then emerged from this scenario.
However, in normal operations, it is common to find no
useful information [1]. Han and Kamber [4] refer to this as
“rich data, poor information”. The effective data mining
transforms data into information, by finding and processing
data patterns with an iterative and interactive way of ana-
lyzing the results [4]. Data mining should consider not only
complex planned queries while aiming at ratifying an
user-generated hypothesis depending on the existing rela-
tions in the data, but also take into account the discovery of
new facts, regularities, constraints, patterns and relations.
Since the 90s, data mining techniques have gained pop-
ularity both in academy and industry environments on sev-
eral areas [3]. In the primary aluminum industry, Soares [5]
and Chermont et al. [6] applied data analysis techniques to
build process data-driven models, while the work of
Xiangtao et al. [7] presented data mining clustering on the
aluminum electrolysis process. Recently, Majid et al. [8]

© The Minerals, Metals & Materials Society 2017 589

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_73
590
used principal component analysis technique to detect
aluminum process faults. Besides, Horvath et al. [9] devel-
oped a data mining model for quality control of aluminum
production process.
This paper shows one of the data mining process tasks;
clustering [10]. The authors perform experiments with two
traditional techniques of clustering, Fuzzy C-Means
(FCM) and K-Means, on aluminum reduction process
database with the aim of identifying cells having similar
behaviors. Subsequently, this information can be used in
further data exploitation, including better data collection,
design of stratified control strategies per cluster of cells, and
statistical investigation of rare phenomena.
This paper is divided into four sections: the first intro-
duces the data mining idea and its use in the primary alu-
minum industry; the second presents a short description of
the variables used, the arrangement of the cells and the basic
statistical data; the third section presents the results of the
real database; and the fourth is the conclusion.
Materials and Methods
Aluminum reduction cells are arranged in potlines, where
each potline has a set of rooms and sections, which contain a
number of aligned cells. In this paper a total of 960 cells are
analyzed. A database collects online data captured by
monitoring sensors. These data include chemical, electrical
and magnetic variables. The number of variables used can be
as huge as the number of cells.
Variables Used to Cluster
We applied the same variables used in the Ph.D. qualifying
thesis of Soares [5] for bath temperature estimation:
(a) Bath Temperature (TMP);
(b) Aluminum fluoride (% de ALF in the bath);
(c) Quantity fluoride added in the bath (ALF3A);
(d) Quantity of fed aluminum (QALr);
(e) Increment of the Temperature Resistance (IncTM);
(f) Power in time percent under-feeding (%TUN);
(g) Power time percent over-feeding (%TOV).
Selection and Data Extraction
As the aluminum production is continuous, the variables are
continuously monitored by sensors and their measurements
recorded in a database, which maintains historical data of
reduction operation. From this large amount of stored
F.A.N. de Lima et al.
Table 1 “Filter” numerical value range by variable
Variable Numerical value range
TMP 940–990 °C
% de ALF in bath 2.65–18.5
ALF3A 1–100
QALr 1820–3000
IncTM 0–1
%TUN 10–140
%TOV 20–80
samples, during the period of 2006–2012, two different data
sets were created:
• Unfiltered
• Filtered
The unfiltered dataset considers samples that have clean
numerical values (no failures in measurement of data lost).
The filtered dataset covers data values inside ranges pre-
sented in Table 1, discarding the outliers.
The histograms in Fig. 1 show visually the data distri-
bution for each variable in the “unfiltered” and “filtered”
datasets.
By viewing the histograms, the outliers and data operat-
ing range are clearly identifiable, this will facilitate the
clustering. To build the dataset used by Fuzzy C-Means and
K-means clustering algorithms, we evaluated average and
median for every variable and cell. This resulted in four
different combinations of experiments listed in Table 2. On
average data calculations, the final result is strongly influ-
enced by outliers. On the other hand, the median is mildly
influenced by outliers, so by excluding the outliers, the
clustering process will be improved. Thus, we have set up
three clusters and the Euclidean distance measure to define
the clusters for all experiments, using only the filtered
dataset (without outliers).
Results and Discussion
After running the FCM algorithm for each experiment
described in Table 2, we found the clustering relation
between each variable pairs, displayed in the scatter plots in
Fig. 2.
Figure 3 shows the scatter plots depicting the cluster
relations between each variable pairs for the experiment #2,
using the median instead of average.
It is noted in Fig. 2 and, that the clusters are well sepa-
rated all over the fourth column and lines, which corre-
sponds to relations with QALr. In most of the cases, the
Clustering Aluminum Smelting Potlines Using Fuzzy … 591

10 5 TMP UNFILTERED 10 4 ALF UNFILTERED

5 15

4
10
3

2
5

0 0
850 900 950 1000 1050 1100 1150 1200 1250 0 10 20 30 40 50 60

10 5 TMP FILTERED 10 4 ALF FILTERED

3 10

2.5 8

2
6
1.5
4
1
2
0.5

0 0
940 945 950 955 960 965 970 975 980 985 990 2 4 6 8 10 12 14 16 18 20

(a) (b)
10 5 ALF3A UNFILTERED 10 5 QALR UNFILTERED
6 6

5 5

4 4

3 3

2 2

1 1

0 0
0 100 200 300 400 500 600 700 800 900 1000 0 1000 2000 3000 4000 5000 6000

10 5 ALF3A FILTERED 10 4 QALR FILTERED

3 12

2.5 10

2 8

1.5 6

1 4

0.5 2

0 0
0 10 20 30 40 50 60 70 80 90 100 1800 2000 2200 2400 2600 2800 3000

(c) (d)
Fig. 1 Histograms of unfiltered and filtered datasets for each variable a TMP b ALF c ALF3A d QALR e INCTMP f TUN g TOV

clustering is more accurate when comparing with total
alumina feed than amongst other variables.
To test the accuracy of the three clusters in crowding
around all the 960 cells which share similar characteristics,
we plotted a 3D chart, where the green, red and black colors
represent the degree of membership of its respective clusters
was created, as shown in Fig. 4, with the axes x: cluster 1
relevance degree (black), y: cluster 2 relevance degree (red),
z: cluster 3 relevance degree (green).
It is also noted in Fig. 4, that in both experiments the
green cluster obtained a higher relevance degree, followed
by the black cluster and finally the red cluster whose
performance on furnace clustering was the worst according
to their relevance degree.
The results by FCM were used to generate a cluster
mapping according to the actual cell layout of the aluminum
production plant, shown in Fig. 5, thereby providing clus-
tering analysis versus localization using different colors for
each cluster.
From Fig. 5 a large predominance of the green cluster in
the first two rooms of can be seen. Besides, the red cluster is
predominant in the rooms 3 and 4 and the blue cluster in the
rooms 5 and 6. In the rooms 7 and 8 there is a sharp cluster
mixing.
592 F.A.N. de Lima et al.

10 5 INCTMP UNFILTERED 10 5 TUN UNFILTERED

2 6

5
1.5
4

1 3

2
0.5
1

0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 0 50 100 150 200 250 300 350

10 4 INCTMP FILTERED 10 5 TUN FILTERED

12 5

10 4

8
3
6
2
4
1
2

0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 20 40 60 80 100 120 140

(e) (f)
10 5 TOV UNFILTERED
8

0
0 20 40 60 80 100 120 140 160 180 200

10 5 TOV FILTERED
5

0
20 30 40 50 60 70 80
(g)
Fig. 1 (continued)

Table 2 Experiments carried out Experiment Clustering technique Statistic measure Dataset type
#1 FCM Average Filtered
#2 Median
#3 KMEANS Average
#4 Median

We also applied another technique applied to cluster After comparing the clustering results of the Fig. 6, it can
smelting cells: the K-Means algorithm. We ran the experi- be noted that Fig. 6b represents a better clustering, since it
ments #3 and #4, whose results can be seen in Fig. 6 con- presented shorter distances between points when compared
sidering the distance between each cluster in two dimensions. to Fig. 6a.
Clustering Aluminum Smelting Potlines Using Fuzzy … 593

10.5 12.0 2400 2550 40 50

962
m_TMP

956
12.0

m_ALF
10.5

35
m_ALF3A

25
2400 2550

m_QALr

0.08
m_IncTM

0.02
50

m_TUN
40

56
50
m_TOV

44
956 962 25 35 0.02 0.08 44 50 56

Fig. 2 Pairwise comparison of variables after clustering with FCM. Experiment #1

The similarity with FCM Fig. 7 exhibits the clustering
analysis versus localization using different colors for each
cluster, generating a clustering mapping according to the
physical layout of the aluminum reduction potline, with
clusters found in the experiment #4. The K-Means algorithm
also showed a predominance of green cluster in the first
room and a mixture of blue and red clusters in the last room.
One notable difference is that the second room is also fully
inside the green cluster, and the cluster mixing repeats in the
3rd, 4th, 5th, and 6th rooms, wherein the 5th room has
slightly greater influence by the red cluster. The 7th room
though presented a great influence of the blue cluster,
behaviour that was found in FCM experiments in 5th and 6th
rooms.
594 F.A.N. de Lima et al.

10.5 12.0 2400 2600 35 45

956 960 964

m_TMP
12.0

m_ALF
10.5

40
30
m_ALF3A

20
2600

m_QALr
2400

0.00 0.04 0.08

m_IncTM
45

m_TUN
35

50
m_TOV

40
956 960 964 20 30 40 0.00 0.04 0.08 40 50

Fig. 3 Pairwise comparation of variables after clustering with FCM. Experiment #2

The FCM algorithm has similar running and to the K-Means: which determines that the closest data to the centroid are
both are based on the concepts of similarity measures and are associated with greater relevance functions and vice versa, as
influenced by subjectivity in clustering quantity determination. the calculation of the centroid uses the relevance function,
The FCM method should minimize an objective function, which is constantly updated to the algorithm convergence.
Clustering Aluminum Smelting Potlines Using Fuzzy … 595

1.0

1.0
0.8

0.8
0.6

0.6
3

3
1.0 1.0

2
0.4

0.4
0.8 0.8

0.6 0.6
0.2

0.2
0.4 0.4

0.2 0.2
0.0

0.0
0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0

1 1

(a) (b)
Fig. 4 Experiments with membership values for each cluster found in FCM. a Experiment #1. b Experiment #2 (Color figure online)

Fig. 5 Clusters mapping versus physical location using FCM (Experiment #1)

The K-Means method consists in a procedure in which,
given a predetermined number of clusters points represent-
ing the “centers” of these clusters are calculated and they are
spread homogeneously in the set of responses from the
quiz and moved, heuristically, until a static balance is
achieved [11].
Both methods were tested using 960 furnaces, arranged in
120 rooms, in order to cluster them according to their sim-
ilarities and synthesize the study and evaluation method of
these furnaces. So, instead of using all the mixed and stored
data to generate models that reflect the furnace behavior [6]
data from a furnace of each cluster is used, simplifying the
596 F.A.N. de Lima et al.

146
2 3
1
1
1 1 3 3 222
318
3 3
2 3 2
2
3 22

144
11 1 3 33 2 2
11 1 3 3 2
1 1 1 13 3 3 3 3 33 3
317

11 1 1 2 1 333 3333 3 3 33 3
3 1 1 11 1 1 2 111 3 333
3
3 3
3 33 33333 3 2 22 2
1 111
1 1 111 111
1 1 1 3 33 333333 333 33 3 2 2 2 22
1 1 113 33333 2222 222 22 22 2

Discriminant Coordinate 2
1 1
Discriminant Coordinate 2

1 11 111111111111 111111111 333 3 333333 3 33

1 1 1 2 311 33333333333 33 3 3 33 2
3 3333333
3 33333 3111 11 1 11 1
1 111 111
1 1 2 1 1111 11 11111 11 111 1 31133 33 33 3333 333
33333 3 2 2 222222 22 2
316

3 3 2

142
1 2 1 11 11 1 1 1 3
11111113333 333 3 3 333 33 3 3 2 2 22222222222 2
3333 3 3333 3111111 11 111 1 1 1
1 2 1 11
111 111111111111
1111
11111111 111111111 3333333333
33333333333
2 2222
2 22222 22222222 22 2
3 3 1 11 111 1 1 1 1 1 2
2 2 2 22
1 1 1 1
111 1 1 1113133333333
1 3 3 33 3 3 222
2 2 2222 222 2
3 3 33 3 3 3 333 131 11 1 1 1111 11 1 1 1 11
1
11 1
1
1
1
1 1
1 1
1
1
11111111 1
1
11
11 1
1
1
1111 1313
1 13
3 3
33
11111111 33 333 33333
33 33333 3 3 2 2 22
2
2 22 2 2
2
2
2 22 22
2
2
2222222 2
222
2
2 2
2 222 2
33
3 33333333 11 1 1 11 11 111111 111 1 111111 3 2
3 3 3 33 3 111111 1 1
1 1 1 2 2 2 2 222 1
111 11111111111111 1
11 111 1 1
1 11 1111113313 33 33 3 3
3 333333333 3 33 3 3 2 22 2 2 2 2 22
2222222222
2 2 2
3
33333 333 33 1
333 331313 111 11 1 1111111 1 1 1 22 1111 1111111
11 111 3 3 3 3 33 3 3 2 2 2222 2222222 222 2222
2 222
315

2 1
1 1 1 11111 33 33 3
333333333333333 11111 111 111111 2 311 33 333 2 22 2 2 2
33 3 11131 11 2 2 22 22222222 2 2 111 111 111 11 133 3 33 33 33 2 2 2222 2 222222 22 2
3
33 3 1 1111
1111 11 11 22222 11 1

140
3 333333333333 33 1111 1 1 2 222222222 2 2 2 11 11
1 1 1 11 3
11 1 2
3 3333333 3333 33333111111 1111111111 1 1 1 2
2222222
22
2 22 222 222 2
2 111 1 11 11 1111113 3 33
3 2 22 2 222 2
333333 33333333 33 3311 1111 111 11 1111 1 2 2222 2222222222222 2 22 1
3 333333 333 3 33 33 11 3131111 1
111 11 1 1 31 2 2
2 22
314

333 333333 33333333 33 1131111 111111111 1111

1 22222222
22
2 222 22222 2 2
222 11 33
3 3 3 3
3 3 3 3 33333333 33 1 1 11
3331111111111 1 1 11
1 2222222222 2222 22 2
2
2
3 33 333333 333333 3333333333 333
3 3333 1 1
33 22 2 2222 2222
22 2 22 1 1
1
3 3 3 3 3 1 11 1 2
2 22 2 22 2
33 3 333 33333 333 33 333333
3333 333333333333
13 1 31 1 11 2 2 2222 22
2 2 222 2222

138
3 33 333 1 1 2222
333 3 33333 333 3
3 33 3333333 31111
11 2 2222222 22 222
313

3 33 33333 333 3 3 1 1 2 2 222 2

3 3 1 2
3 3 33 33 3333 3 333 11 12 2 2 2 22
3 3333 33333 1
3 3 3 2
3 3 3
312

33 3 2

136
3 3 1
2

−224 −222 −220 −218 −216 −214 −212 −190 −188 −186 −184 −182 −180 −178

Discriminant Coordinate 1 Discriminant Coordinate 1

(a) (b)
Fig. 6 Similarities found via K-Means. a Experiment #3. b Experiment #4

Fig. 7 Cluster mapping versus physical location using K-Means. Experiment #4 (Color figure online)

modeling and increasing the accuracy of the models, since to the development of quality solutions for an aluminum
each cluster would make the models more specific and more furnace factory reduction clustering whereby it was possible
general at the same time. To this end, both the FCM and to show that the performance of FCM and K-means algo-
K-Means algorithms have achieved satisfactory results. rithm in the task of clustering performance was similar.
After analyzing the results of many experiments, described
previously, it was verified that these clustering techniques
Conclusions performed satisfactorily the separation among three different
cell clusters, represented by red, green and blue colors. This
Clustering techniques have been successfully used in many represents a great advantage, as the data use to make infer-
areas, especially on those where there is no prior knowledge ences about certain behaviors of the electrolytic cells can be
about the data organization. The presented paper contributes summarized from the three found clusters, instead of using the
Clustering Aluminum Smelting Potlines Using Fuzzy …
entire database, making the analysis simple, synthetic and of a
better understanding. Another advantage which derives from
the clustering potlines concerns about creates specific models
for each cluster. It tends to generate more accurate models and
once these models are used to control the process, then the
control also will be more precise.
References
1. S. Sumathi, S.N. Sivanandam, Introduction to Data Mining and its
Applications (Springer, 2006), p. 2
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(IISA’09), (Qingdao, P. R. China, 28–30 Oct 2009), pp. 193–195
3. M. Bramer, Undergraduate Topics in Computer Science—Princi-
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4. J. Han, M. Kamber, Data Mining: Concepts and Techniques, 3
edn. (Elsevier, 2012), p. 5
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5. F.M. Soares, Neural dynamics modeling and fuzzy control
electrolytic bath furnace of aluminum smelting. Doctoral qualifi-
cation, Federal University of Pará, Belém-Pa, 2015
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bath chemistry variables using neural networks. TMS Light Met.
607–612 (2016)
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L. Qingyu, The development and application of data warehouse
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Light Met. 515–519 (2006)
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R. Young, Aluminium process fault detection by multiway
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(2011)
9. M. Horvath, E. Vircikova, Data mining model for quality control
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Data Mining (Wiley, 2005)
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pp. 381–405
 Application of Multivariate Statistical Process
Control with STARprobeTM Measurements
in Aluminium Electrolysis Cells

Jean-Pierre Gagné, Rémi St-Pierre, Pascal Côté, Pascal Lavoie,

and Albert Mulder

Abstract
Due to the multivariate nature of the aluminium electrolysis process, the usual univariate
control algorithms coupled with the low visibility of the process used in the aluminium
industry intrinsically causes control errors resulting in suboptimal process control. A trend in
the industry consists in applying multivariate statistical process control with specific
responses to the cause of variations. Such a system in the form of a Bath Temperature and
Chemistry Control Module (BTCM) was developed to be used in conjunction with
state-of-the-art STARprobeTM measurements of electrolyte properties, providing the ability
to respond quickly to causes of abnormalities detected from the immediate synchronous bath
measurements. This paper presents the system and results from a smelter’s pilot section.

Keywords

Process control Abnormality detection Root cause analysis Corrective actions
Bath Temperature Chemistry

Introduction consumption. The bath chemistry, the mass balance and the
energy balance are closely connected with each other. Many
The process variables of the Hall-Héroult electrolysis pro- process parameters such as the bath level, metal level, cell
cess need to be tuned into specific ranges to ensure good voltage, excess aluminium fluoride concentration, alumina
efficiency in terms of metal production and energy feed, condition of anode and of anode cover, etc. affect the
outcome of the process. Thus, aluminium smelting is with-
J.-P. Gagné (&) out a doubt a multivariate process.
Electrolysis & Carbon Products, STAS Inc., 1846, rue des However, most smelters still use old process control
Outardes, Chicoutimi, QC G7K 1H1, Canada
systems of “Generation 1” [1] focusing on compensatory
e-mail: gagne.jp@stas.com
actions aiming at returning a process variable to a target.
R. St-Pierre
This very often leads to high levels of type I and type II
STAS Inc., 1846, rue des Outardes, Chicoutimi, QC G7K 1H1,
Canada control errors [1].
e-mail: stpierre.remi@stas.com With regard to process control, a new approach intro-
P. Côté duced in 2014 by Mulder et al. [1] is defined as the Gen-
Development and Innovation, STAS Inc., 1846, rue des Outardes, eration 3 process control. This approach integrates all major
Chicoutimi, QC G7K 1H1, Canada processes linked to process control in a reduction plant,
e-mail: cote.pascal@stas.com
including early detection and diagnosis of process abnor-
P. Lavoie malities by using additional sensors, guided root cause
Consultant, 411, rue du Brome, St-Augustin-de-Desmaures, QC
analysis and automated corrective actions.
G3A 2V7, Canada
The STARprobeTM is a new sensor that fits perfectly with
A. Mulder
this new process control approach. Indeed, four critical
Albert Mulder IT Consultant, Woldjerweg 23, 9792TC Ten Post,
The Netherlands process variables can be measured simultaneously within

© The Minerals, Metals & Materials Society 2017 599

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_74
600
3 minutes directly in the potroom: bath temperature, bath
superheat, excess ALF3 and alumina concentration. These
process parameters are critical for efficient operation.
Moreover, they are obtained synchronously which is a huge
improvement compare to often non-synchronised traditional
bath sampling and temperature measurements [2].
The Bath Temperature and Chemistry Control Module
(BTCM) presented in this paper uses STARprobeTM mea-
surements coupled with the latest developments in terms of
multivariate statistical process control tools and identifica-
tion of root causes to yield efficiency improvements of the
reduction process.
BTCM Structure
As depicted in Fig. 1, BTCM is built around three main
components. The first component shown is the plant process
control system used by BTCM to exchange information.
Although the Manufacturing Execution System (MES) layer
suggests one database system, most of the control systems
encountered are highly heterogeneous. BTCM has the ability
to communicate with different data sources such as Oracle,
MSSQL, Postgres, Excel, or comma separated value sources,
for example.
The link between the BTCM server is bidirectional,
which means not only that the data is collected from the
MES system but that it is also possible to send control
messages to the pot controller.
Fig. 1 BTCM architecture
J.-P. Gagné et al.
A second component is the STARprobe measurement
device with the on-board BTCM interface. This device
collects physical information in terms of bath analysis of a
cell. If required, additional information is requested from the
operator on the basis of the observations needed to find and
address the root cause of a potential problem.
The BTCM server is the third main component and uses a
centralized database. It automatically collects and transforms
the process information it needs to monitor the thermal and
chemical states of the bath in a cell.
BTCM has three main functions. First, as mentioned
before, data collection requires process information on both
individual cells (e.g. anode effects and metal analysis) as on
a group of cells (e.g. fluoride content in secondary alumina).
BTCM uses a number of tools adopted from GEN3, a
supervisory control system built by the Light Metals
Research Centre of the University of Auckland [1]. Next to
keeping track of the condition of the process, the second task
is to maintain a communication protocol with the on-board
BTCM. The information provided to the latter will be used
during the measurement process to ask relevant questions
about the abnormalities found.
Once abnormalities are found, the final task of BTCM is
to analyze and find their actionable root cause. To this end,
all the information provided by the on-board BTCM and the
process data from the smelter are used. Depending on the
actionable cause found, BTCM suggests appropriate cor-
rective actions, either by adjusting process inputs or
addressing physical problems on the cell.
Application of Multivariate Statistical Process Control …
The BTCM server runs on a Windows server capable of
hosting a Postgres database. The “relay” program on the
BTCM server provides the first task, which is collecting data
from different sources. As showed in Fig. 1, BTCM is
equipped with an HMI (human machine interface) running
on any ordinary Windows machine. The HMI shows the
condition of the cells in one picture, as shown in Fig. 1. The
process operator uses the HMI to check the actions that need
to be taken. These control actions may or may not be sent to
the controllers, as appropriate.
As outlined above, the on-board BTCM is integrated to
the STARprobeTM system. It is an additional module run-
ning in background along with the STARprobeTM software
performing all necessary tasks during measurements of the
electrolysis bath properties [3]. Prior to the measurement
campaign, factory parameters and process data are syn-
chronized from the BTCM server to the STARprobeTM
system. This ensures abnormality calculation and detection
are made using the latest control parameters and the latest
states of the cells to be measured.
The on-board BTCM is responsible for collecting the
results of the STARprobeTM measurements as soon as they
are obtained and then performs statistical calculations in
order to detect any abnormality. The electrolysis cell is then
classified whether as ‘in control’ or in one of the five ‘out of
control’ areas [2]. Depending on a preclassification, the
on-board BTCM can ask for appropriate observations to
pinpoint the root cause of the abnormality. This allows the
BTCM server to propose appropriate corrective actions.
Observations on the cell are requested immediately after the
measurement in the form of visual multiple choice questions
so the process operator can easily record his observations to
the STARprobeTM HMI.
Once measurements are completed, all results and relevant
information gathered during the measurement campaign are
synchronized from the STARprobeTM system to the BTCM
server where decisions on corrective actions are made.
Pilot Section Setup
A pilot section was established at a North American smelter
operating side-by-side, point-fed prebaked cells operating
between 175 and 180 kA. Alumina is periodically delivered
Fig. 2 Timeline of implementation stages of BTCM
601
to the cell superstructure by overhead cranes while aluminium
fluoride is delivered in incremental doses of 40–50 lbs, using
hoppers into the alumina bin of the superstructure of indi-
vidual cells. No dedicated AlF3 feeder is used; therefore,
fluoride is fed to the cell through the alumina feeding system
with a delay in the order of hours after the dosage.
The pilot section consists of 14 contiguous cells at the
end of a potroom. Baseline data was gathered from 1
February 2015 until the implementation of BTCM on 17
May 2015. From 18 May 2015, BTCM was used with fac-
tory parameters and initially operated in open loop, meaning
that the normal control actions at the plant were carried out,
but on the basis of abnormality detection by BTCM. This
means that unless a statistical abnormality is detected, no
input changes are made to the process. A reference group
consisting of the other 28 cells of the section was monitored
using the same indicators.
BTCM results are considered according to the following
four stages. Stage 0 (BTCM_0) represents the baseline
timeframe before the implementation of BTCM. Stage 1
(BTCM_1) consists of the initial implementation of BTCM
operated with factory parameters and gradually integrated
control actions prescribed by BTCM. For stage 2
(BTCM_2), changes were made to the initial parameters to
optimise detection and control actions. From this point,
control actions were gradually taken in accordance with the
instructions given by BTCM, but with a few exceptions.
Finally, changes to the logistics of alumina delivery to
reduce the variability of fluoride concentration were made
for stage 3. Figure 2 shows the timeline of the implemen-
tation stages of BTCM.
Over the 340 days during the implementation of BTCM,
including 72 days for stage 4, several indicators were
monitored to evaluate the performance of the system and its
impact on the stability of the process and on the outcome.
These indicators are defined in three categories.
(1) Leading indicators, which are primarily the STARpro-
beTM measurement array: the process variable to be con-
trolled. (2) Lagging indicators, which are process indicators
usually followed daily to represent the stability of the pro-
cess, as impacted by the process inputs through the leading
indicators. (3) Finally, the outcome indicators, which are
further down the process chain but which represent items of
productivity and efficiency. Ultimately, these outcome
602 J.-P. Gagné et al.

Fig. 3 BTCM process control

variable structure Othe
r pro
cess
inpu
ts
Oth
Cell V proc er lead
ess v in
ariab g
les Ot
he
Bath Temperature rL
a
va gging
ria
ble pro
s ce
AlF3 addi ons Bath level ss

Liquidus
Temperature

Na2CO3 addi ons Metal level Current Efficiency

Superheat

Alumina feed rate Noise Energy Efficiency

Excess AlF3

Metal tap Anode Effects

Alumina
Concentra on

Physical
interven on to cell

Process inputs Leading indicators Lagging indicators Process outcome

variables dictate the profitability and acceptability of an

operation. Figure 3 represents the variable structure included
in the scope of the BTCM system.

Results

Leading Indicators

The process variables, controlled by BTCM during this

study and referred to as leading indicators, were the array of
STARprobe measurements: bath temperature, liquidus tem-
perature, superheat, excess AlF3 and alumina concentration.
Upon the initial implementation of BTCM, an immediate
reduction of variation between the measurements (moving
range) of the individual pilot cells was obtained for most
parameters. Figure 4 shows an example of such reduction in
the moving range, on the bottom graph.
As a whole, the reduction in variability achieved during
stage 3 ranged from 17 to 31%, except for the variation in
the alumina concentration, which remained unchanged.
Figure 5 presents the evolution of the moving range for each
leading indicator.
The average of each leading indicator is presented in
Fig. 6. As can be seen in this figure, the liquidus temperature
increased during stages 1 and 2. It was found that the
fluoride input to the pilot cells was often not as expected due
to logistic issues with the reacted alumina delivery. As a
consequence, the excess AlF3 reduced in the early stages of
Fig. 4 Example of reduction of individual moving range for one pilot
cell following implementation of BTCM
the implementation of BTCM, resulting in a higher liquidus
and bath temperature. The problem was corrected at the start
of stage 3, which brought the excess AlF3, liquidus and bath
temperature back on target for the entire course of stage 3.
Superheat increased marginally during the trial, peaking at
12.1 °C during stage 2 but was brought back closer to the
target for stage 3. Alumina concentration was found to be
very high during the baseline period. Changes to the alumina
feeding strategy were made for the start of stage 1, and the
average alumina concentration was maintained around 2.7%
for the duration of the trial.
Application of Multivariate Statistical Process Control … 603

Moving Range Evolu on of Leading Line Plot of Mean( AVGVOLTS )

4.8
Indicators GROUP
BTCM_0
BTCM_1
14.00 BTCM_2
12.00
-31% -22% 4.7 BTCM_3
Ref_0
Moving Range

Mean of AVGVOLTS
10.00 Ref_1
8.00 -17%
6.00 4.6
4.00 -26% +2%
2.00
4.5
0.00
Tb Tliq SH XsAlF3 Al2O3

BTCM_0 BTCM_1 BTCM_2 BTCM_3 4.4

Fig. 5 Reduction of variability (moving range) of leading indicators 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 1 5 15 15 15 15 15 16

2/ 2/ 3/ 3/ 3/ 4/ 4/ 5/ 5/ 6/ 6/ 7/ 7/ 8/ 8/ 8/ 9/ 9/ 0/ 0/ 1/ 1/ 2 / 2/ 1/
1/ 15/ 1/ 15/ 29/ 12/ 26/ 10/ 24/ 7/ 21/ 5/ 19/ 3/ 17/ 31/ 14/ 28/ 2/1 6/1 9/1 3/1 7/1 1/1 4/
1 2 2 2

Fig. 7 Evolution of daily average cell voltage during Implementation

Leading Indicators, average per stage of BTCM
980.00 20.00 SH (oC), XsAlF3 (%), Al2O3 (%)
Temperature: Tb, Tliq (oC)

970.00
960.00 15.00
950.00 Line Plot of Mean( MDEPTH )
940.00 10.00 GROUP
8.5 BTCM_0
930.00 BTCM_1
920.00 5.00 BTCM_2
BTCM_3
910.00 8.0 Ref_0
Mean of MDEPTH

Ref_1
900.00 0.00
BTCM_0 BTCM_1 BTCM_2 BTCM_3
7.5
Tb Tliq SH XsAlF3 Al2O3

Fig. 6 Average of each leading indicator per stage 7.0

6.5
Lagging Indicators 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 16
2/ 2/ 3/ 3/ 3/ 4/ 4/ 5/ 5/ 6/ 6/ 7/ 7/ 8/ 8/ 8/ 9/ 9/ 0/ 0/ 1/ 1/ 2/ 2/ 1/
1/ 15/ 1/ 15/ 29/ 1 2/ 26/ 10/ 24/ 7/ 21/ 5/ 19/ 3/ 17/ 31/ 14/ 28/ 2/1 6/1 9/1 3/1 7/1 1/1 4/
1 2 2 2
DATE
The lagging indicators observed over the course of the pilot
trial were: cell voltage, bath level, metal level, cell instability
(noise) and anode effect frequency. Fig. 8 Evolution of daily average metal depth during implementation
of BTCM
As can be seen in Fig. 7, the cell voltage was lower in the
trial group during the baseline period but was trending up
over the implementation stages of the BTCM stages up until The last lagging indicator monitored the frequency of
stage 4, at which point the cell voltage was gradually anode effects, as shown in Fig. 11. Although not evident
reduced in conjunction with the reduction of the metal level from the line plots, a 29% reduction in the anode effect
to maintain the heat balance and achieve a more efficient frequency was observed in the trial group, going from 0.78
operating point for the individual cells. The adjustment to 0.49 AE/cell.day. The reference group incurred an
process for the heat balance was guided by BTCM after the insignificant increase from 0.65 to 0.66 AE/cell.day.
stabilization of the leading indicators. As a result, the aver-
age operating voltage of the trial cells was 41 mV lower
during stage 4, when compared with stage 0, coupled with a Outcome
reduction of 0.3″ of the metal depth (Fig. 8).
The bath depths were not significantly impacted and The outcome of the process in terms of current efficiency and
followed the same trends as the reference group, as evi- energy efficiency was estimated for the pilot section and its
denced in Fig. 9. Noise had been trending up in both groups reference group. Unfortunately, the exact values in terms of
during the baseline period and, similarly to the bath levels, daily amperage could not be obtained. Therefore, the
followed similar trends over the course of the trial (Fig. 10). amperage value used in the calculation was taken as a
604 J.-P. Gagné et al.

constant reflecting the amperage target (179.5 kA)

Line Plot of Mean( BDEPTH )
throughout the trial period, with fluctuations between the
GROUP
BTCM_0 stages assumed to be negligible.
9 BTCM_1
BTCM_2 As indicated in Figs. 12 and 13, the estimated current
BTCM_3
Ref_0 efficiency increased by 1.3% between the baseline period
8
Mean of BDEPTH

Ref_1
and stage 3, while the specific energy consumption
decreased by 0.34 DCkWh/kg. This substantial improve-
7
ment in the performance is encouraging, but it should be
noted that the performance of the reference group also
6
increased over the course of the trial, although not to the
same level. A diminution in the performance can be noted
5
during stages 1 and 2 and is possibly a result of the reduction
15 15 15 15 15 15 15 1 5 15 1 5 15 1 5 15 1 5 15 1 5 15 15 15 15 15 15 15 15 16
2/ 2/ 3/ 3/ 3/ 4 / 4/ 5 / 5/ 6 / 6/ 7 / 7/ 8/ 8/ 8/ 9/ 9/ 0/ 0/ 1/ 1/ 2/ 2/ 1/
1/ 15 / 1/ 15 / 29/ 12 / 26/ 10 / 24/ 7 / 21/ 5/ 19/ 3/ 17/ 31/ 14/ 28/ 2/1 6/1 9/1 3/1 7/1 1/1 4/
1 2 2 2
of excess AlF3 in the trial section, according to observations
DATE and mechanisms determined by Tarcy on industrial cells and
Solli et al. on laboratory cells [4, 5]. The use of a higher cell
Fig. 9 Evolution of daily average bath depth during implementation of voltage also negatively impacted the specific energy con-
BTCM sumption during stages 1 and 2.
The pilot trial ended when the potline went through a
sustained power failure and was not restarted. At that time,
Line Plot of Mean( AVGNOISE ) the performance of the trial cells was still being improved,
GROUP
BTCM_0
with more voltage reduction expected. However, the true
0.07
BTCM_1
BTCM_2
potential of the system was not completely assessed.
BTCM_3
0.06
Mean of AVGNOISE

Ref_0
Ref_1

0.05
Current Efficiency
0.04 93.5%
93.0%
0.03 92.5%
Current Efficiency

92.0%
0.02 91.5%
15 15 15 15 15 15 15 15 15 15 1 5 15 15 15 15 15 15 15 15 15 15 15 15 15 16
91.0%
2/ 2/ 3/ 3/ 3/ 4 / 4/ 5/ 5/ 6/ 6/ 7/ 7/ 8/ 8/ 8/ 9/ 9/ 0/ 0/ 1/ 1 / 2/ 2/ 1/
1/ 15/ 1/ 15/ 29/ 12 / 26/ 10/ 24/ 7/ 21/ 5/ 19/ 3/ 17/ 31/ 1 4/ 28/ 2/1 6/1 9/1 3/1 7/1 1/1 4/ 90.5%
1 2 2 2
DATE 90.0%
89.5%
89.0%
Fig. 10 Evolution of daily average noise during implementation of 88.5%
BTCM BTCM_0 BTCM_1 BTCM_2 BTCM_3 Ref_0 Ref_1

Fig. 12 Estimated current efficiency during implementation of BTCM

Line Plot of Mean( TOTALAES )
4 GROUP
BTCM_0
BTCM_1

3
BTCM_2
BTCM_3
Specific Energy Consump on
Mean of TOTALAES

Ref_0
Ref_1
15.40
Specific Energy Consump on

15.20
2
15.00
(DCkWh/kg)

14.80
1
14.60

14.40
0

15 15 15 15 15 15 15 1 5 15 1 5 15 1 5 15 1 5 15 1 5 15 15 15 15 15 15 15 15 16
14.20
2/ 2/ 3/ 3/ 3/ 4 / 4/ 5 / 5/ 6 / 6/ 7 / 7/ 8/ 8/ 8/ 9/ 9/ 0/ 0/ 1/ 1/ 2/ 2/ 1/
1/ 15 / 1/ 15 / 29/ 12 / 26/ 10 / 24/ 7 / 21/ 5/ 19/ 3/ 17/ 31/ 14/ 28/ 2/1 6/1 9/1 3/1 7/1 1/1 4/
1 2 2 2 14.00
DATE BTCM_0 BTCM_1 BTCM_2 BTCM_3 Ref_0 Ref_1

Fig. 11 Evolution of daily average noise during implementation of Fig. 13 Estimated specific energy consumption during implementa-
BTCM tion of BTCM
Application of Multivariate Statistical Process Control …
Discussion
Challenges Encountered
During the implementation of BTCM, several challenges
were encountered. In most cases, solutions were found to
adapt the system to the operations, or inversely to improve
operations as the use of BTCM highlighted such issues.
Logistics and Timing of STARprobeTM
Measurements
STARprobe measurements were carried out by a dedicated
crew working on day shifts during the week. Therefore, the
measurements were not made at the same point of the work
cycle. Ideally, making the STARprobe measurements in the
hour preceding metal tap in a clean hole reduces the risk of
biased measurements and the impact of the structural heat
balance variation brought by the work cycle. In the case of the
pilot trial, a proportion of the 14 cells could not be measured
on the scheduled days, but this was improved over the course
of the trial, with adjustments of the measurement logistics
(breaking the tap hole in advance). However, the communi-
cation between the dedicated measurement team and the
operating team was sometimes lacking.
Acceptance and Execution of Control Actions
During the early stages of the implementation, BTCM was
mostly used in open loop, with control actions sporadically
carried out. This was also improved over the course of the
trial, with higher compliance during the later stages and a
better communication of the physical issues requiring the
attention of the operations team. Finally, the recommenda-
tions given BTCM to adjust the heat balance in order to
reduce the voltage and/or metal level began to be followed
during stage 3 only.
Alumina Delivery Logistics
As mentioned previously, the alumina delivery logistics
resulted at times in the use of unreacted alumina in the test
section. This was found to be the primary cause of the
inability to attain the excess AlF3 target during stages 1 and 2.
The logistics were corrected at the start of stage 3 to ensure
constant delivery of reacted alumina to the trial section,
including the reference group. This resulted in an immediate
improvement in the ability to control bath chemistry to target.
Aging Technology
With AlF3 delivered by dose increments of 40–50 lbs, it was
not possible to finely control the bath chemistry. Nonethe-
less, the results achieved, particularly those of stage 3, were
satisfactory.
605
Conclusion
Summary
A state-of-the-art measurement technology coupled with a
modern statistical process control approach adapted to the
aluminium smelting process was built into a Bath Temper-
ature and Chemistry Control Module System and piloted in a
smelter over 340 days.
The results showed an immediate reduction in the
day-to-day variability of most of the variables measured
ranging from 17 to 31%. Several of the lagging indicators,
namely cell operating voltage, noise and anode effect fre-
quency, improved as a result. It was also estimated that the
current efficiency improved in the order of 1.3% and the
specific energy consumption reduced by 0.34 DCkWh/kg.
Although the pilot trial was stopped due to force majeure,
the improvements achieved were encouraging and the per-
formance still improving when the pilot trial was stopped
due to the curtailing of the plant. The true potential has yet to
be fully assessed.
Future Work
BTCM is now tested in a larger cell group at a European
smelter with a more recent reduction technology and logis-
tics capabilities. The complete implementation of the plant is
scheduled in 2017.
References
1. A. Mulder et al., New generation control for daily aluminium
smelter improvement generation 3 Process control for potlines.
Light Metals 2014, 835–840
2. X. Wang et al., Alcoa STARprobeTM. Light Metals 2011,
483–488
3. Y. Gao, M. Gustafsson, M.P. Taylor, J.J.J. Chen, The control ellipse
as a decision making support tool to control temperature and
aluminium fluoride in aluminium reduction. 9th Australasian
Aluminium Smelting Technology Conference and Workshop, 2007
4. G.P. Tarcy, Current efficiency theory and practices for continuous
improvement. Paper presented at the Industrial Aluminium
Electrolysis Short Course, Knoxville, 12–16 Sept 2005
5. P.A. Solli, T. Haarberg, T. Eggen, E. Skybakmoen, Å. Sterten,
A laboratory study of current efficiency in cryolitic melts.
Essent. Read. Light Met. Alum. Reduction Technol. 2, 195–203
(2013)
 Study of the Impact of Anode Slots
on the Voltage Fluctuations in Aluminium
Electrolysis Cells, Using Bubble Layer
Simulator

Sándor Poncsák, László I. Kiss, Sébastien Guérard,

and Jean-François Bilodeau

Abstract
There is a constant effort from aluminium producers to reduce energy consumption of the
Hall-Héroult cells in order to decrease cost and environmental fingerprint. Among others,
slotted anodes were introduced in order to promote faster evacuation of the electrically
isolating anode gas bubbles and thus diminish their contribution to the total cell voltage.
A bubble layer simulator was developed to reproduce cell voltage fluctuations, caused by
the dynamics of anode bubbles. Results of simulations show that the slots cut in the right
position and direction can reduce both the amplitude of fluctuations and the average cell
voltage. This impact is even higher for new, almost horizontal flat anode bottoms. It is also
revealed that the slots are acting mainly as a simple bubble sink, but they also contribute to
the acceleration of the bubble layer as well and thus their role in the momentum exchange
between liquid and gas must be taken into account.

Keywords
Aluminium electrolysis Slotted anode Bubble Cell voltage Simulator

Introduction
The reduction of energy consumption and green house gas
emission is a priority for aluminum producers. As alu-
minium smelters are using very high forced current to
increase the production rate, even a small decrease in elec-
trical resistance (and thus cell voltage) can be advantageous.
For this reason, among others, they introduced slotted
anodes, reduced anode-cathode distance (ACD) and in some
cases increased the bath conductivity.
Originally, slots were cut into the anode bottom in order
to prevent the cracking of cold anodes by thermal shock
S. Poncsák (&)
L.I. Kiss
GRIPS, Université du Québec à Chicoutimi, 555 Boulevard de
l’Université, Chicoutimi, QC G7H 2B1, Canada
e-mail: sponcsak@uqac.ca
S. Guérard
J.-F. Bilodeau
Arvida Research and Development Center, Rio Tinto Aluminium,
1955 Boulevard Mellon, Jonquière, QC G7S 4K8, Canada
when they are inserted into the hot molten cryolite based
bath. Later, it was observed that the slots have an additional
advantage. Namely, they promote the faster evacuation of
the electrically isolating anode gas bubbles and thus
diminish their contribution to the total cell voltage [1, 2].
However, this positive effect disappears gradually with time
as the carbon anodes are consumed by anodic reaction. Big
efforts have been made to optimise the design of the slots,
including their number, position and direction. The tests in
industrial cells are expensive, time consuming and can affect
the earlier well-established operations. Direct observation of
the phenomenon is not possible due to the high temperature,
corrosive environment and low transparency of the bath.
Effectiveness of the slots can be evaluated by the analysis of
the cell voltage recordings. However, the variation of some
other independent parameters (such as temperature, bath
height and composition, anode consumption etc.) can also
affect the readings. Mathematical modeling of the influence
of the slots can help to choose the most promising designs
before testing in real cell. Several CFD models were pub-
lished [3–6] which consider the two-phase fluid as a

© The Minerals, Metals & Materials Society 2017 607

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_75
608
homogenous medium with average property values without
describing the details at the scale of individual bubbles.
The mathematical model development was supported in
many cases by different experimental setups, including big,
room temperature water tanks [3, 7–9] or reduced scale
see-through cells with molten cryolite bath [10–13]. In the
first approach, the gas is produced either by injection at high
pressure through a porous plate or by electrolysis. Due to the
difference in physical properties, water models can be used
mainly to validate mathematical models. The kinematic
viscosity of room temperature water is relatively close to that
of molten cryolite, but the difference in densities and espe-
cially in the wetting of the anode can make it difficult to
transfer experimental results directly to industrial cells.
On the other hand, the see-through cells went through a
great progress from the first graphite crucible of Haupin with
small sapphire window [10] to the latest multi-chamber
quartz containers [12]. Observations, using X-ray technique,
were published as well [11]. However, the small size with
different bubble dynamics remains a limitation to draw valid
conclusions for the real cells [12]. However, the experiments
confirmed the effectiveness of appropriate slots in the
reduction of average cell voltage as well as its fluctuations
[12].
A bubble layer simulator has been developed and pre-
sented in an earlier paper [7] that can reproduce the evolu-
tion of the structure of the bubble laden layer around the
anodes and predict the additional cell voltage and stirring
effect caused by the presence of those bubbles. This tool can
effectively support anode design, including the optimisation
of the slot’s geometry. There are a few published attempts to
create similar models [5, 14], but according to the knowl-
edge of the authors, they do not describe the whole bubble
layer and its impact on the cell voltage with the same details
and precision. In this paper, some revelations obtained by
our bubble layer simulator are presented, concerning the
mechanism of the bubble evacuating effect of the slots.
Simulations
Bubble Layer Simulator
The bubble layer simulator deals with one single anode. It is
using a Lagrangian approach where each and every bubble
are followed from the nucleation, through the growth,
detachment, gliding under the anode bottom and rising until
it disappears either by coalescence with other bigger bubbles
or by escaping into the air [7, 15]. The evolution of the
bubble shapes along their travel is better described by this
simulator than those mentioned by other publications, where
only spherical and hemi-spherical shapes were used. The
simulator does not try to solve the Navier-Stokes equation
S. Poncsák et al.
for the typical number of several thousand bubbles dispersed
in the bath around an anode as some other tried without
success, despite the powerful computation tools they used.
Instead it uses a simplified momentum balance between the
bubbles and the surrounding liquid as well as the viscous
momentum transfer between the dominant liquid layers as
well as between the liquid and the solid surfaces in contact.
The development of the simulator was supported by obser-
vations made in a large scale, low temperature liquid-
liquid-gas experimental setup. The graphical output of the
simulator helped greatly the understanding of the behaviour
of the bubble laden layer and the comparison between the
model and the experimental. The excess cell voltage caused
by bubbles is determined by an original mathematical model
as function of the structure of the bubble layer [16]. More
details about the simulator were published earlier [7].
Anode Geometry and Simplifications Used
for the Simulation
A hypothetical anode with bottom size of 1 m  0.5 m
immersed 15 cm into the bath was considered in this study.
These dimensions are similar to the ones used by most of
aluminium producers but does not fit exactly any existing
technology for confidentiality reasons. Both planar and
rounded bottoms with 5 cm radii of curvature at the corner
(Fig. 1) were examined. The first represents a new anode
while the last corresponds to an anode after a short period of
electrolysis because of erosion and higher reaction rate due
to higher current density at the corners. The shape of the
rounded bottom is approximated by two circular arcs of
different radii, connected smoothly at 5° slope.
As anodes are symmetrical, only half anodes were used
for the simulations in order to decrease computation time.
Anodes with and without slots were compared. The slotted
half-anodes contained one slot at the middle, parallel either
to the longer or the shorter sides (longitudinal and
transversal cases respectively). The top of the slots was
horizontal and they were 1 cm wide with 10 cm in height.
Both the size and position of the slots were hypothetical and
did not correspond to any existing technology.
As only one anode is modelled, redistribution of indi-
vidual anode currents due to any local increase of resistivity,
observed in the real cells [17], cannot be considered here.
The impact of MHD on the bath velocity was not taken into
account neither. Generally, most of the bubbles escape at the
side that is closest to their nucleation sites, which is the most
often the longer side. The vertically escaping bubbles in the
inter-anode gaps accelerate the liquid by drag force and this
creates a certain suction effect in the same direction for the
other bubbles situated under the anode bottom. For this
reason, the simulation was carried out with unidirectional
Study of the Impact of Anode Slots on the Voltage … 609

Fig. 1 Profile of rounded anode,

inserted into the electrolytic bath,
as used for simulation

two-phase fluid flow in the direction perpendicular to the
longer side.
The ACD and anode-anode gap were 4 and 20 cm
respectively. The temperature of bath is 960 °C and its
composition corresponds to that used in modern RTA plants.
Results and Discussion
Table 1 presents the average values and the amplitude of
fluctuations of anode covering by bubbles (henceforth called
covering), the excess voltage drop due to the bubble layer

Table 1 Average values of Covering Horizontal planar Rounded corner

anode covering by bubble (italic), Voltage [V]
excess voltage drop due to the Simple sink Sink + acceleration Simple sink Sink + acceleration
presence of bubble layer and bath Without slot 0.592 (0.2–0.88) 0.376 (0.3–0.45)
velocity computed with different 0.453 (0.05–1.19) 0.131 (0.06–0.21)
anode geometries for a period of
30 s 0.573 (0.3–0.6) 0.501 (0.35–0.62) 0.37 (0.3–0.41) 0.34 (0.29–0.38)
0.244 (0.06–0.3) 0.188 (0.09–0.3) 0.074 (0.06–0.11) 0.072 (0.05–0.1)

0.579 (0.28–0.86) 0.571 (0.27–0.75) 0.376 (0.29–0.46) 0.373 (0.29–0.45)

0.385 (0.09–1.08) 0.358 (0.07–0.82) 0.127 (0.08–0.27) 0.125 (0.09–0.23)

Average Horizontal planar Rounded corner

velocity [cm/s] Simple sink Sink + acceleration Simple sink Sink + acceleration
Without slot 3.75 9.95
2.63 3.9 8.29 9.36

3.56 3.81 9.83 9.85

610
(henceforth called bubble voltage drop) and the average bath
velocity, computed by the simulator with different anode
geometries for a period of 30 s. The covering and voltage
data shown in the brackets indicate the minimum and
maximum values. In a simplified approach, the slots can be
treated as simple sinks that swallow the bubbles. In reality,
the gas entering the slots contributes also the acceleration of
the bubble layer.
The average voltage drop varies between 72 and 453 mV,
depending on geometry. The biggest computed gain was
obtained with perfectly horizontal anode. This range is in
good accordance to the literature [2], except that the maxi-
mal bubble voltage drop is smaller in a real cell due to the
possibility of current redistribution toward other anodes. The
results confirm the observations reported in the literature,
obtained both at industry and laboratory scale; namely the
appropriate slots reduce significantly both the average value
and the amplitude of fluctuations of the voltage drop. The
simulator suggests that the slots decrease strongly the
amplitude of fluctuations but only slightly the average value
of the covering. In fact, the slots reduce both the average
path length of evacuation for the bubbles and their maximal
possible size. The strong fluctuations of covering and of
bubble voltage drop are caused by the huge bubbles formed
by coalescence, which can occupy and then sweep off a big
portion of the anode bottom when released. Huge bubbles
deviate more the current lines than a large number of small
coexisting bubbles [16]. Consequently, even if the covering
is reduced only slightly, the prevention of the formation of
huge bubbles itself can decrease significantly the bubble
voltage drop (Fig. 2).
Maximum values of bubble voltage drop—obtained when
a large bubble formed by a series of consecutive coales-
cences can be seen overestimated by the model. However,
Fig. 2 Impact of a longitudinal slot on the covering and the bubble voltage drop for curved anode bottom, computed with the simulator
S. Poncsák et al.
the reader must keep in mind that this is a single anode
model and in a real cell, increased local resistance will
redistribute the current toward the other anodes and thus
prevents the creation of such a high bubble voltage drop
even for a short period.
Impact of the Shape of Anode Bottom
Rounded anode bottom promotes the evacuation of the
bubbles as the accelerating buoyancy force increases with
anode slope. Consequently it increases the velocity of bub-
bles and the bath, while decreases the covering and bubble
voltage drop by decreasing average residence time and
maximal possible size of the bubbles. All those tendencies
can be seen when analysing the results shown in Table 1. As
the rounded shape itself accelerates evacuation and decrea-
ses the maximal bubble size, the presence of slots (which
have similar effects) gives a smaller additional gain for
rounded anode bottom, compared to the horizontal one
(Table 1 and Fig. 3).
It must be mentioned that anode consumption decreases
gradually the height and thus the impact of the slots. This
phenomenon is not investigated in this paper.
Impact of the Direction of the Slot
The direction of the slot has much bigger impact on the
bubble voltage drop than on the covering or the bath
velocity. Especially for the rounded anode bottom, its
influence is very limited on the covering. This observation
suggests that the role of the slot to limit the biggest possible
Study of the Impact of Anode Slots on the Voltage … 611

Fig. 3 Impact of a longitudinal slot on the bubble voltage drop for horizontal and curved bottom anodes, computed with the simulator

Fig. 4 Bottom view of the computed distribution of bubbles under a horizontal anode with longitudinal (right) and transversal slots (left). Arrows
show the dominant direction of fluid flow

size of the bubbles is the key design factor when the optimal
slot geometry must be chosen (Table 1 and Figs. 4 and 5). In
the simulated case, the slot parallel to the longer side seems
to be more efficient as it greater reduces the maximal pos-
sible size of the bubbles.
Contribution of the Slot to the Momentum
Balance Between the Liquid and the Gas
Slots can be seen as simple sinks, which decrease the
average evacuation path length and the biggest possible size
612 S. Poncsák et al.

Fig. 5 Impact of the orientation of the slot on the bubble voltage drop for horizontal and curved anodes as computed by the simulator

for the bubbles. However as water modeling showed, bub-
bles rising inside the slot and then exiting under the effect of
buoyancy force exert a “suction” effect on the other bubbles
still residing under the anode bottom [8]. In fact, they con-
tribute also to the acceleration of the liquid under the anode
through the coupling by the drag force. This phenomenon is
considered by a separate subroutine in the simulator. By
omitting this subroutine, the relative importance of the
simple sink effect versus contribution to the acceleration of
the bath can be investigated. Results show that the sink effect
is dominant but the acceleration term cannot be neglected in
certain cases (Table 1 and Fig. 6). In fact, if the contribution
of the bubbles entering into the slots, to the acceleration of
the two-phase layer under the anode bottom is neglected, the
average velocity of the bath will be lower, which in turn
slows down the evacuation of the bubbles as well. However,
this affects the covering more than the bubble voltage drop.
Role of the Size of the Anode
As see-through cells are often used to investigate the
dynamics of bubble layer under slotted and non-slotted
anodes, a 5  5 cm anode, inserted 15 cm deep into the
cryolite based bath was analysed with the simulator as well.
Such systems do not work long enough to create rounded
corners; therefore only planar, horizontal anode bottom was
examined. Results obtained with this geometry were com-
pared to the horizontal anode of 1  0.5 m with the same
immersion and without slot (Fig. 7). Table 2 resumes the
two cases.
Strongly reduced anode size results in some decrease of
covering but in a very strong diminution of bubble voltage
drop. For the latest, both the average value and the amplitude
of fluctuations fall drastically. This is related to the reduction
of the biggest possible bubble that can exist under the anode.

Fig. 6 Impact of slots on the computed bubble voltage drop for horizontal and curved anodes if the slot considered as a simple sink or a sink with
a contribution to the global momentum exchange between the bath and the bubbles
Study of the Impact of Anode Slots on the Voltage …
Fig. 7 Impact of anode size on covering and bubble voltage drop in case of horizontal bottom, computed with the simulator
Table 2 Impact of the anode
size on covering, bath velocity
and bubble voltage drop, Average covering
computed with the simulator Amplitude of fluctuations of covering
Average velocity of the bath (cm/s)
Average bubble voltage drop (V)
Amplitude of fluctuations of bubble voltage drop (V)
The same tendency must be valid for curved or inclined
anodes but with smaller difference.
Conclusions
The simulator presented earlier was used to investigate the
effect of slots with different geometries on square and
rounded bottom anodes, representing new and used anodes
respectively. Analysis of the results permitted to draw the
following conclusions:
• Anode slots definitely decrease the voltage drop created
by the presence of bubbles. The gain varies between 71
and 453 mV with the simulated geometries for a single
anode system. The biggest computed gain was obtained
with perfectly horizontal anode but this gain should be
smaller in a real cell due to the possibility of current
redistribution toward other anodes.
• The slots reduce the bubble voltage drop by three
mechanisms:
– Reducing average path length for bubble evacuation
– Limiting the maximal possible size of individual
bubbles
613
1  0.5 m2 0.05  0.05 m2
0.592 0.37
0.68 0.65
3.75 5.48
0.453 0.048
1.14 0.078
– Similarly to the anode-anode gaps, they accelerate the
bath by the drag force of the rising bubbles
The second mechanism seems to be the most important as the
amplitude of fluctuation of the covering decreases generally
stronger than the average value in the presence of a slot. By
preventing the formation of very big bubbles, which deviate
more the current, the bubble voltage drop will decrease sig-
nificantly even when the average covering does not.
• The role of the slot to limit the biggest possible size of
the bubbles is the key design factor when the optimal slot
geometry (orientation, number) must be chosen. In the
examined cases, the slot parallel to the longer side was
more efficient.
• Both the slot and the slope of the anode bottom reduce
the average residence time for the bubbles and the big-
gest possible size. For this reason, a bigger gain of
voltage can be obtained by the slots for a perfectly hor-
izontal anode bottom than for a curved or inclined one.
• The use of small, laboratory scale anodes results in a
drastic reduction of bubble voltage drop, due to the
limitation of the biggest possible bubble that can strongly
increase ohmic resistance. For this reason, the effect of
anode size is more important on the voltage than on the
gas covering.
614
Acknowledgements The authors would like to thank the valuable
financial support of Rio Tinto Aluminium and its predecessors.
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13. Z. Zhao, Z. Wang, B. Gao, Y. Feng, Z. Shi, X. Hu, Anodic bubble
behaviour and voltage drop in a laboratory transparent aluminum
electrolytic cell. Metall. Mater. Trans. B 47(3), 1962–1975 (2016)
14. K. Zhang, Y. Feng, P Schwarz, M. Cooksey, Z. Wang, Numerical
investigation of bubble dynamics in aluminium electrolytic cells.
Light Met. 881–886 (2012)
15. N. Richards, H. Gudbrandsen, S. Rolseth, J. Thonstad, Character-
ization of the fluctuation in anode current density and bubble
events in industrial reduction cells. Light Met. 315–322 (2003)
16. A. Perron, L.I. Kiss, S. Poncsák, Mathematical model to evaluate
the ohmic resistance caused by the presence of a large number of
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ogy Conference, Launceston, Australia, 9–14 October 2011, 12 pp
 Detecting, Identifying and Managing
Systematic Potline Issues with Generation 3
Process Control

Nursiani Indah Tjahyono, Yashuang Gao, David S. Wong,

Ron Etzion, and Albert Mulder

Abstract
Due to the nature of the process, aluminium smelting can have many issues/abnormalities/
problems. One type is systematic issues, which are those that occur on multiple pots
simultaneously and can result in prolonged issues across a potline if not identified early.
However, detecting and identifying these issues can be a difficult task for smelter engineers
and management, particularly when information sources are not recorded, integrated and
available in a centralised location. In addition, they are often not displayed in a way that is
convenient for tracking and identifying systematic problems. For example, an increasing
trend in cryolite ratio (CR) on all pots can be difficult to spot if graphical CR trends are only
displayed for individual pots, or worse, in a tabulated format. This paper presents two case
studies in detecting systematic issues in smelting process using the Generation 3 process
control system that highlights the importance of a centralised data location and appropriate
data presentation. The cause of the systematic issues and the actions taken to manage the
impact will also be discussed.

Keywords
Systematic issues Process control Data presentation Centralised data

Introduction pots simultaneously (e.g. on a group of pots, a section, a

Aluminium smelting is a dynamic process, with continuous
addition of various raw materials (e.g. alumina, AlF3, carbon
anode, anode cover) and periodic removal of metal and spent
carbon anodes that utilises a wide variety of parameters to
control the process. As such, changes in pot conditions are
always to be expected. These changes can either be planned
or come suddenly, and may become an issue that needs to be
fixed. Depending on the source of the change or issue, its
effect can be experienced by individual pots or on multiple
N.I. Tjahyono (&)
Y. Gao
D.S. Wong
R. Etzion
Light Metals Research Centre (LMRC), The University
of Auckland, Private Bag 92019, Auckland, New Zealand
e-mail: n.tjahyono@auckland.ac.nz
A. Mulder
Albert Mulder IT Consultant, Woldjerweg 23,
9792TC Ten Post, The Netherlands
potline or the entire smelter). The latter is referred to
henceforth as a systematic issue or change. Examples of
systematic changes and their effects on pot’s conditions are:
• Different properties of raw material, such as alumina, due
to different shipment batch and/or supplier. Certainly, a
change in alumina shipment batch occurs frequently in a
smelter and provided that the new batches of alumina
have similar properties to their predecessor, it should not
have any detrimental effect on the pots. However, it is
possible for their properties to be vastly different, espe-
cially with different alumina suppliers. A different bulk
density in alumina, for example, requires an adjustment
in the dump weight setting in volumetric-based point
feeders to ensure that the same amount of alumina is
being delivered to the pots, otherwise sludging (when
changing to a higher density) or anode effect (lower
density) issues may occur in the pot.

© The Minerals, Metals & Materials Society 2017 615

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_76
616
• Reduction in efficiency/capacity of one gas treatment
centre (GTC) or dry scrubber: this means that the sections
or part of a potline that is being supplied by this particular
GTC would have lower fluoride (%F) levels in the
incoming secondary alumina. In turns, the AlF3 addition
for chemistry control needs to be increased accordingly to
maintain similar liquidus temperature/CR in these pots.
• Change in potline amperage: for example lowering of
amperage to allow for different rectifiers to be maintained
in sequence or due to increasing production cost and/or
reduction in metal price. This means that strategies need
to be developed in consideration of pots’ mass and heat
balance to prevent any detrimental effects on pots con-
dition due to amperage adjustment. Example case studies
have been presented by several authors [1, 2].
The issues or changes mentioned above only represent a
small handful of unavoidable scenarios in the running of a
smelter. In many cases, detection, identification and treat-
ment of systematic issues may not occur until a noticeable
reduction in key performance indicators (KPI’s) such as
current efficiency (CE) and energy consumption, have
occurred. Furthermore, performing such an investigation is
often not an easy task due to challenges like: needing to
search through and process large amount of available data,
relevant information being stored on different databases from
different data sources (e.g. potroom, laboratory, carbon
plant, etc.), time delays between causes and effects, strong
correlation among some variables (e.g. bath temperature,
operating voltage, CR, AlF3 addition, soda (Na2O%) content
in alumina, etc.) [3] and ineffective data presentation.
For example, a systematic increasing trend in CR on
multiple pots due to increasing soda (Na2O%) content in the
incoming alumina will be difficult to detect if a graphical CR
plot is only displayed for individual pots or in a tabulated
format. Further difficulties or delays in identifying this sys-
tematic cause arise if data on alumina properties cannot be
easily obtained. To enable appropriate diagnostic and treat-
ment in a timely manner when an issue occurs requires
meaningful information through better data organisation and
presentation.
Collecting and combining data to generate information
when required is a difficult task as most smelters possess
heterogeneous data architectures. The following challenges
are often faced when binding data from different sources:
• Widespread distribution—data is spread all over the
smelter with each department having its own database
format and structure.
N.I. Tjahyono et al.
• Legacy systems—multiple and possibly incompatible
data systems, e.g. new and outdated data systems, present
at different parts of the smelter.
• Task specific—most of the data requirement and storage
is structured around meeting a specific need and not
always in a suitable format for long term storage, for
example, the use of blackboards to display daily bath and
metal level measurements by the pot.
• Inconsistency—not all data is sampled in the same fre-
quency or format (e.g. not all are stored with a
timestamp).
• Different accessibility—for example, data recorded on
paper will be harder to access compared to that inputted
into electronic files.
Generation 3 process control, referred to as ‘Gen3’
henceforth, is a new generation process control system for
aluminium smelting. As described in an earlier publication
[4], it integrates all major processes across a smelter, com-
bining information into a single control centre. Gen3 adopts
the Extract, Transform and Load (ETL) process within its
data acquisition module to obtain the required data. The ETL
process is a three-phase technique to extract data from dif-
ferent data sources, transform them into the correct format
(including the addition of statistical values, etc.) before
storing the data in a specific database structure and load the
data, when required, to perform a wide range of tasks, such
as early detection and diagnosis of abnormalities, provide
consistent guidance on root cause analysis and corrective
actions, and present data systematically that allows for easy
detection of issues. With Gen3 integrating all information in
the smelter, data from different sources is also accessible
from a single control centre.
In this paper, two case studies in detecting systematic
issues in smelters with Gen3 are presented. The cause of the
systematic issue and the action taken to manage its impact
and/or return pots to its original condition will also be
described and discussed.
Case Studies of Detecting, Identifying
and Managing Systematic Issues
Two case studies on detecting, identifying and managing
systematic issues by Gen3 will be presented in this section.
One case study is related to poorly managed raw material
changeover while the other is related to repeated detection of
a certain abnormality, leading to the discovery of systematic
hardware issue within the smelter.
Detecting, Identifying and Managing Systematic Potline …
Case Study 1—Utilising Display of Systematic
Data Trends to Detect Raw Material Quality
Changes
An important part of the Gen3 process control is data pro-
cessing and display to assist in decision making. One format
of a data display is referred to as ‘4plots’. It provides a visual
way to statistically analyse trends for a single parameter,
such as bath temperature, CR and voltage, for a group of
pots (e.g. a group of test pots, a section, a potline, the entire
smelter) and observe their performance as a whole. It also
allows for clear identification of any major systematic issues
affecting multiple pots. An example of 4plots from a smelter
is shown in Fig. 1. 4plots consist of four charts:
• X and S charts (Fig. 1a): mean and standard deviation
graphs over time, which enable quick identification of
trends on an entire group of pots and whether the
parameter is in control. For both graphs, the line and
shaded area represent the mean and 3r (three standard
deviations) away from mean, respectively, for the spec-
ified monitoring period.
Fig. 1 An example of a 4plots of CR from a smelter, consisting of X and S charts (a), boxplot by date (b), histogram (c) and boxplot by pot
number (d). The arrows signify the start of a strong reduction in CR
617
• Boxplot by date (Fig. 1b): box and whisker graph that
aggregates data from all available pots for each day of the
monitoring period. They summarise information about
shape, distribution and centre of the data. Each box
portion of the graph (both shades of colour) represents
where 50% of the data distribution lies and the horizontal
line drawn through the middle of the box represents the
median of the data. This chart provides easy identifica-
tion of trends for the group by date, such as when the
distribution of the pots start to change and when pots are
more in control.
• Histogram (Fig. 1c): used to visualise overall shape of
distribution and variation of data as a whole, from all
pots for the specific duration within the monitoring per-
iod. The analysis divides sample values into intervals
called bins, whereas bars represent the number of
observations falling within each bin (i.e. its frequency).
Outliers or extreme values can also be observed here.
• Boxplot by pot (Fig. 1d): box and whisker graph that
aggregates data from the entire monitoring period for
each pot. They share similar features to boxplot by date.
This chart provide a clear and visual method to detect
618
which specific pots are in control and which abnormal
pots need to be improved.
Background and Role of Gen3
At this smelter, a monitoring program was established to
review pot performance once a week. The purpose is to
detect any undesired systematic trends in pot parameters of a
group of pots as a whole, not specifically looking into each
individual pot. As such, 4plots is the main avenue to perform
this task. Prior to using the Gen3 process control system, the
smelter was only able to observe either individual pot data in
basic graphical or tabulated format, or average values for the
pot section in a simple tabulated format. Hence, the use of
Gen3 has enhanced the smelter’s ability to utilise its data
more effectively.
In this example, a strong reduction in mean CR (from
about 2.36) was observed from March 8th as shown by the X
chart (refer to arrow in Fig. 1a). Based on the relatively
stable standard deviation for the same period (from S chart),
it could be determined that this reduction in mean CR was
representative of the entire group and was a systematic issue,
rather than due to a few pots being extremely out of control.
This was also supported by the boxplot by pot chart
(Fig. 1b) showing similar range of CR distribution over the
reducing CR period. A similar trend was also observed in
bath temperature. When data display for individual pots
were investigated, similar declining CR and bath tempera-
ture trends exist, although they did not occur at exactly the
same time.
Overall correlation to AlF3 addition was investigated and
in this period, AlF3 addition was significantly reduced.
However, it did not appear to return the CR to its target level
but rather CR continued in a decreasing trend. Hence, other
factors were at play for this systematic issue. Some possible
causes for this scenario were reduction in soda content in
alumina, higher fluoride content in secondary alumina and
incorrect setting for chemistry control.
Findings
Upon further investigation, the root cause of this systematic
issue was found to be due to raw material changes, specif-
ically a change in AlF3 bulk density. Despite the smelter
expecting a change in raw material, its approach and strategy
to manage this changeover was to look at the lagging
response, like the sharp reduction in bath temperature and
CR in this example, before any action was considered. This
was too late, resulting in poor pot condition on all pots
before being corrected.
N.I. Tjahyono et al.
Due to infrequent density measurement, the timing of
when the new AlF3 batch would reach pots had been com-
pletely missed. Furthermore, the incoming AlF3 had almost
double the density of the previous batch. As the feeder shot
weight setting for the AlF3 addition was not adjusted when
the new AlF3 reached the pots, a significantly higher amount
of AlF3 was actually added to pots compared to that being
recorded by pot control systems. Hence, although ‘less’ AlF3
addition was prescribed and recorded due to the lowering
CR, in actuality, similar AlF3 was being added into all pots,
further reducing the CR and bath temperature. Once the
weight setting for AlF3 addition was adjusted on March 14th
(six days after the CR trend started), the mean CR slowly
returned to its target value. Examples of the daily bath
temperature, CR, AlF3 addition, AlF3 density and AlF3
weight setting plots from a few pots are shown in Fig. 2.
While it may be difficult for a smelter to avoid any
changes in the quality of raw material, it is possible to
manage and reduce any detrimental impact on pot condition.
For this smelter, its strategy to manage any change in raw
material needed to shift towards an anticipatory response,
rather than wait until a major process change occurred. For
this particular example, this could be done by:
• More proactive routine measurements of AlF3 density,
especially when the new batch of AlF3 is expected at the
smelter.
• Input measurements data into Gen3 so that results were
observable by all users (refer to examples in Fig. 2).
• Monitor 4plots during the changeover period to enable
early identification of potential issue.
• Improve communication between laboratory, potroom
and supply departments to enable the correct change in
AlF3 weight setting to be made at the appropriate time.
Case Study 2—Utilising Automatic Abnormality
Identification to Detect Systematic Feeder
Hardware Issue
Another major feature of Gen3 to help in the day-to-day
running of aluminium process is its ‘automatic abnormality
detection ! guided root cause identification ! corrective
action’ generation process. This process is elaborated in an
earlier publication [4]. Gen3 also provides an easy means to
track and record data, including information on every
detected abnormality and its identified root cause, and
physical changes or issues that occur in the potroom, which
enable further data processing to be done to uncover deeper,
not too apparent systematic issues, as shown in the following
case study. This capability is very important as usually,
Detecting, Identifying and Managing Systematic Potline …
Fig. 2 Examples of daily bath temperature, CR, AlF3 addition, AlF3 density and AlF3 weight setting from three different pots for the same
monitoring period as the 4plots in Fig. 1
physical changes or issues are not recorded, or if recorded, it
is not in an easily accessible format from a centralised
database.
Background
At one smelter, a feed problem, specifically, ‘alumina
feeding too high’ or ‘high feed’ was frequently detected. An
example is shown in Fig. 3. This abnormality is detected
Vast
amount of
overfeeds
Fig. 3 Automatic detection of ‘alumina feeding too high’ by Gen3 in
one smelter due to excessive feed and/or high number of AE
619
when Gen3 identifies that a pot is getting excessive feed
using pot controller data (based on alumina cusum moni-
toring) and/or high number of anode effects (AE). In this
example, the excessive feed is also evident by a vast amount
of overfeeds before and after the abnormality is detected.
This abnormality can be caused by many factors, such as
breakers stuck in feeder hole, empty alumina hoppers and
excessive bath build-up on breakers (‘elephant feet’).
Role of Gen3
After an abnormality is detected, Gen3 guides users by
providing a checklist to go through to find the root cause of
the detected abnormality. An example of this checklist is
illustrated in Fig. 4. In this particular smelter, the root cause
of ‘high feed’ abnormalities was almost always plugged
feeder holes. This was evident from ‘plugged feeder holes’
being identified as the highest frequency root cause, as
shown in Pareto chart in Fig. 5. Hence, a systematic issue
with plugged feeder holes in this smelter was clearly
deduced. This prompted an investigation to find its cause.
Findings
Correlation was found between frequency of plugged feeder
holes and AE frequency as shown by the bar graphs in Fig. 6
(left part, the “before trial” side), whereby more frequent AE
620
Fig. 4 Example of guided root cause analysis for ‘alumina feeding too
high’ abnormality
Plugged feeder hole is the most
dominant issue at this smelter
Fig. 5 Pareto chart of identified root cause of issues at the smelter,
with plugged feeder hole having the highest frequency
occurred during a period of higher plugged feeder hole
frequency, as this prevents the alumina from reaching and
dissolving in the bath. A cycling trend with a frequency of
about two weeks was also observed in both parameters.
Further correlation was also found with the anode setting
rota displayed below the bar graphs in Fig. 6, where anode
locations in black signify those adjacent to feeder holes. This
shows that feeder holes were most often blocked after anode
change around the feeder area (referred to henceforth as
feeder hole anode change).
N.I. Tjahyono et al.
Due to the proximity of the feeder and anode, the frozen
bath layer formed on the newly set anode often extended into
the feeder hole area, which could not be unblocked during
normal break and feed cycles of the feeder. Often it would take
at least a day before this frozen bath would melt and unblock
the feeder hole as the anode picked up current. However, as
multiple feeder hole anode changes were concentrated toge-
ther in this anode rota, it means that on the following days,
other feeder holes would be blocked, increasing the occur-
rence of AEs and plugged feeder holes towards the middle to
end of each series of feeder hole anode change. Furthermore,
there was a reduction in amperage and operating voltage at
similar time during this monitoring period. Based on these
observations, it could be concluded that the systematic plug-
ged feeder hole issue at this smelter was due to (1) poor design
and placement of point feeders in relation to anodes and
(2) insufficient superheat before anode change to keep feeder
holes open and dissolve alumina in the bath.
To address these issues, a trial was started in late
February of:
• Using slightly shorter length anodes to create more space
in centre channel, thus minimising any frozen bath
material on the newly set anode reaching the feeder hole
area and allowing more liquid bath to flow in the centre
channel. This would also potentially increase the bath
circulation rate in the dissolution zone, which further
minimise any risk of AEs or ‘high feed’ issues [5]. While
the reduction in anode size affected the anode current
density, it was still within an acceptable limit (less than
the critical anode current density).
• Increasing the duration of the anode set modifier (extra
voltage after anode change) for feeder hole anode chan-
ges so they reach operating temperature and normal
anode current draw faster, which would assist in melting
any remaining solid bath or alumina material in the
cavity after pacman; this also promotes sludge back-
feeding, hence, promoting cleaner cathodes.
The comparison for plugged feeder hole and AE fre-
quencies for before and after the trial is shown in Fig. 6 and
is summarised in Table 1. Although some cycling trend in
both AE and plugged feeder hole due to feeder hole anode
change was still observed after the trial, their magnitude was
significantly lower than before the trial period, reducing by
more than 40% for both parameters. This shows that the trial
was successful in reducing the systematic plugged feeder
hole issue at this smelter.
Detecting, Identifying and Managing Systematic Potline …
Fig. 6 Bar graphs of plugged feeder hole (top) and anode effect frequencies (middle), which correlate well with anode setting rota (bottom). The
anode locations marked in black signifies those adjacent to a feeder hole
Table 1 Summary of results for Plugged feeder hole frequency (/pot.day)
the shorter anode and longer
anode set modifier trials Before 0.49
After 0.28
Change 42.8% reduction
Conclusions
This paper demonstrates the importance of a centralised data
location and appropriate data analysis using statistical
method and appropriate data presentation through Gen3 in
detecting, identifying and managing systematic issues in
smelters. In particular:
• Displaying smelter data in 4plots provides a visual
approach to statistically analyse the mean, standard
deviation and distribution trends in a group of pots on a
single page, allowing quick and easy identification of any
systematic issues or trends in a smelter. This enhances
the smelter’s ability to utilise its data more effectively.
• The recording of all abnormalities and identified root
causes found (including physical issues at the pot) in a
centralised database enable further data processing to be
done, which can be used to discover deeper systematic
621
Anode effect frequency (/pot.day)
1.23
0.73
40.6% reduction
issues, such as those related to pot design and hardware,
as illustrated in this paper.
References
1. Y. Gao, N.I. Tjahyono, D.S. Wong, M.P. Taylor, A. Mulder,
Managing amperage reduction in a Chinese smelter. Paper presented
at the 11th Australasian Aluminium Smelting Technology Confer-
ence, Dubai, UAE, 2014
2. D. Whitfield, G. Oldenhof, Reduction of amperage at New Zealand
aluminium smelters. Paper presented at the Light Metals, TMS
135th Annual Meeting and Exhibition, San Antonio, TX, 2006,
pp. 237–241
3. J. Tessier, C. Duchesne, G.P. Tarcy, C. Gauthier, G. Dufour,
Analysis of a potroom performance drift, from a multivariate point
of view. Paper presented at the Light Metals, TMS 137th Annual
Meeting and Exhibition, New Orleans, LA, USA, 2008,
pp. 319–324
622
4. Mulder, Y. Gao, D. Zhou, D.S. Wong, L. Ming, P. Lavoie, M.
P. Taylor, X. Yang, New generation control for daily aluminium
smelter improvement: Generation 3 process control for potlines.
Paper presented at the Light Metals, TMS 143rd Annual Meeting &
Exhibition, San Diego, California, USA, 2014, pp. 835–840
N.I. Tjahyono et al.
5. P. Lavoie, M.P. Taylor, J.B. Metson, A review of alumina feeding
and dissolution factors in aluminum reduction cells. Metall. Mater.
Trans. B 47(4), 2690–2696 (2016)
 Predicting Instability and Current Efficiency
of Industrial Cells

Patrice Côté, Olivier Martin, Bertrand Allano,

and Véronique Dassylva-Raymond

Abstract
New statistical models were developed to predict the behavior of industrial potlines. A first
model, based on a multiple linear regression analysis, predicts the instability (cell noise) of
P155 potlines and is used as a tool to investigate drifts. An example of the usefulness of
such a model is presented. A second model that predicts the current efficiency was built
using a similar approach. It is based on 10 years of data from 30 potlines. The non-linearity
of the relationship between current efficiency (CE) and anode-cathode-distance (ACD) was
investigated and confirmed during the course of this study. These current efficiency and
instability models provide new ways to anticipate potline performance and to conduct gap
analysis.

Keywords
Aluminum Current efficiency Instability Prediction Multivariate analysis

Introduction
The lower aluminum prices of the last several years have
pushed the industry towards new strategies to reduce pro-
duction cost quickly. One such strategy was to aggressively
reduce the anode-cathode distance (ACD) in order to either
increase amperage or lower specific energy consumption
P. Côté
Arvida Research and Development Centre, Rio Tinto, 1955,
Mellon Boulevard, Jonquière, QC G7S 4K8, Canada
O. Martin (&)
B. Allano
LRF, Rio Tinto, rue Henri Sainte Claire Deville, CS 40114, 73302
Saint-Jean-de-Maurienne Cedex, France
e-mail: olivier.martin@riotinto.com
V. Dassylva-Raymond
Reso-Lean Conseil, 1322, rue Anne-Gagnier,
La Baie, QC G7B 4T3, Canada
without the need for a new cell design. This new paradigm,
however, came at the price of putting the process under
stress, leading to uncertain results. Figure 1, published by
Segatz et al. [1], represents the economic results (profit) as a
function of the operational set point (ACD and current) of a
given cell. Note that decreasing the ACD beyond a certain
threshold actually leads to lower profitability, as the loss in
CE becomes dominant.
In a context where the profitability is very sensitive to a
smelter operational strategy, plant personnel need new tools
to quickly identify drifts and perform gap analyses. Two
examples of such tools were developed by Rio Tinto to
predict the trends of instability and current efficiency of
potlines. They are now used by plants to identify drifts and
react appropriately (Fig. 2).
When a drift is observed, there are two possibilities:
(a) the model does predict the drift (drift likely driven by
predictors already in the model), or (b) the drift is not pre-
dicted by the model and an investigation should take place.
In the latter situation, the problem can be isolated from the
variations caused by predictors already in the model. Once
completed, the findings from the investigation should be
integrated into the model.

© The Minerals, Metals & Materials Society 2017 623

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_77
624 P. Côté et al.

instability. In this study, cell noise represents the amplitude

of the low frequency resistance signal over one minute and is
known as “Average Intra-Minute Resistance Range”.

Building the Instability Model Through Statistical

Analysis

The purpose of this work was to build a simple model that

could help technical staff in determining the causes of
variations of cell noise for a group of P155 cells.
A multiple regression analysis was performed. Over 178
weekly results (from January 2010 to May 2013) from 384
cells including two different cell designs (referred to as “old”
and “new” in Fig. 4) were used, and predictors were
screened based on their significance. Only five predictors
were significant enough to be included in the final model and
they accounted for 91% of the variance (R-squared). Table 1
lists the predictors and their coefficients.
In this particular case, amperage and target resistance were
identified as collinear (which should not come as a surprise)
but were both kept in the model, as removing either of them
would significantly reduce the accuracy of the regression.
Fig. 1 Profit as a function of operational strategy (ACD and Current).
This can be explained by the fact that although these vari-
Published by Segatz et al. [1]
ables are often adjusted together, and are thus correlated,
there are also cases where they vary independently. The
model therefore gains in predictive power by being able to
represent such situations. It should be noted that the coeffi-
cients of collinear variables may be less reliable, although
this does not affect the validity of the overall model.

Application of the Model

One indicator followed by the plant technical team was the

gap between the predicted and actual noise. Figure 3 shows
Fig. 2 Continuous improvement loop for models in an industrial
context an important gap that started suddenly in April 2014.
Fortunately, an investigation quickly helped identify the
culprit due to the easy identification of the week when the
change occurred. The gap was eventually explained by an
Multivariate Regression Model for P155 Cell increased anode resistance linked to an anode cracking
Instability problem. Furthermore, it was also discovered that an

The magnetic fields generated by the physical arrangement

of electrical conductors of a group of cells can create Table 1 Predictors for the instability model and their coefficients,
accounting for 91% of the variance
magneto-hydro-dynamic (MHD) perturbations in the metal
pad, referred to as “cell instability”. Predictors Coefficients from multiple regressions
Cell instability is complex and cannot be described sim- Intensity (kA) −0.41
ply by a number. It does however affect cell control through CaF2 in bath (%) 1.69
the introduction of noise in the resistance signal, impairing AlF3 excess (%) 1.59
the ability for the system to regulate alumina concentration, Target resistance (µOhms) −8.73
ACD and bath temperature. The amplitude and frequency of
Bath height (cm) 0.680
this noise are typically used as indicators of overall MHD
Predicting Instability and Current Efficiency of Industrial Cells 625

Current efficiency is difficult to evaluate with precision in

Predicted and Actual Intra-Minute Resistance Noise
a smelter. A month-to-month standard deviation between 0.5
18
and 1% is typical for a whole potline, while most plants
16 would like to react to much smaller performance drifts.
Noise (uOhms x 100)

In this context, a model could be useful because it would

14
allow continuous monitoring of the predicted CE as well as
12 the different predictors involved. A model could also provide
Actual
insights into identifying gaps between different potlines or
10 Predicted
smelters.
In order to account for the less than ideal precision of CE
1 1 1 12 2 2 13 13 13 14 4
-1 -1 -1 r- -1 -1 s- il- v- r- t-1
nv ai pt év in ct ar av oû results, and because a very large set of data was accessible,
-j a -m -s
e
-f - ju 4-o m 5-j u -no - a
05 11 21 01 13 2 - 1 25 07 18
-
06 only trimestral CE results were considered in this study. Ten
Week
years of data for 30 potlines were used. While common data
was available for 29 predictors, it is worth pointing out that
Fig. 3 Gap between predicted and actual noise
other predictors could have been important but were not
systematically available.
Contribution of Variables to Intra-Minute Resistance Noise
Intra-Minute Resistance Noise (uOhms x 100)

15
Amp erage & Target Resistance (O ld Design)
Amp erage & Target Resistance (New Design)
%A lF3 excess & %CaF2 Statistical Analysis
Bath Height
10 Anod e Resistance
Unslotted Anod es
UNEXPLAINED Several current efficiency models are available in the liter-
5
ature but few of them have been known to predict industrial
cell results with accuracy. They were also meant to be used
to predict individual cell results. Knowing this, a new sta-
0
tistical model had to be developed.
Several tools were used throughout the data screening
10 10 -1
0 11 -1
1
-1
2
-1
2
-1
3
t-1
3
-1
4
v- n- éc n- ov ai ov ai vr
an ui -d ui -n -n oc -a phase. Principal component (PC) analysis has proven to be
-j 3-j 5 8-j 0 3-m 4 8-m 8- 1
06 2 1 0 3 2 1 0 2 2
Week useful to make sense of the dataset. Interaction diagrams
were also used to assess potential dependencies between
Fig. 4 Contribution of predictors with new variables (Color online variables. To account for the collinearity of some of the
figure) predictors, a partial least square (PLS) regression was used
as a final step.
increased proportion of anodes were not slotted. These Figure 5 shows a list of the seven predictors that were
changes had not been taken into account in the cell target kept in the model with their standardized coefficients.
resistance, which led to an overly squeezed ACD. Standardized coefficients range from −1 to 1, 0 being no
The impact of cracks on the anode resistance was mea- correlation while −1 and 1 are respectively perfect negative
sured, and calculations were made to estimate the effect of and positive correlations. The predictors are listed in order of
slots. Figure 4 shows the individual contribution of each importance. Most predictors will be discussed in the next
predictor which is stacked. With these added variables sections.
(anode resistance in orange, non-slotted anodes in pink), the
unexplained variations (in black) are now within reasonable
historical values. ACD: Non-linear CE Loss

As mentioned previously, several smelters are now operating

Predicting Current Efficiency of Large Cell at a lower ACD. As was the case for instability, current
Groups efficiency is also sensitive to ACD, especially when it gets
very low. Leroy et al. [2] and Alcorn et al. [3] (Fig. 6) both
Current efficiency (CE) is the fraction of current that directly reported a non-linear relationship between ACD and CE for
contributes to aluminum production. The theoretical maxi- industrial cells. Dorin and Frazer [4] later observed a similar
mum is given by the Faraday law. It corresponds to a pro- behavior in laboratory cells. Some studies, however, did not
duction of 8.053 kg of aluminium per kA over a period of report that non-linearity. One possible explanation being that
24 h. Most modern smelters report CE results between 90 ACD variations were not important enough, or that the setup
and 96%. in small laboratory cells could not reproduce all the
626 P. Côté et al.

Predictors Standardized Coefficients

ACD (exponential CE loss / mm)

C*Al (solubility of metals in bath)

Iron content (Fe ppm in Al)

Cell Noise * Intensity (mV)

Metal height (cm)

Average age (days)

Duration of no feed tracks (min.) Fig. 7 Non-linear behavior of %CE as a function of ACD (Rio Tinto
calculation)
Fig. 5 Predictors from PLS regression analysis and their standardized
coefficients

Fig. 6 Non-linear effect of ACD on current efficiency, as reported by

Alcorn et al. [3]

Fig. 8 Output from two regression analyses showing a better

interactions happening in an industrial context, at a com-
pletely different scale.
In order to evaluate CE loss as a function of ACD, an
analysis was conducted using data from several AP18 and
AP30 series for a period of three years (twelve semesters CE
results per potline). Specific results from experimental cells,
operated at very low ACD, were also integrated. Figure 7
shows the non-linear effect established in our own analysis,
which confirms studies from the literature mentioned earlier.
It was also found that better relationships between pro-
cess parameters could often be obtained by first controlling
the effect of the ACD. As an example, Fig. 8 shows the
output of two linear regression analyses for CE as a function
of bath temperature, where R-squared passed from 29 to
44% once this transformation was completed. Due to the
exponential nature of the correlation, this worked better than
simply adding the ACD as a predictor in a linear regression
analysis.
R-squared once the impact of the ACD was added
Solubility of Metals in Bath
Solubility of metals in bath (C*Al) is the saturation concen-
tration for dissolved metals (Na, Al and Li). It is a function
of bath temperature, bath chemistry and their interactions.
Everything else being equal, the higher the AlF3 excess and
the lower the bath temperature, the lower the solubility of
metals in bath.
C*Al is the driving force for the dissolution of metals in bath,
metals which then participate in parasite reactions that reduce
the amount of electrons available for aluminum production.
It will therefore not come as a surprise that the solubility
of metals was the next most significant factor. It could be
argued that it is the most important factor for single cell CE
results, because the range of values explored in this study
was quite narrow (averages of large groups of cells). C*Al is
Predicting Instability and Current Efficiency of Industrial Cells
in fact included in one form or another into every CE model
investigated during the course of this study. Tarcy [5]
mentioned, in his own empirical analysis, that “its impor-
tance could almost not be overstated”.
Yosida and Dewing [6], Ødegård [7] and Wang et al. [8]
all published papers on solubility of metals in bath. For all
practical purposes, it did not matter very much which C*Al
definition was used, from a statistical analysis standpoint, as
their studies all reported similar slopes for bath temperature
and AlF3 excess in the narrow range of values that was
investigated in this study. A comparison of the values for
C*Al from those three papers is presented in Fig. 9.
Iron Content in Aluminum Metal
As demonstrated by Sterten et al. [9], the presence of
impurities (Fe, Si, V, Zn, Ga, Ti and P) is known to con-
tribute to CE loss through their involvement in redox reac-
tion loops. These experiments report a loss of 0.232% CE
per 100 ppm Fe(bath), which equates to a loss of 0.034% CE
per 100 ppm Fe(Al) in aluminium once a partition coeffi-
cient (bath/aluminum) of 0.147 (Qiu et al. [10]) is applied.
The correlation coefficient for Fe content in this analysis
is four times more important (−0.14% CE per 100 ppm Fe
(Al)). In a similar study, Dion et al. [11] reported −0.17%
CE per 100 ppm Fe(Al), which is very close. The greater
effect of Fe in an industrial context could be indirect, as Fe is
often affected by other factors (such as the quality of oper-
ations) that can also have an impact on the CE.
Metal Height
The positive correlation for metal height was unexpected but
ended up being important in the model. One possible reason
for the correlation is that metal height plays a role on the
Fig. 9 Comparison of AlF3 excess and bath temperature effect on solubility of metals (Yosida and Dewing [6], Ødegård [7] and Wang et al. [8])
627
MHD stability of the bath-metal interface that might not be
fully captured in the cell noise. However, there is also the
possibility that it could be linked to the specific character-
istics of this dataset and might not show up in a different
one. The mechanisms behind this correlation were not fur-
ther investigated.
Duration of no Feed Tracks and Alumina
Concentration
The alumina concentration is included in most models in the
literature, either directly or through the calculations of the
cryolite ratio (CR), bath density, bath viscosity or superheat.
For similar cell designs operated with the same control
system, it is possible to evaluate relative alumina concen-
tration with the duration of no feed tracks. An interaction
was identified between this predictor and C*Al. It was not kept
in the model because it was not significant enough.
Nonetheless, it interestingly reproduced Tarcy’s findings [8],
which were based on more precise LECO measurements.
This in itself could confirm the validity of this predictor in
the model.
The original interaction uncovered by Tarcy is shown in
Fig. 10, while the one identified in this study is shown in
Fig. 11. This interaction suggests that the effect of alumina
concentration depends on C*Al or, at the very least, on the
properties of the bath included in C*Al calculation. This could
well be the reason behind the divergent positions in the lit-
erature regarding the effect of alumina concentration on CE.
Performance of the Current Efficiency Model
The new model was compared to other models from the
literature, namely Lillebuen’s theoretical model [12], Sol-
heim’s semi-empirical model [13] and Tarcy’s empirical
628 P. Côté et al.

Table 2 Sensitivity of Tarcy’s model [5] and the new model, to

common parameters at typical values
Variation of parameters having a Tarcy model New model
correlation with CE [5] CE (%) CE (%)
+1 °C superheat −0.07 −0.08
+1% AlF3 @ constant bath temp. 0.18 0.2
+1% AlF3 @ constant superheat 0.46 0.51
+1% CaF2 @ constant bath temp. 0.02 0.03
+1% CaF2 @ constant superheat 0.27 0.3
Noise (+0,005 µOhms) −0.07 −0.1
Fig. 10 Interaction between C*Al and alumina concentration as mea-
sured by the LECO (Tarcy [5])

Actual CE vs Prediction of statistical model

CE = 4,161 + 0,9550 CE_MODEL
97 Régression
IC à 95 %
96 IP à 95 %

S 0,593758
95 R carré 74,2 %
R carré (ajust) 74,1 %

ACTUAL CE (%)
94

93

92

91

90

89
90 91 92 93 94 95 96
PREDICTED CE (%)

Fig. 12 Actual CE versus predicted CE for 40 trimesters of 15 plants

Fig. 11 Interaction between C*Al and duration of no feed tracks (DPFC
in Alpsys control system)

model [5], amongst others. Only the model from Tarcy could Statistical model applied to a smelter (last 10 years)

predict this set of data reasonably well, with an R-squared of 2 Variable

CE%
Model
56% once the effect of the ACD was added. It should be 1
Current Efficiency (%)

noted that due to lack of data, some terms had to be kept

constant for this comparison at the expense of the models. 0

While Tarcy’s model was done with more than a thousand

-1
individual cell current efficiency measurements, over short
periods (by Ag dilution), the new model was done with large -2

groups of cells (potlines) over long periods of time (trime-

-3
sters). Nonetheless, the results are very similar for predictors
1 1 1 1 1 1 1 1 1 1 1
common to both models (Table 2). The fact that the results -0 -0 -0 -0 -0 -0 -0 -0 -0 -0 -0
04 03 02 02 01 01 12 04 03 03 02
06- 07- 08- 09- 10- 11- 11- 13- 14- 15- 16-
are also close to most studies from the literature confirms the 20 20 20 20 20 20 20 20 20 20 20

validity of both models for these predictors. More impor-

tantly, it suggests that as far as current efficiency is concern,
the same rules that apply to a single cell can be generalized to
a group, at least for these parameters. Table 2 shows the
sensitivity of the models to their common parameters.
Figure 12 shows the fit for the new model when predicting
results over a period of 10 years (40 trimesters) for 15 plants
(R-squared of 74%). An example of prediction over several
months, for a smelter, can be seen in Fig. 13. The prediction
(in red)—although not perfect—is less variable than actual CE
results (in black) and could be a useful indicator of CE trends.
Fig. 13 Prediction of monthly results over 10 years for a smelter
(Color figure online)
Conclusion
New multivariate models were developed to predict insta-
bility and current efficiency of potlines. These models are
simple, yet powerful in their ability to predict the behavior of
large groups of cells.
Predicting Instability and Current Efficiency of Industrial Cells
The instability model developed for P155 technology
can predict over 90% of the week-to-week variance using
only five predictors, namely intensity, %CaF2, %AlF3
excess, target resistance and bath height. An example was
shown where the model was successfully used to correct a
problem that would have been difficult to identify
otherwise.
A statistical model for current efficiency (CE) was also
developed. The lack of precision of industrial CE results was
compensated for by a large set of data. Out of the seven
predictors that made it through a thorough screening
(Fig. 5), ACD was found to be the most important predictor
for this dataset.
The non-linear behavior of anode-cathode-distance
(ACD) versus CE was investigated and confirmed.
A pre-calculated CE loss, as a function of ACD, was used in
the linear model to cover up for this non-linearity. The rest
of the predictors were considered linear. As expected, sol-
ubility of metals in the bath (C*Al) was the next most
important factor, while metal height and a 7. R. Ødegård, On the solubility and electrochemical behaviour of
higher-than-expected effect from Fe(Al) were more surpris-
ing. These effects were not investigated thoroughly but could
be related to indirect causes or to specific characteristics of
the dataset. Duration of no feed tracks has been confirmed as
an indicator of alumina concentration, at least for similar
cells.
While it was developed in a completely different way, the
new model matches very closely with an empirical model
from the literature (Tarcy [5]) with regards to the impact of
the different operating parameters. This suggests that the
same general rules are valid whether they are applied to
single cells at one point in time or to a large group of cells
over longer periods.
These models are useful in the identification of reasons
for performance drifts or to determine whenever an
629
investigation is appropriate. They are currently being inte-
grated as standard tools across Rio Tinto aluminum smelters.
References
1. M. Segatz, J. Hop, P. Reny, Hydro’s cell technology path towards
specific energy consumption below 12 kWh/Kg. Light Met.
301–305 (2016)
2. M.J. Leroy, T. Pelekis, J.M. Jolas, Continuous measurement of
current efficiency, by mass spectrometry, on a 280 kA prototype
cell. Light Met. 291–294 (1987)
3. T.R. Alcorn, C.J. McMinn, A.T. Tabereaux, Current efficiency in
aluminum electrolysis by anode gas analysis. Light Met. 683–695
(1988)
4. R. Dorin, E.J. Frazer, Operational characteristics of laboratory
scale alumina reduction cells with wettable cathodes. J. Appl.
Electrochem. 23, 933–942 (1993)
5. G.P. Tarcy, Current efficiency in prebake and soderberg cells.
Light Met. 319–324 (2015)
6. K. Yosida, E. Dewing, The apparent solubility of aluminium in
cryolite melts. Metall. Trans. 3, 1817 (1972)
aluminium and aluminium carbide in cryolitic melts. Dr. Techn.
Thesis, The University of Trondheim, NTH, Norway, 1986
8. X. Wang, R.D. Peterson, N.E. Richards, Dissolved metals in
cryolitic melts. Light Met. 323 (1991)
9. A. Sterten, P.A. Solli, E. Skybakmoen, Influence of electrolyte
impurities on current efficiency in aluminum electrolysis cells.
J. Appl. Electrochem. 28, 781–789 (1998)
10. Z. Qiu, Y. Yu, M. He, X. Yu, B. Li, Impurity distribution in
bath and metal in aluminum electrolysis. Aluminium 75(12),
1100–1120 (1999)
11. L. Dion, L. Kiss, P. Chartrand, G. Dufour, F. Laflamme, Sodium
content in aluminum and current efficiency—correlation through
multivariate analysis. Light Met. 741–746 (2013)
12. B. Lillebuen, S.A. Ytterdahl, R. Huglen, K.A. Paulsen, Current
efficiency and back reaction in aluminium electrolysis. Elec-
trochim. Acta 25, 131–137 (1980)
13. A. Solheim, H. Gudbrandsen, K.S. Osen, J. Kvello, Current
Efficiency In Laboratory Aluminium Cells (ICSOBA, Dubai, 2015)
 Part XV
Aluminum Reduction Technology: Electrolyte and
Fundamentals
 Sodium in Aluminium as a Cell Performance
Indicator: A Quantitative Framework

Asbjørn Solheim

Abstract
The relationship between the content of sodium in the metal in aluminium production cells
and the current efficiency (CE) was analysed, using available theory and experimental data.
The sodium concentration as well as the CE varies with the bath composition (the bath
ratio) and the cathodic overvoltage. The mentioned parameters are all functions of the same
type of ratio between the activities of sodium fluoride and aluminium fluoride, thus
enabling an internally consistent and quantitative description. The “ideal” relationships
between the sodium concentration in the metal, the CE, and the cathodic overvoltage are
illustrated. It is suggested that the sodium content in the metal can indeed be used as an
indicator of the cell performance. However, it is necessary to use adequate sampling and
analysis techniques. The exact cell conditions during sampling should be taken into account
as well, such as the bath composition and the overfeeding/underfeeding cycle.

Keywords
Current efficiency Cathodic overvoltage Sodium

Introduction [4–8]. Thirdly, the variation of the NaF/AlF3 ratio at the

Using the content of sodium in aluminium as an indicator of
the current efficiency in aluminium electrolysis cells is not a
new idea. Tabereaux [1] was probably the first who clearly
explained the underlying principles and relationships. He
published a graph based on data from different industrial
cells, showing that the cells with higher CE also had higher
sodium concentration in the produced metal. The explana-
tion given by Tabereaux was based on three apparently
independent observations and hypotheses: Firstly, the
observation that the CE decreases with increasing degree of
convection at the metal-bath interface [2, 3]. Secondly, the
fact that that the equilibrium concentration of sodium in
aluminium increases with increasing NaF/AlF3 molar ratio
A. Solheim (&)
SINTEF Materials and Chemistry, P.O. Box 4760 Sluppen
NO-7465, Trondheim, Norway
cathode with the mass transfer coefficient at the cathode [9].
The reasoning behind the idea of using sodium in alu-
minium as a performance indicator appears to be well known
and understood in the aluminium community. Still; perhaps
surprisingly, nobody has tried to quantify this relationship by
using available theories, models, and experimental data—at
least, not in the open literature. The intention of the present
work was to systemise the already existing ideas and to present
an internally consistent theoretical description, accurate
enough to serve as a quantitative theoretical framework.
Concept
The relationship between sodium in the metal and the CE is
indirect, and coupled through mass transfer at the cathode (in
this paper, the term “cathode” refers to the metal-bath
interface, which is the cathode in the electrochemical sense).
The relationship can be explained qualitatively in the fol-
lowing way:

© The Minerals, Metals & Materials Society 2017 633

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_78
634 A. Solheim

3e 3
4C
Low mass transfer High NaF/AlF3
coefficient at cathode at cathode
Carbon
AR CE

Inc
3 i ng

re
4 CO2 as

as
r e

ing
1 c
2 Al2 O3 De

CE
High cNa in metal
(D) 3 Na +
Bath (M) Effect of mass
High CE
3 NaF AlF3 transfer dominates
(D) (D)
Fig. 2 Schematic representation of the relationship between current
CR
efficiency and sodium in the metal
Aluminium
3e Al
4
Fig. 1 Schematic representation of the electrode reactions in alu-
minium cells. CR Cathode reaction site, AR Anode reaction site,
M Migration (motion of ions in an electric field), D Diffusion. AlF3 can 2
be regarded as the “inner core” of cation complexes such as AlF63− and
AlF4−

ln(aNaF ) - 3 ln(aAlF3 )
0
1100 oC

1
1. Aluminium is deposited at the cathode by reduction of 1000
-2 900
aluminium fluoride, while the sodium ion carries most of 800
the current through the bath. Therefore, aluminium
-4
fluoride must approach the cathode by ordinary mass
transport across the boundary layer at the cathode, while
sodium fluoride forms at the cathode and diffuses back -6
1 2 3 4 5 6
into the bath. These phenomena lead to higher NaF/AlF3 r
molar ratio at the cathode (r*) than in the bulk (r), r* > r.
Fig. 3 The activity ratio determining the sodium activity (see the text)
The main transport paths related to the cell reaction are
as a function of the NaF/AlF3 molar ratio at different temperatures.
illustrated schematically in Fig. 1. Symbols Original data for NaF-AlF3 by Solheim and Sterten [10], curve
2. The sodium concentration at the cathode (c*Na, at the bath Graphical representation of Eq. 2
side of the cathode as well as on the metal side) depends
on the NaF/AlF3 molar ratio at the cathode, in such a way 1=3
that increasing r* gives higher c*Na. Activity ratio ¼ aNaF
aAlF3 ð1Þ
3. If the mass transfer coefficient at the cathode decreases
Solheim and Sterten [10] derived activity data for the
due to less convection, r* will increase due to the con-
system NaF-AlF3-Al2O3, partly in order to revise and
ditions described in item 1 above, which gives higher
replace earlier work [11, 12], and partly to express the data
c*Na according to item 2.
in the form of analytical equations that are easier to use in
4. The rate-limiting step for the loss in CE is the transfer of
spreadsheets and mathematical models than the earlier tab-
dissolved metal (mainly sodium) across the cathode
ular presentations. The resulting functions were rather
boundary layer. The transport rate increases with
complex, so it was found beneficial to express the activity
increasing mass transfer coefficient (k) and increasing
ratio by the following much simpler function:
c*Na. The effect of decreasing k normally dominates over

  
the effect of increasing c*Na. Therefore, decreasing k gives 1=3 9080 45700
lower rate of metal loss—i.e., increasing CE—and at the ln aNaF
aAlF3  1:63 þ þ 19:45 
T T 
same time, increasing levels of sodium in the metal. 1 1 5400 000

þ 20960 þ
1þr T
The overall concept is illustrated schematically in Fig. 2. 1


ð1 þ rÞ12
ð2Þ
Activity Data
A comparison between Eq. 2 and the original activity
It is noteworthy, and crucial in the present account, that the data is placed in Fig. 3.
above parameters can all be described in terms of the same Strictly, Eq. 2 is valid only for the system NaF-AlF3. The
ratio between activities (a) of NaF and AlF3, which will be effect of alumina on the activity ratio is shown in Fig. 4. It
referred to as the “activity ratio” in the following text: appears that the presence of alumina does not affect the
Sodium in Aluminium as a Cell Performance Indicator … 635

2 300
r = 3.0 1050 300 Tingle et al.
950 1000 Thonstad et al., Danielik
r = 2.5 1050
1 Danielik and Fellner
950 1000 Yoshida and Dewing

ppm Na in Al, calculated

r = 2.0
ln(aNaF ) - 3 ln(aAlF3 )

1050
0 200
1000
950
1

-1 r = 1.5
1000 100
-2 950
900

-3
0 5 10 15 0
0 100 200 300
[Al2O3 ] / wt%
ppm Na in Al, experimental

Fig. 4 The activity ratio as a function of the alumina concentration at Fig. 5 Comparison between experimental data for the equilibrium
different NaF/AlF3 molar ratios and different temperatures (°C). The amount of sodium in aluminium and the concentration calculated from
curves are drawn up to alumina saturation according to the activity Eq. 10. The experimental data comprise measurements made with r in
model the range of 1.2–3.5, temperatures from 850 to 1080 °C, and alumina
concentrations from zero up to saturation. Experimental data by Tingle
et al. [4], Danielik [5], Danielik and Fellner [6], Thonstad et al. [7], and
activity ratio much. Therefore, it was decided that there is no Yoshida and Dewing [8]
need to modify Eq. 2 by considering alumina, at least for
industrial bath compositions (r > 2.0). Unfortunately, there Based on experimental data, the activity coefficient for Na
is no activity data available for melts containing calcium in Al could be expressed as:
fluoride.
   11500
ln cNa ppm1 ¼ 1:17  ð6Þ
T
Equilibrium Concentration of Sodium At equilibrium conditions, the NaF/AlF3 ratio at the cath-
in Aluminium ode and in the bulk are the same. By insertion of Eqs. 4–6 into
Eq. 2 we obtain:
The sodium concentrations in the metal and in the bath  
depend on the following equilibrium at the cathode, 4994 45700
lnðcNa =ppmÞ  5:44 þ þ 19:45 
T T 
1 1 1 1 5400 000
NaF þ Al ¼ Na þ AlF3 ð3Þ
þ 20960 þ
3 3 1þr T
1
The equilibrium sodium concentration in the metal as
ð7Þ
well as in the bath can be calculated by ð1 þ rÞ12

C A comparison between the experimental data and Eq. 7 is

1=3
cNa ¼
aNaF
aAlF3
c
where C is the equilibrium constant and c is the activity
coefficient. Only the activity coefficients are different for
sodium in the metal and sodium in the bath. Most of the
sodium disappears into the bath; only a small fraction leaves
with the metal, e.g., 0.1 kg/t Al.
The equilibrium constant for the sodium-forming reaction
(Eq. 3) can be calculated by linearization of data for Gibbs
energy for the reaction. By using solid AlF3, liquid NaF, and
liquid Na as standard conditions, the change in Gibb’s
energy can be derived from JANAF [13]:
DG03 ¼ 129590  68:50 T
ð4Þ shown in Fig. 5. The experimental data contain measure-
ments obtained at different temperatures and with different
NaF/AlF3 ratios, alumina concentrations, and CaF2
concentrations.
Cathodic Overvoltage and Mass Transfer
The main part of the overvoltage at the cathode (η) is due to
the concentration differences of AlF3 and NaF between the
bulk of the bath and the cathode. The overvoltage can be
described by regarding that the bulk bath region and the
cathode forms a concentration cell [14], in which case the
ð5Þ Nernst equation can be applied,
636 A. Solheim

RT n
 1=3


1=3
o 0.15
jgj ¼
ln aNaF
aAlF3  ln aNaF
aAlF3 ð8Þ
F k = 1.5 .10 -5ms-1

where R is the universal gas constant [8.3143 Jmol−1K−1] 2.0

and F is Faraday’s constant [96 485 Cmol−1]. 0.10
The flux of AlF3 across the cathode boundary layer

|h | / V
3.0
becomes
4.0
i
e
MAlF3 2 1 0.05
j¼ kgm s ð9Þ
3F 5.0

where i is the current density [Am−2], e is the fractional

current efficiency (e.g., e = 0.94), M is the molar weight 0
[0.084 kg mol−1], and F is Faraday’s constant [96,485 As 0 2 4 6 8 10 12
Current density / kAm-2
mol−1]. The concentration difference across the cathode
boundary layer becomes Fig. 6 Cathodic concentration overvoltage as a function of the
cathodic current density with different mass transfer coefficients for
j
Dw ¼ kgm2 s1 ð10Þ AlF3 (see the text for conditions)
k
q

where Dw is the difference in mass fraction of AlF3 between 250

the bulk and the cathode, k is the mass transfer coefficient for
AlF3 [ms−1], and q is the density of the bath [kgm−3]. The k = 1.5 .10 -5ms-1
200
density of the bath shows little percentual variation with the
bath composition. By using q  2080 kgm−3 Eqs. 9 and 10 Na in Al / ppm 150
2.0
combine to give
3.0
ie 100 4.0
Dw  1:4
1010
ð11Þ
k 5.0
50
By disregarding the concentrations of CaF2 and Al2O, the
weight fraction of NaF can be expressed as 1−w. By
translating this into molar ratios we obtain: 0
0 2 4 6 8 10 12
10 Current density / kAm-2
1 2  ðr þ 2Þ
1:4
10 ði e=kÞ
 ð12Þ
r þ 1 2 r þ 2 þ ðr þ 2Þ
1:4
1010
ði e=kÞ Fig. 7 Concentration of sodium at the metal side of the cathode as a
function of the cathodic current density with different mass transfer
The cathodic overvoltage can be calculated using Eqs. 2, coefficients for AlF3 (same conditions as in Fig. 6, see the text)
8, and 12. It is an almost linear function of the current
density, as shown in Fig. 6. The fractional CE used in
Eq. 12 was computed from the CE model discussed below. Current Efficiency
It was assumed that the bath contains 11.6 wt% excess AlF3
(r = 2.2), 5.0 wt% CaF2, and 3.5 wt% Al2O3 at 959 °C. The The main cathode reaction in the aluminium electrolysis can
overvoltage is quoted to be about 40-120 mV in normal be written (see Fig. 1)
situations [15], corresponding to a mass transfer coefficient AlF3 þ 3 Na þ þ 3 e ¼ Al þ 3 NaF ð13Þ
for AlF3 of about 1.5–5  10−5 ms−1. It is likely, however,
that the mass transfer coefficient is outside this range in some The loss in current efficiency is caused by formation of
situations (cells running very smoothly with high CE, or metal species that are soluble in the bath. The dissolved
unstable cells with much noise). metal is transported across the cathode boundary layer and
The concentration of sodium at the metal side of the becomes oxidized at the anode or by carbon dioxide. It
cathode was computed from Eqs. 2 and 7, and the result is appears that sodium is the most important species, since its
shown in Fig. 7. presence gives electronic conductivity in the bath. It is
Sodium in Aluminium as a Cell Performance Indicator … 637

formed in a parasitic side reaction at the cathode, “stealing” 100

electrons that would otherwise be used in the main cathode
reaction,
95

Current efficiency / %
Na þ þ e ¼ Na ð14Þ
The fractional CE can be expressed as 90

iloss
e¼1 ð15Þ
itot 85

where iloss is the loss current density and itot is the total
cathodic current density.
80
The CE loss is governed by the transport rate of dissolved 1 2 3 4 5
metal from the cathode towards the bulk of the bath. NaF/AlF3 molar ra o
Therefore, iloss is a function of the dissolved metal concen-
Fig. 8 Current efficiency as a function of the NaF/AlF3 molar ratio.
tration at the cathode (represented by sodium) and a trans- Symbols Experimental data by Solli et al. [17], curve Current efficiency
port coefficient, the latter representing ordinary mass transfer model [18]
as well as electronic conduction.

The current efficiency was studied extensively in the 0:70½CaF2 14
work by Solli and Sterten [16, 17]. Experimental data were fðaddÞ ¼ 10
8:92 
1þ0:08½CaF2 
achieved using a well thought out laboratory cell (the 
“Sterten-Solli cell”). Contrary to most previous laboratory 2:10½MgF2  0:18½LiFðr  2:4Þ 0:50½KF
 þ þ
investigations; the measured current efficiencies were r3=2 1  0:05½LiF 1þ0:02½KF
similar to or even higher than industrial CEs, probably ð18Þ
owing to the fact that contact between aluminium and
carbon was avoided, thus eliminating aluminium carbide A comparison between the above CE model and some of
formation. the experimental data is shown in Fig. 8.
The following should be regarded as a new It should be noted that Eq. 18 does not contain a term for
semi-empirical fit of Solli and Stertens data, utilizing the alumina. The effect of alumina was studied by Solli et al.
newer activity description shown in Eq. 2, and with the [17], without finding any significant effect on the CE. This
addition of data for lithium fluoride, magnesium fluoride, could also be expected, in light of the data shown in Fig. 4.
and potassium fluoride [18]. However, the equation is based on theory and laboratory
It has been substantiated [16, 19] and shown by experi- data. The effect of some parameters that are specific for
ment [17] that the loss in CE is close to proportional with the industrial cells cannot be predicted (in any model), such as
square root of the sodium concentration at the cathode, the presence of sludge, alumina particles or agglomerates
residing at the metal-bath interface and variation in the
pffiffiffiffiffiffi
ffi 1=2 1=6 sideledge situation.
iloss / k
cNa / k
aNaF
aAlF3 ð16Þ

where k is the mass transfer coefficient for AlF3 and the

activity ratio can be computed by taking the square root of
Synthesis: Quantitative Framework
Eq. 2, using the molar ratio at the cathode calculated from
Eq. 12.
Basic Model
It is also necessary to add a term for representing the
The basic model for the relationship between the concen-
temperature dependence of the concentration of dissolved
tration of sodium in the metal and the CE simply consists of
metal, as well as an empirical term f(add) that describes the
(i) the model for sodium concentration in the aluminium,
effect of bath constituents other than NaF and AlF3:
(ii) the relationship between mass transfer coefficient, current
  density, and molar ratio at the cathode, and (iii) the CE
1=2 1=6 22 000
iloss ¼ k
aNaF
aAlF3
exp 
fðaddÞ ð17Þ model. The result is shown graphically in Fig. 9.
T
It can be observed in Fig. 9 that lower cathodic over-
The empirical function given in Eq. 18 below was based voltage (caused by increased mass transfer coefficient) gives
partly on the experimental data by Solli et al. [17] and partly lower CE as well as lower sodium concentration. On the
on measurements carried out at SINTEF [18], other hand, increasing amounts of excess AlF3 in the bulk
638 A. Solheim

0.20 300 6
240
98
96
180

Al2O3 concentra on / wt%

0.15 250 5
94 140

Na in Al / ppm
100
|h | / V

200 4
0.10 92 80
60
90
40 150 3
0.05 88
86 Overfeeding Underfeeding

100 2
0 0 2 4 6 8
0 5 10 15 20 Time / h
[Excess AlF3 ] / wt%
Fig. 10 Sodium in the metal of an industrial cell (left hand scale) and
Fig. 9 Current efficiency (black curves, percent) and sodium content alumina concentration in the bath (right hand scale) during overfeeding
in the metal (green curves, ppm) as a function of the amount of excess followed by underfeeding. Experimental data by Thonstad et al. [7].
aluminium fluoride in the bulk of the bath and the cathodic overvoltage. The curves are not theoretically justified
The bath contains 5 wt% calcium fluoride and 3.5 wt% alumina. The
temperature was assumed to be 8 °C above the liquidus temperature
computed from the “SINTEF equation” [20], corrected by subtracting
3 °C to account for trace elements. The current density was 9000 Am−2
cc
Ac þ cs As cc þ cs
As =Ac
cm ¼ ¼ ð21Þ
As þ Ac 1 þ As =Ac

also decreases the sodium concentration, while the current
efficiency increases. This illustrates the importance of
knowing the bath composition and temperature at the time of
metal sampling.
The Role of Sludge
As was explained above, the sodium concentration in the
metal is governed by the NaF/AlF3 ratio at the cathode (r*).
However, the metal “sees” not only the cathode, but also
sludge at the bottom of the cell. A simplified model can be
derived concerning the relationship between sludge and
sodium in the metal, starting with the assumption that there
is a dynamic equilibrium between the metal side of the
cathode and the surface of the sludge. The flux of sodium
from the cathode and into the metal becomes
jðcmÞ ¼ kc
Ac
ðcc  cm Þ
where the subscripts “c” and “m” represent the cathode
(metal side) and the bulk of the metal, respectively. The flux
of dissolved sodium from the bulk of the metal is:
jðmsÞ ¼ ks
As
ðcm  cs Þ
In a cell with 10 wt% excess AlF3, 120 mV cathodic
overvoltage, and generally the same conditions as used in
Fig. 9, the sodium content in the metal will be 200 ppm in
the sludge-free situation. If the cell bottom (same area as the
cathode) is completely covered by “fresh” sludge having the
same molar ratio as the bulk of the bath, the metal concen-
tration becomes only 133 ppm.
It can be assumed that “fresh” sludge is being formed
mainly during periods with overfeeding, while underfeeding
may cause the contact area between metal and sludge to
decrease. Therefore, the model described above predicts that
the sodium concentration decreases during overfeeding and
increases during underfeeding. This is exactly what was
observed by Thonstad et al. [7], as shown in Fig. 10.
It is known that the excess AlF3 concentration in the
sludge is much lower than the concentration in the bath.
Keller et al. [9] suggested that this is due to sludge taking up
sodium from the metal. This means that there is a difference
ð19Þ between “old” and “fresh” sludge. “Fresh” sludge attracts
sodium, resulting in lower concentrations in the bath than
what can be expected from the situation at the cathode.
Eventually, “old” sludge ends up with the same NaF/AlF3
ratio as at the cathode.
ð20Þ

where the subscript “s” represents the sludge. Assuming that Time Constant
the mass transfer coefficients are equal and that a
quasi-stationary equilibrium exists (i.e., j(c−m) = j(m−s)), we One can assume that the reaction forming sodium at the
obtain: cathode is rapid. If fresh sludge forms, sodium must be
Sodium in Aluminium as a Cell Performance Indicator …
transferred from the cathode through the metal boundary
layer and into the bulk of the metal. It can be shown that the
time constant for the variation of the bulk concentration
becomes h/km where h is the metal height and km is the mass
transfer coefficient for sodium. Taking kc = 1  10−4 ms−1
and h = 0.2 m the time constant becomes 0.56 h, which
seems to be compatible with the data in Fig. 10.
Metal Sampling
In order to use sodium as an indicator of CE, it is obvious
that the analysis of sodium in the metal has to be precise.
Possibly, it is less known that the metal sampling also is
critical. The metal is usually sampled using a ladle, followed
by pouring the metal into a form where is solidifies to form a
disc. During the pouring, much sodium is lost due to its high
vapour pressure (e.g., 0.04 atm). By using a closed metal
sampler, Thonstad et al. [7] analysed much higher sodium
concentrations.
Concluding Remark
In the author’s opinion, it is indeed possible to use the
sodium concentration in the metal as an indicator of cell
performance. However, besides proper techniques for metal
sampling and analysis, this requires additional information
concerning bath composition, temperature, and the
overfeeding/underfeeding cycle.
Acknowledgements The present work was supported by the project
“Sustainable Production and Recycling of Metals” (SUPREME),
financed by the Research Council of Norway and Hydro Aluminium,
Boliden, Glencore, and Permascand. The author would like to thank Dr.
Per Arinn Solli, Hydro Aluminium, for the inspiration to initiate this
work.
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 Bauxite Processing via Chloride Route
to Produce Chloride Products and Subsequent
Electrolysis of Aluminium Chloride to Produce
Aluminium Metal

Sankar Namboothiri and Subash Mallick

Abstract
Based in Mumbai, India, Gharda Scientific Research Foundation (GSRF) is working to
produce aluminium chloride and primary aluminium via carbochlorination of bauxite
followed by electrolysis step. In this paper, a literature review of the chloride route based on
published literature and concept proof experiments in various small setups are discussed.
Bauxite was chlorinated with calcined petroleum coke in an externally heated small
bubbling fluidized bed reactor. Aluminium chloride thus produced was purified by
reductive distillation in a small setup and used for aluminium chloride electrolysis in a 50 L
cell. The study aimed to generate scale up data for optimizing the chloride conversion,
recovery and purity as well as electrolysis efficiency. The findings are used for process scale
up to a kg scale setup and then to a larger demonstration plant. Presently, GSRF is
operating a demonstration plant for carbochlorination of bauxite.

Keywords
Carbochlorination Reductive distillation AlCl3 electrolysis

Introduction
There has been progressive improvements in the steps
involved in processing of bauxite to aluminium metal, which
has helped to keep the processing sustainable since it
became the industrial route in the late 1800s. Bauxite is
processed to isolate alumina (Al2O3) by Bayer process.
Aluminium is produced by the Hall-Héroult process by
electrolysis of Al2O3 dissolved in molten cryolite bath.
Bayer process is energy intensive and generates approxi-
mately from 1 to 1.5 T of Red mud per ton of Al2O3. Hall
Héroult process consumes more than double the energy
theoretically required for producing a kg of aluminium metal
(13–14 vs. 6.34 kWh) [1, 2].
However, these processes need further rapid improve-
ments to meet the stringent demands for reducing emissions
S. Namboothiri (&)
S. Mallick
Gharda Scientific Research Foundation, 48, Hill Road, Bandra
West, Mumbai, 400050, India
e-mail: sknamboothiri@gharda.com
and also for reducing the cost of value addition. The present
processing has reached a plateau for further step changes
and hence looking at alternate routes for processing, which
are in line with present demand is relevant. There has been
considerable effort in this regard, but with little success
to-date.
One of the alternative electrolytic process routes for
production of aluminium employs chemical conversion of
Bayer alumina or aluminous ore to aluminium chloride
(AlCl3), aluminium sulphide (Al2S3) and aluminium nitride
(AlN) and subsequent electrolytic conversion to aluminium
metal [3–7]. Out of the alternatives, process path involving
AlCl3 was explored more compared to other intermediates.
Most obvious advantages of AlCl3 electrolysis in compar-
ison with the Hall Héroult process are [8, 9]:
• lower working temperature (*700 °C)
• carbon based anodes are not consumed in the electrolysis
• bi-polar cell is possible with carbon based electrodes and
in this way, cell can be operated with increased pro-
ductivity and power efficiency

© The Minerals, Metals & Materials Society 2017 641

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_79
642 S. Namboothiri and S. Mallick

• relatively higher current densities could be achieved Fe2 O3 þ 1:5C þ 3Cl2 ! 2FeCl3 þ 1:5CO2 ðDG  107:03Þ
• with ledge free operation, process can better handle ð2Þ
power interruptions/swings.
TiO2 þ C þ 2Cl2 ! TiCl4 þ CO2 ðDG ¼ 56:21Þ ð3Þ
AlCl3 electrolysis was tested at a pilot scale by Alu-
minium Company of America (Alcoa) previously and sub- SiO2 þ C þ 2Cl2 ! SiCl4 þ CO2 ðDG ¼ 35:52Þ ð4Þ
sequently abandoned due to a number of reasons [9]. One of
Reactivity of various oxides present in bauxite vary with
the reasons could be insufficient economic benefits to replace
process conditions, hence, one way of enriching bauxite with
the Hall-Héroult process. This was mainly because Bayer
Al2O3 is by sequential separation of Fe2O3 and TiO2 and
alumina was used as raw material for production of cell
then further second stage chlorination of enriched bauxite.
grade AlCl3 which added extra processing steps for raw
Alpha alumina form is not preferred for carbochlorination as
material production, in addition to the Bayer process.
it is a stable form [10]. Hence, the process conditions should
However, it is recognized that production of cell grade AlCl3
be such that alpha alumina is not formed during the process.
via bauxite chlorination route (BCR) is more economical as
Carbon is preferred than CO as a reducing agent in car-
the Bayer process can be by-passed. In addition, valuable by
bochlorination [11], The production of pure AlCl3 from
products such as titanium tetrachloride (TiCl4) and iron
carbochlorination of bauxite depends on efficient separation
chloride (FeCl3) can be extracted.
of chlorides impurities from AlCl3.
AlCl3 is a widely used industrial chemical and it has a
Carbochlorination of alumina has been the subject of
number of application areas such as in organic synthesis and
many investigations to understand the mechanism and
petroleum refining. Current production of AlCl3 is mainly
kinetics of the reaction. The chlorination of pure alpha alu-
carried out by direct chlorination of metallic aluminium [10].
mina was investigated by several authors and found that the
BCR process would be far cheaper than the current process,
kinetics is slow [12–14]. The rate of reaction depends on
provided sufficient purity of AlCl3 can be obtained.
physical contact of solid carbonaceous material with chlo-
GSRF have been working to develop the chloride process
rine gas to form a complex and further reaction with bauxite
route for bauxite processing to AlCl3 and aluminium. The
particle [10]. Hence, surface area of bauxite particle is
technologies are at various stages from laboratory scale to kg
important for better reactivity. The alpha form has a lower
scale to semi commercial scale. In this paper, a relevant
surface area compared to gamma form. Formation of alpha
theoretical consideration, literature review and concept proof
phase starts at above 850 °C [10]. Hence, controlled calci-
experiments conducted at GSRF laboratory are described,
nation of bauxite below 850 °C is desirable to prevent onset
along with the process scale up pathway. Carbochlorination,
of alpha phase formation.
purification of impure AlCl3 and electrolysis are discussed in
separate sections.
Experimental Details

Carbochlorination of Bauxite
Al2O3 and other aluminium bearing minerals such as
bauxite, clay minerals can be carbochlorinated to AlCl3 and
other chlorides by reaction of chlorine in presence of carbon
or carbon monoxide (CO). The reaction of Al2O3 occurring
during carbochlorination with carbon as reducing agent is
given in Eq. (1).
Al2 O3 þ 1:5C þ 3Cl2 ! 2AlCl3 þ 1:5CO2 ðDG  49:17Þ
ð1Þ
where ΔG is the Gibbs free energy of reaction at 800 °C,
kcal.
In addition to Al2O3, all other oxide impurities in bauxite
such as iron oxide (Fe2O3), titanium oxide (TiO2) and silica
(SiO2) are also carbochlorinated, depending on the temper-
ature of operation, as shown in Eqs. (2–4).
Bauxite used in the study was from Satara deposit of Wes-
tern Ghat region. The ore composition was Al2O3 (*64%),
Fe2O3 (*8.5%), TiO2 (*2.2%), SiO2 (*3%) with volatile
and water of hydration (*25%) as major components. The
lumpy ore was crushed in a jaw crusher and reduced to
25–50 mm size. The crushed ore was then pulverized in
impact pulverizer to make fine powder of particle size in the
range of 70–1000 µm. Required particle size range (mesh
size) was then prepared by vibro-screening. The sieved ore
was calcined at 750 °C in an electrical furnace to reduce the
moisture to less than 1% bound moisture. The calcined
bauxite was used as feed for carbochlorination. Carbona-
ceous material used was calcined petroleum coke (pet coke)
with less than 1% volatile materials. Particle size of pet coke
was selected such that fluidization velocity is similar with
that of the bauxite particle. Chlorine gas used was of
industrial grade and was stored in a chlorine toner.
Bauxite Processing via Chloride Route to Produce Chloride Products …
Fig. 1 Schematic drawing of Carbochlorination setup (FBR—flui-
dized bed reactor, Tp-Thermocouple)
Carbochlorination was carried out in an externally heated
quartz fluidized bed reactor with condensers and alkali
scrubber, as shown in Fig. 1.
The initial bed was prepared by taking 1.5 kg calcined
bauxite and 1.5 kg pet coke. The bed material was heated by
external electrical coil and the temperature was raised to
650 °C. Measured quantity of chlorine gas was passed
continuously through a rotameter from the tonner. Car-
bochlorination was carried out in bubbling bed condition and
excess chlorine (1.5 times excess on stoichiometry) was
supplied to ensure maximum reaction. The product gases
were condensed in condensers and non-condensable gases
were passed through an alkali scrubber containing 4N NaOH
solution. The chloride products AlCl3, FeCl3 and TiCl4 were
collected and analyzed. The alkali scrubber solution was
analyzed to check the chlorine slip, CO/CO2 ratio and
escaped chlorides, particularly TiCl4 and SiCl4 (if any).
Number of carbochlorination stages, temperature, particle
size and chlorine flow rate was varied to determine the
selectivity of FeCl3/TiCl4 in the first stage, bauxite conver-
sions and purity of AlCl3. Variables used in the experiments
reported in the paper are shown in Table 1.
Table 1 Variables used in the Particle size range (mesh)
carbochlorination experiments
−200,
−100 to +150,
−60 to +100,
−18 to +60
643
Results and Discussion
Calcination
The pulverized bauxite was calcined at controlled tempera-
ture of 750 °C ± 20 to remove all bound water molecules
and convert aluminous compound to Al2O3. The calcined
bauxite containing Al2O3 (*80%), Fe2O3 (*12%), TiO2
(*3.2%), SiO2 (*4%) and bound moisture (less than 1%)
was obtained and was used for carbochlorination. The BET
surface area of the calcined bauxite was seen to increase with
decrease in particles size range. The BET surface area of the
calcined particles are 98 m2/g (−200 mesh), 52 m2/g (−100
to +200 mesh), 25 m2/g (−60 to +100 mesh) and 16 m2/g
(−18 to +60 mesh).
Two Stage Carbochlorination
Two stage carbochlorination was investigated where first
stage was employed to remove selectively Fe2O3 and TiO2
and thereby, enriching Al2O3 in bauxite. Enriched bauxite
was further subjected to a second stage carbochlorination at
a higher temperature.
Selectivity of Fe2O3 was highest when first stage car-
bochlorination is conducted at 650 °C. As the temperature
was increased, more Al2O3 was also carbochlorinated and
came along with FeCl3. Selectivity of Fe2O3 was found to be
independent of particle size in the trials conducted. This was
startling as the hypothesis was to see better selectivity at
finer particle size range. This may be due to the use of
bauxite with lower Fe2O3 content (8.8%). Further grinding
of particle was not facilitating availability of more Fe2O3 for
reaction. Overall, 60–80% Fe2O3 was removed in the first
stage along with 50–60% TiO2 and 2–6% Al2O3.
Overall conversions of the oxides obtained in the trials
were in the range of 80–90%. Purity of AlCl3 product was in
the range of 90–94%.
Single Stage Carbochlorination
Single stage carbochlorination is more convenient if the
impurities in AlCl3 product can be removed. Results from
single stage carbochlorination are tabulated in Table 2.
Overall conversion of Al2O3 was found to be slightly better
Carbochlorination Temperature Cl2 flow rate
mode/Stages range °C (m3/h)
Single stage Single stage at 800–850 0.1
Two stage First stage at 650–750 0.15
Second stage at 800–850 0.2
644 S. Namboothiri and S. Mallick

Table 2 Results from single Particle size (mesh) Overall conversion, % Purity of AlCl3, % Particle elutriation, %
stage carbochlorination
−200 80–88 >90 11–14
−100 to +150 80–90 >90 10–13
−60 to +100 88–94 >90 6–9
−18 to +60 60–70 >90 3–5

Table 3 Boiling point and Product Boiling point, °C Form Separation method from AlCl3
separation methods of FeCl3,
TiCl4 and SiCl4 FeCl3 320 Solid Reductive distillation
TiCl4 136 Gas Simple condensation/reductive distillation
SiCl4 57 Gas Simple condensation

for batches with particles between −60 and +100 mesh. such as NaCl-AlCl3 to which impure chloride is added. It is
Beyond this size range, the reactivity was found to decrease shown that TiCl4 and FeCl3 is reduced to lower chlorides or
in bubbling bed conditions. The particle carry over was metals, distilling out pure AlCl3 [16]. The reduced chlorides,
found to be higher for finer particle size and this was oxides and other solid impurities were remained in the liquid
reflected in the overall conversion. The purity of AlCl3 bath and pure AlCl3 is separated by distillation. The basic
obtained was in the range of 90–94%. reactions of the process are given by Eqs. (5–9).
In single stage carbochlorination, higher particle size was
found to be advantageous; as particle elutriation was reduced 3FeCl3 þ Al ! 3FeCl2 þ AlCl3 ð5Þ
without compromising on bauxite conversion and purity of
3FeCl2 þ 2Al ! 3Fe þ 2AlCl3 ð6Þ
AlCl3. A typical impurity profile of AlCl3 product obtained
from carbochlorination was Fe2O3 −0.7 to 1.2%, Al2O3 −0 2FeCl3 þ Fe ! 3FeCl2 ð7Þ
to 3.8% TiO2 −0.25 to 0.6%, FeCl3 −0.8 to 3%, TiCl4 −1%,
Carbon −0 to 1.5%. Chlorine slip was found to be negligible 3FeAlCl6 þ Al ! 3FeCl2 þ 4AlCl3 ð8Þ
initially and found to increase as the trial progressed. This is
due to the batch mode experiment, where there was a pro- 3TiCl4 þ Al ! 3TiCl3 þ AlCl3 ð9Þ
gressive depletion of solid reactant.
The reduced chlorides have very high boiling point and
remain in the bath as solids. The base electrolyte NaAlCl4 is
stable as it has a lower vapor pressure at the operating
Purification/Separation of AlCl3 from Other temperature compared to AlCl3.
Chlorides

The electrolysis process requires pure AlCl3 feed for pro-
ducing commercial grade aluminium metal. Main chloride
impurities from bauxite carbochlorination include FeCl3,
TiCl4 and Silicon tetrachloride (SiCl4). Separation of TiCl4
and SiCl4 can be achieved mostly by simple condensation
steps due to higher difference in their volatilities, relative to
AlCl3 and absence of vapor phase complexes. Sublimation
temperature of AlCl3 is 183 °C and boiling points of rele-
vant chlorides and possible separation method are shown in
Table 3.
Some FeCl3 forms mixed chloride complex with AlCl3 in
vapor phase and it forms solid solution when condensed and
cannot be fully separated by simple condensation steps,
despite high difference in volatilities between pure AlCl3 and
pure FeCl3 [15–17].
Single stage reductive distillation is an option to separate
the mixed chloride complex and produce high purity AlCl3.
A metallic reducing agent can be used in a molten salt bath
Experimental Details
Impure AlCl3 (crude) produced in carbochlorination was
purified by reductive distillation and setup used is shown in
Fig. 2. AlCl3 obtained in carbochlorination contain FeCl3
(up to 10 wt%), TiCl4 (up to 3 wt%) and insoluble
(1–5 wt% entrained fine oxides and carbon). Base elec-
trolyte (bath) was prepared by taking pure NaCl and AlCl3
in a ratio of 30 and 70 mol% respectively. The bath was
electrically heated from outside by electrical coil to keep
the bath molten. Distillation was carried out at
210 °C ± 10. Aluminium metal powder was added to the
bath and the concentration was maintained at 1% (w/v)
initially. During continuous feed, stoichiometric amount
with 10% extra aluminium powder was added to reduce
FeCl3 and TiCl4. Pure AlCl3 vapor was condensed in a
condenser. The reduced mass accumulated in the bath was
drained from time to time. Several experiments were
Bauxite Processing via Chloride Route to Produce Chloride Products … 645

aluminium powder was required to be maintained to produce

consistent quality of >99.8% AlCl3. The distillation of AlCl3
was found to be slow at 200 °C and increased with tem-
perature. This was evident as mole ratio of AlCl3 in the bath
was increased from 70% up to 90% at 200 °C. Impurity
levels of up to 5 wt% of oxides and carbon was seen to have
minimal effect on the rate of reaction. Beyond 5 wt%, the
reaction rate was drastically reduced. Hence, it is important
to ensure that carbochlorination process is tuned accordingly
to get crude AlCl3 of required quality.
Metallic iron/FeCl2 solids were filtered out and iron free
molten bath was recycled back to the reactor. The final
distilled AlCl3 was white to pale yellow in color and pow-
dery in nature. Average FeCl3 content in AlCl3 distilled
product was around 1000 ppm.

Electrolysis of AlCl3

AlCl3 can be electrolyzed to aluminium and chlorine gas by

dissolving AlCl3 in a chloride based molten salt as per
Eq. (10).

AlCl3 ! Al þ 1:5Cl2 ; Edecomposition ¼ 1:76 V at 700  C

ð10Þ
In 1857 Bunsen and Deville first succeeded in getting
aluminium by electrolysis of AlCl3 in sodium chloride—
aluminium chloride melt. There was a renewed interest to
Fig. 2 Schematic drawing of reductive distillation set up
produce aluminium metal by alternate methods in 1960s.
One of the efforts initiated was production of aluminium
chloride and subsequent electrolysis to produce aluminium
Table 4 Variables used for purification of crude AlCl3 with much less energy consumption [18]. It was perceived
FeCl3 Oxides/carbon Al usage/particle size Temperature that the production of aluminium metal by electrolysis of
content content, % range °C AlCl3 in molten salt has many advantages, as mentioned
%
previously in the paper. The electrolysis process used higher
1–10 1–7 1–1.5 times of 200–250 conductive molten salts composed of alkali and alkaline
stoichiometry for
complete reduction to
earth metal chloride at around 700 °C. The aluminium
iron metal/particle size producing companies like Alcoa and Nippon Light Metals
−0.04 to 2000 µm had conducted many years of research and development on
AlCl3 electrolysis. Alcoa’s efforts had taken the AlCl3
electrolysis process, nearly to the commercial production
carried out by varying input purity of crude AlCl3 to level. It was reported that Alcoa was operating a plant based
determine an acceptable range and the required aluminium on bi-polar technology with an annual rated production
concentration in the bath. The variables used for purifica- capacity of 15,000 Ton in late 1970s [9]. However, due to
tion experiments are summarized in Table 4. various reported reasons such as production of chlorinated
hydrocarbon, by-pass current in the cell, issues with raw
material production and handling and other unreported rea-
Results and Discussion sons, project was discontinued [18–20].
The economic advantage for this process is strongly
Reduction of FeCl3 with aluminium metal powder was dependent on cost of producing AlCl3 and if Bayer alumina
found to be completed in less than 1 min at the operating chlorination is used, it would partly negate the benefits
temperatures. However, in continuous operation 1% (w/v) offered by electrolysis process.
646
Experimental Details
The AlCl3 produced from carbochlorination and purchased
laboratory grade AlCl3 was used as raw material in the
electrolysis trials. Electrolysis was carried out in a 50 L
crucible cell containing clay graphite crucible. The cell was
connected to a condenser (catch pot) for condensing any
un-reacted AlCl3 and bath chloride vapors. Further an alkali
scrubber was installed in line for scrubbing chlorine gas
generated during electrolysis. The experiment set up is
shown in Fig. 3. The base electrolyte (mixture of NaCl,
LiCl, KCl, CaCl2 and MgCl2) was prepared by melting the
salt mixture in situ by passing AC current for resistance
heating of a removable carbon wedge, which was placed in
the cell. The AlCl3 concentration was made up by intro-
ducing solid AlCl3 and maintained around 5 wt%. Elec-
trolysis was carried out at 720 °C ± 10 in electrolyte
comprising of 3–7 wt% AlCl3, 35–45 wt% LiCl/KCl, 45–
55 wt% NaCl and 1–2 wt% CaCl2/MgCl2. Graphite elec-
trodes were used for both cathode and anode (supplied by
SGL carbon, Germany). Electrodes were arranged in vertical
disposition and the cell was operated in mono-polar mode.
The anode-to-cathode distance (ACD) was maintained in the
range of 1–2.5 cm and operating cathode current density was
varied from 0.6 to 1.5 A/cm2. Several experiments were
Fig. 3 Schematic drawing of
electrolysis set up
S. Namboothiri and S. Mallick
carried out to determine the key cell parameters such as the
specific energy consumptions, current efficiency and metal
purity. Also, a working electrode-electrolyte combination
was tested in short to medium term electrolysis trials (up to
600 h).
Results and Discussion
Electrolysis with KCl-NaCl-AlCl3 melt was not successful
as after 4–5 days of electrolysis, the cathode got disinte-
grated in situ and cell had to be stopped. This was attributed
to the vigorous intercalation of potassium ions through the
graphite structure and thereby, damaging the electrode.
Electrolysis in LiCl-NaCl-AlCl3 bath was used for further
study The lithium/sodium impregnated cathode has shown
much more resistance compared to potassium intercalated
cathode. Both carbon and graphite are reported to be stable
to sodium, lithium and AlCl3 intercalation between the
temperatures of 500 and 800 °C. At above 800 °C sodium
intercalate while below 500 °C, AlCl3 intercalate into the
cathode [21].
The electrolysis was conducted in a stable manner for up
to 600 h. The electrodes were found to be intact after the
electrolysis trial. The net operating cell voltage was in the
Bauxite Processing via Chloride Route to Produce Chloride Products … 647

Table 5 Status of Quartz reactor Inconel reactor Refractory lined Refractory lined
carbochlorination experiments (1.5 kg (5 kg bauxite) fluidized bed reactor fluidized bed reactor
bauxite) (10 kg/h) (200 kg/h)
Status: completed Completed Completed On-going
Features: Batch mode, Batch mode Semi continuous mode, Continuous mode,
bubbling bed, externally bubbling bed, fluidized bed, internally fluidized bed
heated internally heated heated
Main investigation Effect of internal Continuous mode Longer term operation
areas: Bauxite reactivity, heating, operation, bauxite/coke and performance,
product recovery by confirming of feeding, overall bauxite product recovery and
simple condensation and bauxite reactivity reactivity and product purity, MOC stability in
purity of AlCl3 and product recovery longer term operation
recovery Testing of materials of
construction (MOC)

range of 2.6–3.3 V for the range of current densities and
ACDs used. The specific energy consumption was calculated
based on the aluminium tapped and it was found to be
between 9 and 10 kWh/kg Al. Overall current efficiency
obtained was 80–85%. The metal purity obtained was up to
99.9%.
KCl based bath is preferable due to its cheaper cost and
also it is easier to handle due to its lower hydrophilicity
compared to LiCl. Lithium/sodium intercalated graphite was
tested in KCl based bath. Stability of graphite electrode in
KCl-NaCl-AlCl3 bath was enhanced by initial electrolysis
for a period of seven days in LiCl-NaCl-AlCl3 bath and then
afterwards, progressively changing over to potassium based
bath by bath tapping. The electrode was stable for up to
25 days. Further confirmatory trials are underway.
Process Scale up
Carbochlorination
Concluding Remarks
Aluminium production using chloride route was a subject of
extensive R&D in the period 1960 to mid 1980s when major
aluminium producing companies such as Alcoa had set up
and operated a large demonstration plant. There were tech-
nical and economic challenges to overcome which prevented
it from replacing the Hall-Héroult process.
In the current scenario, in the back of technological
progress in process and material modeling and advanced
instrumentation and control, the perceived advantages of the
chloride route may be realized. The direct bauxite chlori-
nation would eliminate the energy intensive Bayer process
for producing AlCl3 and AlCl3 electrolysis can be conducted
with up to 30% lower energy consumption compared to
Hall-Héroult process.
GSRF has taken up this challenge and concept proof
experiments are favorable in obtaining the perceived
advantages. Further process scale up is ongoing to system-
atically test all aspects of the process.

Process scale up is considered based on the laboratory scale
experiments in a stepwise manner. The approach taken for
carbochlorination and status is shown in Table 5.
AlCl3 Electrolysis
Acknowledgements The authors would like to thank Dr. K.H.
Gharda, the founder of Gharda Scientific Research foundation for
envisioning this project, for his invaluable support and advices and also
for granting permission to publish this paper. The authors would also
like to thank rest of GSRF team members for contributing in the
project.

Electrolysis cell is also scaled up in a stepwise manner from References

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configuration, MOC compatibility and pot operations such
as AlCl3 feeding, metal tapping, moisture management etc.
Once, sufficient data is available, plan is to go for 1000 L
cell as a demonstration unit.
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 Stability of Chlorides in Cryolitic Electrolyte

Xiangwen Wang and Luis Espinoza-Nava

Abstract
Chloride is considered one of the most important contaminants in cryolitic electrolyte
system for aluminum smelting, and yet at the same time, chloride salts such as NaCl,
MgCl2 and others have also been chosen for potential additives to change the electrolyte
physical chemical properties for smelting efficiency improvement. This paper studied the
chloride stability in the cryolitic electrolyte system. The behavior of NaCl and MgCl2 was
investigated when there is a moisture present with or without electrolysis or when there is
anode effect. HCl will be generated along with HF during a normal electrolysis even when
chloride in the electrolyte is at a low level. CF3Cl gas is generated along with CF4 and CxFy
when anode effect occurs. The results confirm that even though chlorides (NaCl/MgCl2) are
considered the most important contaminants, the level of the contaminants remains
relatively low in the smelting electrolyte without obvious accumulation over time.

Keywords
Cryolite Chloride Hall cell Electrolyte stability Hydrolysis Electrolysis Anode
effect

Introduction The cryolitic electrolyte system is also chemically or ther-

Cryolite based electrolyte has been and will continue to be
the only choice for the Hall-Heroult process in aluminum
smelting. The molten fluoride electrolyte system offers the
unique properties that no other salt systems can match as a
solvent to dissolved solid alumina (Al2O3) into ionic forms
so that electrochemical conversion to metallic aluminum
becomes possible. The overall electrolytic reaction is typi-
cally expressed/described by:
1=2Al2 O3 þ 3=4C ¼ Al þ 3=4CO2
X. Wang (&)
L. Espinoza-Nava
Alcoa Corp, New Kensington, USA
e-mail: Xiangwen.Wang@alcoa.com
L. Espinoza-Nava
e-mail: Luis.Espinoza-Nava@alcoa.com
modynamically stable as an inert media. The fluoride compo-
nent is not consumed during the normal electrolysis process.
The cryolite system actually contains many “additives” as
a part of the electrolyte components so that normal electrol-
ysis production can be carried out at a temperature range from
950 to 965 °C. The physical chemical properties are modified
so that the electrolysis proceeds in an efficient way—less
energy consumption, optimal current efficiency and most
process stability and operability. These key properties may
include alumina solubility and dissolution, electrical con-
ð1Þ ductivity, density, surface tension, to name a few. The com-
monly seen additives may include AlF3, CaF2, MgF2, LiF or
other salts. Some of them can be accumulated to a certain
level due to the use of alumina (SGA) which contains a certain
residual levels of the elements in oxide form and converted to
fluoride [1, 2] while some of the additives are intentionally
added [3]. AlF3 is added to maintain a target level of excess
AlF3 and also to neutralize Na2O from the alumina.

© The Minerals, Metals & Materials Society 2017 649

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_80
650
Not commercially applied for aluminum electrolytic
production, chloride electrolyte is another widely used
electrolyte system for other metal productions such as Li,
Na, Mg, Ca and other reactive metals [4]. The typical
electrolytic process can be described:
MeClx ) Me þ xCl2 ðgÞ ð2Þ
As the electrolytic reaction indicates, the electrolyte
component, MeClx, will be continuously consumed by
producing the metal and generating Cl2 gas. Depending on
the metal produced, the chloride electrolyte system may be
composed of one or two other chloride salts as additives
which are more electrochemically stable. The chloride
electrolytes, in general, do not dissolve the metal oxide or
have a limited oxide solubility, any hydrolysis from mois-
tures or hydrates from such as feed would form solid oxy-
chlorides which are undesirable in the process:
MeClx þ yH2 O ) MeOy Clz ðsÞ þ 2yHClðgÞ ð3Þ
The electrolyte system has to be free of moisture (H2O) or
hydrates (OH−) in order to maintain its electrolyte and
process stability.
Chlorides such as MgCl2, NaCl or KCl is reported that
they can be added to the cryolitic system to modify the
electrolyte physical chemical properties [5]. These compo-
nents can effectively reduce the electrolyte liquidus tem-
perature and reduce the electrical resistivity for energy
efficiency improvement. Addition of NaCl to industrial cell
was also reported [6] not only to improve electrical con-
ductivity, but also to increase the capability of carbon par-
ticles separation from the electrolyte. A latest study reported
the NaCl impact on liquidus temperature of the cryolite [7].
A low temperature electrolysis of aluminum oxide using
chloride containing fluoride electrolyte is also reported [8].
All of these studies have no mention of any concerns of
chloride stability as part of the electrolyte media.
During the normal Hall cell electrolysis operations, alu-
mina is continuously fed in the cells. Alumina, depending on
its refinery process, does contain a low level of hydrates (in
forms of AlxOy(OH)z as gibbsite or boehmite or free mois-
ture (Al2O3.XH2O). Once the hydrates are in contact with
molten electrolyte, hydrolysis will occur to form HF [9]:
Alx Oy ðOHÞz þ AlF3 ) zHF þ ð1 þ xÞAl2 O3 ð4Þ
When moisture air happens to be in contact with molten
electrolyte, hydrolysis will also occur:
3H2 OðgÞ þ 2AlF3 ) 6HFðgÞ þ Al2 O3 ð5Þ
Cryolitic as bath vapor product, atmolite, NaAlF4, reacts
with a source of hydrogen, such as water-bound to alumina
during pot feeding [10]:
X. Wang and L. Espinoza-Nava
2NaAlF4 þ 3H2 O ! 2NaF þ Al2 O3 þ 6HFðgÞ ð6Þ
Chloride (NaCl) is considered one of the most important
contaminants in cryolitic electrolyte system. Residual
amount in raw materials can be accumulated to a certain
level because of the relatively electrochemical stableness.
Attempt in recycling cast house dross in which NaCl and
KCl may be present, can bring further complications [11].
To understand the chloride behavior in the cryolitic elec-
trolyte system, special studies were carried out in both
smelter and laboratory. This paper is to report our findings
on the chloride stability in the cryolitic electrolyte system.
Experimental
Chloride Accumulation Test in Industrial Pots
To determine how chloride behaves in smelting pots, i.e.
how the chloride additions impact the chloride concentration
in bath during the normal operation, an 8-pot trial was car-
ried out with addition of various amount of chloride for a
period of three months. 230 KA cells were used for this
special trial. The intent was slowly to establish a certain level
of chloride in bath and then determine how and what to take
to maintain the desired chloride level, and how the chloride
would impact performance. The chloride containing material
(free of water) was preheated and slowly added to pot
through open tap hole. The chloride content was monitored
through periodically bath sampling and analysis. Bath
samples were usually taken one day after the chloride
material addition. The bath samples were then such prepared
for standard XRF analysis.
Laboratory Study on Chloride Containing Bath
Based on the findings in the industrial trial, special follow up
studies were carried out in a laboratory environment under
more controlled conditions. A 150 A electrolysis cell was
setup and used which can carry out multiple tasks inde-
pendently or at the same time:
• Hydrolysis with moisture air
• Electrolysis
• Initiation of anode effect
• Off gas composition analysis.
The setup, as shown in Figs. 1 and 2, consisted of an
electrolytic cell with graphite crucible, TiB2 plate cathode,
graphite anode, alumina tube for passing moistured argon
(Ar) into molten bath, alumina feeding tube, stainless steel
tube for dry Ar (when there was no hydrated Ar used), and
Stability of Chlorides in Cryolitic Electrolyte 651

Fig. 1 Schematic diagram

showing cell set-up for
hydrolysis, electrolysis and
off-gas measurement studies

FTIR

Teflon tubing, and dust filter to extract the off-gases at 1–

Fig. 2 Laboratory setup—electrolysis cell and off-gas FTIR measure-
ment equipment
2 l/min and measuring continuously using a multi-pass
gas-cell based process Fourier transform infrared (FTIR)
spectrometer (CIC Photonics, Albuquerque, NM) equipped
with DTGS detector. Type K thermocouple not shown in
Fig. 1 is inserted in the graphite crucible for bath tempera-
ture monitoring. An external electrical furnace is used for
maintaining the required bath temperature. Hydrated
(moisture) Argon is realized by first flowing Ar through two
water spargers.
An industrial bath (tapped from an industrial cell) with a
typical smelting composition was used without any special
treatment. Chlorides (NaCl and MgCl2) were analytical
grade and used as is without further treatment. For each
batch test, the cell was preloaded with the industrial bath
(and pre-determined amount addition of chlorides) and kept
overnight at approximately 110 °C for drying off free
652 X. Wang and L. Espinoza-Nava

moisture. The cell was then heated up to test temperature
(960 °C) and once the temperature is stabilized, tests began
to carry out all special measurements under targeted test
conditions. The NaCl added in the smelting bath were 0 (as
is), 0.25, 0.5, and 1.0%.
Results and Discussion
Plant Trial Results
The chemical and electrochemical stability of chloride salts
in the cryolitic smelting bath of Hall cells is one of the
critical but basic requisites if any can be used to modify
physicochemical properties of the cryolitic electrolyte. In the
smelting community, it is common belief that chlorides
would be stable and accumulate in the cryolitic electrolyte
because of their relatively high decomposition potential. On
the other hands, some studies in other molten fluoride sys-
tems containing NaCl salt indicate that when higher voltage
or when a high anode current density is applied, Cl2 can
co-generated along with CO2 [12, 13]. Special trials were
carried out in one Alcoa 230 kA smelter by addition of
chlorides in smelting pots to determine the long term accu-
mulation and its impact to pot behavior and performance.
Only the chloride behavior—accumulation in pots is repor-
ted here. Eight pots were used for the trial and they were
divided into four groups (two pots in each group). The
addition was made on weekly basis and lasted for three
month. Figure 3 (Group 1 to Group 4) respectively shows
the expected chloride accumulative addition (dotted line)
versus the real concentration in bath.
All pots started with a residual level of NaCl averaging
around 0.2%. Same amount of the chloride was added to
each pots targeting 0.1% NaCl increase per month as
shown in the graphs (accumulative). The analytical results
of the actual increase was significantly lower and the initial
rate of the increase in each pot was also different. Pots in
group 2 and 3 had a greater increase than pots in group 1
and 4. After a lower than expected increase, all pots
experienced a reduction of the NaCl concentration during
the third month and the NaCl concentration was even lower
than the starting concentration (<0.2% NaCl) at the end of
three months even though the NaCl was continuously
added. The results, contrary to the common belief that
chloride can be accumulated, indicate that the chloride is

0.50 0.50
Group 4 Group 2
0.40 0.40
%NaCl (equivalent)

%NaCl (Equivalent)

0.30 0.30

0.20 0.20

0.10 0.10

0.00 0.00
5/31 6/14 6/28 7/12 7/26 8/9 8/23 9/6 9/20 5/31 6/14 6/28 7/12 7/26 8/9 8/23 9/6 9/20
Months Months
Accumula ve addn Results 2 per. Mov. Avg. (Results)
Accumula ve addn Results 2 per. Mov. Avg. (Results)

0.50 0.50
Group 3
Group 4
0.40 0.40
%NaCl (Equivalent)

%NaCl (Equivalent)

0.30 0.30

0.20 0.20

0.10 0.10

0.00 0.00
5/31 6/14 6/28 7/12 7/26 8/9 8/23 9/6 9/20 5/31 6/14 6/28 7/12 7/26 8/9 8/23 9/6 9/20
Months Months

accumula ve Series3 2 per. Mov. Avg. (Series3) Accumula ve addn Results 2 per. Mov. Avg. (Results)

Fig. 3 Chloride addition and accumulation in bath over the trial period in 230 kA cells: Group 1 and 2 and Group 3 and 4
Stability of Chlorides in Cryolitic Electrolyte
not stable and the concentration may not be able to
maintain at an expected level in the cryolitic smelting bath
during electrolysis.
To follow up the plant trial findings, laboratory studies
were then carried out to investigate the chloride behavior in
the cryolitic bath with and without electrolysis under some
special controlled conditions.
Hydrolysis of Cryolitic Bath
Industrial bath typically contains residual amount of chlo-
rides. The bath used for this study contains 0.097% Cl (0.16%
NaCl). A hydrated Ar was bubbling (sparging) through the
molten bath and resulting off gas composition was analyzed.
The results of the gas composition are shown in Fig. 4.
As shown in Fig. 4, HF(g) is formed as expected once the
moistured Ar in contact with molten fluoride:
2Na3 AlF6 þ 3H2 O ) Al2 O3 þ 6NaF þ 6HFðgÞ ð6Þ
Or
3H2 OðgÞ þ 2AlF3 ) 6HFðgÞ þ Al2 O3
It is interesting to note that about the same magnitude of
HCl(g) was also generated even though only a residual
amount of chloride was present, indicating the chloride
reactivity is significantly higher than the fluoride
components:
NaCl þ H2 OðgÞ ) HClðgÞ þ NaOH
As expected, when the moisture (H2O) is absent (by
turning off the hydrated Ar), both the hydrolysis reactions
and resulting HF and HCl were diminished.
Addition of NaCl in the bath significantly increases HCl
(g) formation while HF(g) maintains a fairly constant.
150
120
HCl and HF, ppm
90
60
30
0 Ar during the hour before electrolysis and the system con-
11:24 11:28 11:32 11:36 11:41 11:45 11:49 11:54 11:58 12:02 12:07 12:11
Time, min
HCl
Fig. 4 Hydrolysis of industrial bath showing generation of HCl and
HF (0 NaCl addition, 0.097% Cl)
653
5.0
4.0
RaƟo (HCl/HF)
3.0
2.0
1.0
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
%NaCl
Fig. 5 Ratio of HCl/HF generation as a function of %NaCl in bath
under hydrolysis conditions
Figure 5 shows the ratio of HCl/HF as analyzed in the gas
stream when moistured Ar was passing through the molten
bath containing varying amount of NaCl.
The result shown in Fig. 5 reveals that even though a
small amount of NaCl presence in bath can generate a few
ð7Þ
times higher of the amount of HF if there is a moisture (H2O)
present, indicating the relatively high reactivity of chloride
with H2O.
Electrolysis with and Without Hydrolysis
in Cryolitic Bath
ð8Þ
Without the presence of free H2O in the system, gas com-
position may reveal another reaction mechanism rather than
hydrolysis under normal electrolysis. Figure 6 shows the
HCl generation along with CO2 (including CO) and HF
before and after electrolysis start. Again the bath composi-
tion contained a residual amount of chloride (as shown in
Fig. 4), no HCl was detected prior to electrolysis. Once
electrolysis started as indicated by the generation of CO2
(and CO), HCl was immediately generated—also shown as
electrolysis was turn off and on, HCl started to drop and then
Off hydrated/
increased again. As the electrolysis continued and off gas
moistured Ar
composition stabilized, HCl was increased to 30 ppm from
residual level while HF was relatively constant at 23 ppm.
Additionally the higher HCl level further indicates the higher
reactivity of chloride than fluoride.
The molten bath was “hydrated” with sparging moistured
tinued to be purged with dry Ar. No alumina was fed during
the electrolysis to make sure no free water is present (alu-
HF
mina concentration was about 3.5%). The HCl and HF
generation had to come from the hydroxyl (OH−) dissolved
in the molten cryolitic bath. It is the electrochemical
654 X. Wang and L. Espinoza-Nava

50 60000 80 80000

50000 70 70000
40
60 60000
HCl and HF, ppm

40000

Co+CO2, ppm

CO2+CO, ppm
30

HCl, HF, ppm

start 50 50000
off 30000
40 40000
20
20000
30 Electrolysis 30000
10 Bubbling start
10000 20 start 20000

0 0 10 10000
12:36 12:40 12:44 12:48 12:53 12:57 13:01 13:06 13:10 13:14 13:19 13:23
Time, min 0 0
13:40 13:48 13:55 14:02 14:09 14:16 14:24 14:31 14:38 14:45
HCl HF CO+CO2 HCl HF CO2+CO

Fig. 6 HCl and HF generation during electrolysis (0 NaCl addition, Fig. 8 Hydrated Ar impact on the HCl generation in the cryolitic bath
0.097% Cl) during electrolysis (No NaCl addition, 0.097% Cl)

60 80000 no HCl (and HF as expected) before electrolysis started.

70000 Once the electrolysis began, HCl and HF in the off gas
50
60000
started to increase along with CO2. The HCl concentration
40 reached as high as 50 ppm while HF was below 20 ppm.
50000
CO2+CO, ppm

The results indicate the cryolitic bath (tapped from an

HCl, HF, ppm

30 40000
industrial cell) contains a certain amount of stable hydroxyl
20
30000 ion (OH−) since it was previously used in electrolysis (fed
start 20000 with SGA ores), and the dissolved hydroxyl can co-exist
10
10000 with Cl− and F− ions at molten state of high temperatures.
Solidification, crushing and remelting processes may not
0 0
10:26 10:30 10:35 10:39 10:43 10:48 10:52 10:56 alter the previously dissolved hydroxyl in the bath. The
HCl HF CO2+CO hydroxyl ions become reactive once electrolysis starts. Since
transforming from OH− hydroxyl to H+ (HCl or HF) does
Fig. 7 HCl and HF generation before and during electrolysis in molten
bath with no NaCl addition and no prior “hydration”
not involve electron transfers, the exact electrodic processes
need further to be understood.
To determine the impact of increased hydroxyl (OH−)
reactions, not the H2O hydrolysis that were occurring during concentration on the formation of HCl and HF, hydrated Ar
the electrolysis. was passing to the molten bath. Figure 8 shows the results of
The complete electrodic reaction may be formulated as HCl and HF formation along with the CO2 generation when
follows: electrolysis started. The magnitude of HCl formation was
6NaCl þ 4AlF3 þ 2AlðOHÞ3 þ 3=2 C increased to as high as 75 ppm and HF was also increased to
) 6HClðgÞ þ 2Al þ 2Na3 AlF6 þ Al2 O3 þ 3=2CO2 ðgÞ 50 ppm. The increase was purely due to the increase of OH−
concentration in the bath and the hydrolysis due to the free
ð9Þ H2O presence.
And similarly, the complete electrodic reaction for gen- NaCl increase in the bath would increase HCl formation.
erating HF may be formulated as follows: Figure 9 shows the HCl and HF evolution as long with CO2
generation when electrolysis started after 0.25% NaCl was
2AlF3 þ 2AlðOHÞ3 þ 3=2C ) 6HFðgÞ þ 2Al þ Al2 O3 added in the molten bath. Addition of NaCl (0.25%) did
þ 3=2CO2 ðgÞ increase the magnitude of HCl formation in hydrolysis and
during electrolysis.
ð10Þ
Figure 10 summarizes the results of HCl/HF ratio as a
To determine if the industrial cryolitic bath contains function of NaCl in bath. Similar to the hydrolysis with
stable hydroxyl ions (OH−), another electrolysis run was moistured Ar, the electrolysis produced the same magnitude
carried out without previous hydrolysis: first the bath was of HCl/HF ratio when NaCl concentration was increased up
pre-dried at 110 °C for overnight, and then melted under dry to 1.2%. The HCl/HF ratio increased from around 1.5 (with
Ar purged condition. Figure 7 shows the HCl and HF residual amount of chloride in bath) to 5 when NaCl was
generation prior to and after the electrolysis start. There were added up to 1.0%.
Stability of Chlorides in Cryolitic Electrolyte 655

80 80000 50 60000
AE ini ated
70 70000

HCl, HF, CF4 and CClF3, ppm

50000
40
60 60000

CO+CO2,ppm
40000
No current

CO2+CO, ppm
HCl, HF, ppm

50 50000 30
30000
40 40000
20
30 30000 20000
Bubbling Electrolysis
start start
20 20000 10
10000
10
Add NaCl 10000
0 0
0 0 13:40 13:45 13:49 13:53 13:58 14:02
15:14 15:18 15:23 15:27 15:31 15:36 15:40 15:44 Time, min
HCl HF CO2+CO HCl HF CClF3 CF4 CO+CO2

Fig. 9 Impact of NaCl addition and H2O presence on HCl and HF Fig. 11 Off gas composition before and during an AE occurrence (0
formation during electrolysis (0.25% NaCl was added prior to NaCl addition, 0.097% Cl)
electrolysis)

6.0 100 180000

160000
5.0
80
140000

4.0 120000
HCl, HF, CF4 and CClF3, ppm
RaƟo (HCl/HF)

60

CO2+CO, ppm
100000
3.0
80000
40

2.0 60000

40000
20
1.0
20000

0 0
0.0 13:26 13:30 13:35 13:39 13:43 13:48 13:52
0.0 0.2 0.4 0.6 0.8 1.0 1.2
HCl HF CF4 CClF3 CO2+CO
%NaCl

Fig. 12 Off gas composition showing CClF3(g) generation in bath

Fig. 10 Ratio of HCl/HF generation as a function of % NaCl in bath containing 0.50% NaCl addition
under the electrolysis conditions

Anode off-Gas Generation During Anodic Effect HF saw a decrease. Surprisingly, a chloro fluoro compound,
chlorofluoro methane (CClF3(g)), was also formed and its
HCl(g) is generated both during hydrolysis and electrolysis
magnitude was comparable with CF4(g) toward the end of
even if there is only a residual amount of chloride present in
the anode effect even though the bath only contained a
the cryolitic bath. Anode effect does occur during the normal
residual amount of chloride.
electrolysis in aluminum production. The chloride behavior
The generation of CClF3(g) may be electrochemically
during the anode effect occurrences is of the interest in this
similar to CF4(g):
section.
Anode effects were initiated in this study by increasing 4AlF3 þ 3NaCl þ 3C ¼ 3CClF3 ðgÞ þ 3NaF þ 4Al ð11Þ
carbon anode current density instead of depleting alumina
concentration during the electrolysis. As shown in Fig. 11, Or chemically:
when an anode effect is initiated, CO2(CO) had a dramatic CF4 ðg) þ HClðgÞ ! CClF3 ðgÞ þ HFðgÞ ð12Þ
reduction while CF4(g) started to be produced. We managed
to pass some current without totally passivating the anode so NaCl addition to bath increases CClF3(g) generation
that enough anode gas could be produced for the gas com- during anodic effect. Figures 12 and 13 show the CClF3(g)
position analysis. As can be seen from the graph, the elec- versus CF4(g) at 0.50 and 1.0% NaCl addition. The peak
trolysis was totally stopped due to the anode passivation ratio of CClF3(g) to CF4(g) is about 2 for both chloride
after 10 min. During the anode effect period, both HCl and concentrations.
656 X. Wang and L. Espinoza-Nava

50 80000 For gibbsites, Al(OH)3:

40 Na3 AlF6 ðlÞ þ AlðOHÞ3 ðsÞ

60000
ð15Þ
HCl, HF, CF4 and HClF3, ppm

! Na þ þ AlOx FZ
y þ AlðOHÞn Fm þ HFðgÞ
l

CO2+CO, ppm
30
40000
20 Na3 AlF6 ðlÞ þ AlðOHÞ3 ðsÞ ! Na þ þ AlOðOHÞn Fl
m ð16Þ
20000 For boehmite, AlO(OH):
10

0 0
Na3 AlF6 ðlÞ þ AlOðOHÞðsÞ
ð17Þ
! Na þ þ AlOx FZ
13:55 13:58 14:00 14:03 14:06 14:09 14:12 14:15
y þ AlðOHÞn Fm þ HFðgÞ
l
CF4 HCl HF CClF3 CO2+CO

Fig. 13 Off gas composition showing CClF3(g) generation in bath Na3 AlF6 ðlÞ þ AlOðOHÞðsÞ ! Na þ þ AlOðOHÞn Fl
m ð18Þ
containing 1.0% NaCl addition
And for gamma phase, (Al2O2.8(OH)0.4):

Discussions Na3 AlF6 ðlÞ þ Al2 O2:8 ðOHÞ0:4

ð19Þ
! Na þ þ AlOx FZ
y þ AlðOHÞn Fm þ HFðgÞ
l
Chlorides (MeClx) have been reported as additives to cry-
olitic bath to modify physical chemical properties for energy
Na3 AlF6 ðlÞ þ Al2 O2:8 ðOHÞ0:4 ðsÞ
efficiency improvement. Some studies and reports (7, 14) ð20Þ
indicate that chlorides (NaCl, KCl, MgCl2, …) are used to ! Na þ þ AlOðOHÞn Fl
m
modify cryolitic based electrolyte for aluminum production.
HCl(g) will be generated in a similar manner by hydrol-
The results from this study do raise questions of the chloride
ysis (reactions 1–20) if chloride is present in the molten
stability as an inert media because hydrolysis, electrolysis
electrolyte. Additional HCl and HF will be generated by
and anodic effect events will generate HCl and CClF3 even
reacting with hydroxyls through electrolytic process as
for a very low chloride concentration condition (*0.1%
described by reactions 9–10. CClF3(g) will be produced
Cl−) when either free moisture or hydrates are present.
along with CF4(g) in the event of anode effect as described
SGA alumina is fed to Hall cells for aluminum produc-
by reactions 11–12.
tion. It is converted from aluminum hydrate (Al(OH)3), by
In summary, the chlorides may not be the choice of
calcining process, and contains a certain amount of water in
additives to the cryolitic electrolyte for aluminum electrol-
different forms i.e. free water (Al2O3.xH2O), gibbsite
ysis because they are not stable in cryolitic fluoride elec-
(gamma-Al(OH)3), boehmite (gamma-AlO(OH)), and
trolyte—both chemically and electrochemically. The results
gamma (Al2O2.8(OH)0.4). SGA provides a constant stream of
also explain that even though chlorides (NaCl and others)
water (or hydrates in forms of H2O or OH−to be specific)
are considered the most important contaminants, the level
during electrolysis. Once the hydrates are in contact with
of these contaminants remains relatively low in the smelting
molten bath, HF (and HCl if molten bath contains any
electrolyte without obvious accumulation overtime. Addi-
chloride) would generate and a certain amount of hydrate
tion of chlorides to the smelting cell may not increase the
would remain in the molten bath. Thermodynamically, the
chloride concentration up to a desired level due to the
OH− may be stable in some sort of complex species:
instability.
When a solid phase alumina (Al2O3) is dissolved in
molten cryolite, the dissolved oxide forms oxofluoroalumi-
nate complex species:
Summary
Al2 O3 ðSÞ þ AlF36 þ ! AlOx Fz
y ð13Þ
Chlorides (NaCl, MgCl2, …) have been considered as
The hydrates associated with alumina would partially potential additives to cryolitic bath for efficiency improve-
form hydroxyl in the molten bath: ment in aluminum production by modifying cryolitic bath
For free water, H2O: physical and chemical properties. The behavior, specifically,
the chemical and electrochemical stability of these chlorides
Na3 AlF6 ðlÞ þ Al2 O3 :H2 OðsÞ
ð14Þ (NaCl) were investigated in this study. Those key learnings
! Na þ þ AlOx FZ
y þ AlðOHÞn Fm þ HFðgÞ
l
are summarized below:
Stability of Chlorides in Cryolitic Electrolyte
• Trial in industrial cells indicates that the cryolitic bath
contains a low concentration (residual level) of chloride
and cannot sustain a certain high level even with con-
tinuous chloride addition.
• Any chloride present in molten cryolitic electrolyte will
be subject of hydrolysis in the presence of moisture
(H2O) to form HCl and up to five times of HF magnitude
when NaCl is at 1.0%.
• Molten cryolitic bath dissolves and contains a certain
level of hydroxyl (OH−) and the hydroxyl can co-exist
with Cl− (NaCl) and be thermodynamically stable with-
out forming either HCl or HF.
• Once the molten salt is energized by passing current under
Hall cell electrolysis conditions, the dissolved hydroxyl
immediately reacts with Cl− and F− and generates HCl and
HF as off-gas along with CO2 and CO even without the
presence of free water (H2O). The presence of H2O pro-
motes even higher formation of HCl during electrolysis.
Higher chloride concentration also results in higher HCl.
Similar to the hydrolysis, HCl can have as high as five
times of HF formation when NaCl is increased up to 1.0%
with or without the presence of free moisture.
• For the cryolitic bath containing even residual amount of
NaCl, any anode effect will result formation of chloro
flouro methane, CClF3, a greenhouse gas along with CF4,
the peak concentration can be as high as two times of
CF4 when NaCl in bath reached to 0.5%.
657
• Chloride is not stable in cryolitic bath and may not be used
as additives in the cryolitic electrolyte for the Hall process.
Acknowledgements Authors wish to thank Mr. Bob Hosler for setting
up and carrying out the experimental work and Alcoa Corp for allowing
to publish this work.
References
1. H. Qin: The characteristics of complex aluminum electrolyte
system. Proceedings of MS10 & AMS 5, Shenyang, China, June
10–14, p. 444. Y. Di et al, in Light Metals 2013, p. 681
2. Y. Di et al., Light Metals 2013, p. 681
3. K. Grjotheim et al., Aluminium Electrolysis—fundamentals of the
Hall-Heroult Process, 2nd edn. (Aluminium-Verlag, Dusseldorf, 1982)
4. Y.I. Dvinin, A.V. Shcherbakov: Tsvet, Met. 39(8), 56 (1966)
5. D. Shi et al., in Light Metals 2013, p. 701
6. J.N. Balaraju et al., J. Electrochem. Soc. 142(2), 439 (1995)
7. K. Osen et al., in Light Metals 2011, p. 263
8. X. Wang et al., in Light Metals 2000, p. 541
9. Y. Yang et al., in Light Metals 2010, p. 277
10. J. Thonstad, E. Sandness, in Molten Salts Chemistry and Technol-
ogy, ed. by M. Gaune-Escard, G. Haarberg (Willey, 2014), p. 3
11. E. Sandness et al., in Molten Salts Chemistry and Technology, ed.
by M. Gaune-Escard, G. Haarberg (Willey, 2014), p. 17.13. L.E.
Dastolfo: US patent 5378325, 1995
12. A. Tabereaux et al., in Light Metals 1993, p. 221
13. P. Duby, Review of developments in electrometallurgy in 1982.
JOM 35, p48 (1983)
14. L. E. Dastolfo., US Patent 5378325, 1995
 Role of Heat Transfer and Interfacial
Phenomena for the Formation of Carbon
Oxides in Smelting Cells

Mark M.R. Dorreen, Nolan E. Richards, Alton. T. Tabereaux,

and Barry J. Welch

Abstract
Thermochemically CO should be the dominant product and various theories have been
proposed to explain the electrochemical dominance of CO2. Following publication of the
proposed correlation between current efficiency and cell gas composition by Pearson and
Waddington [1], smelting operators have considered the presence of high amount of CO to
be a direct indicator of poor cell performance. However substantial deviations occasionally
occur in the gas composition [2, 3] yet the rigour of correlations and reaction mechanisms
interpretation have not been questioned. As a consequence of anode gas composition trends
associated with large multi-electrode smelting cells, and aided by supplementary data, the
mechanistic interpretation for the formation of CO and CO2 during aluminium
electrowinning has been re-analysed. The data indicates interfacial heat transfer to satisfy
the entropic energy plays an important role in determining the proportions of the gas.

Keywords
Smelting anodes Reactions mechanisms Heat transfer

Introduction lowering the proportion of carbon monoxide formed beneath

With the increasing emphasis on lowering energy for
smelting production and the simultaneous need to lower
greenhouse gas emissions associated with anode reactions, it
is important that all conditions are considered when opti-
mising cell operation, including controlling the proportions
of the various anode reactions. While lowering heat loss
from cells by lowering the electrolyte superheat is one way
of lowering cell energy consumption, another would be
M.M.R. Dorreen
LMRC, University of Auckland, Auckland, New Zealand
B.J. Welch
C&M Eng. University of Auckland, Auckland, New Zealand
N.E. Richards
Alton.T. Tabereaux
Independent Consultant, Florence, Alabama, US
B.J. Welch (&)
Department of Chemical Engineering, University of New South
Wales, Kensington, Australia
e-mail: barry@barry.co.nz
the crust of operating cells, as all chemical and electro-
chemical reactions evolving gaseous products require the
supply of extra entropic energy proportional to the volume
of gas released. While some of this energy demand can be
supplied by the reaction over potential, it can also be sup-
plied by interfacial heat transfer, which is also influenced by
electrolyte superheat.
The completion of the electrode reaction when elec-
trowinning requires transfer of a total amount of energy
equal to the enthalpy (DHreaction) of the process across the
electrolyte-electrode interface, even though the reaction can
initiate at any electrode potential exceeds is magnitude
derived from the Gibbs energy (DGreaction) for that reaction
as given by the following equation
DGreaction =nF þ TDSreaction =nF ¼ DHreaction =nF ð1Þ
where TDSreaction is the energy required to satisfy the
entropy of the reaction. n is the number of electrons trans-
ferred, and F faradays constant.

© The Minerals, Metals & Materials Society 2017 659

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_81
660
Some of the energy gap is provided by the electrode
overpotential for that reaction (η reaction), but unless the
overpotential equals or exceeds TDSreaction/nF. Additional
heat transfer is needed. Since gas evolution invariably occurs
at the anode smelting cell anode, the heat transfer require-
ments to satisfy the entropic energy is given by the following
equation
Qtransfer for reaction ¼ TDSreaction  nF greaction
Vogt [4] drew an analogy the interfacial heat transfer can
play an important part in determining the range of electrode
products released. In aluminium smelting cells the situation
is complicated by heat conduction away from the surface
because of the anode heat loss, so the anode interface is
usually at the temperature below that of the adjacent elec-
trolyte. However the temperature gradient will be less than
the operating superheat, as otherwise some electrolyte
freezing would occur.
As seen in Table 1, the thermochemistry of all reactions
leading to formation of carbon oxides have significant gaps
between the Gibbs energy required for enabling reactions
and the enthalpy for completion of reaction and if the
electrode potential exceeds that for initiating another reac-
tion parallel reactions will occur at a rate the dependent on
the heat transfer and reaction mechanism. (It should be noted
that consistent with general trends. in subsequent discussions
the potential of the cathodic reaction of the cells is arbitrarily
set at 0 V since the cathode reaction is the same for all
reactions, and known to show limited polarisation.)
Various laboratory measurement techniques coupled with
cell gas analysis have been used to propose mechanisms for
the reaction occurring at the anode during various stages of
Table 1 Thermochemical analysis for the initiation and completion of the various reactions
Eqn. DG
# Over-potential
Reaction kJ/mol
Al2O3
Electrochemical
3 Al2O3  3C = 2Al + 3CO(g) 621.5
4 Al2O3  1.5C = 2Al + 1.5CO2(g) 689.6
5* 1/2 Al2O3  Na3AlF6(1) + 9/4 1029.6
C = 2Al + 3/2CO(g) + 3/4CF4(g) + 3NaF
Chemical
6 C + CO2(g) = 2CO(g) −52.2
7 2Al (diss.) +3CO2(g) = Al2O3 + 3CO(g) −754.7
8 1/2 Al2 + Na3AlF6(1) + 3/2 1068.0
C = 2Al + 3/2COF2(g) + 3NaF
9 3/2COF2(g) + 3/4C = 3/2CO(g) + 3/4CF4(g) −38.4
*Reaction 5 is a depolarized combination of following reactions (8 = Electrochemical, 9 = Depolarizing Chemical)
M.M.R. Dorreen et al.
the electrolysis including cycling and sweep voltammetry,
chronopotentiometry (with and without current reversal),
electrode impedance measurements and steady state
voltammetry. Within this range there are also differences
associated with experimental cell design and DC equipment
usage, such as whether performed under electrode potential
control (both with and without ohmic compensation), cell
voltage or current control, or applied power limited. There-
ð2Þ fore small subtle differences in results appear.
However the mechanistic interpretation has been preju-
diced towards steady state current versus voltage changes
where the dominant result is associated with the anode
potential. Several authors have concluded that the anode
overpotential follows Tafel behaviour [5–8] with the rate
being controlled by activation energy associated with a
charge transfer step. However both Haupin [5] and Dewing
et al. [8] considered there were two different controlling
steps depending on operating current density.
As a consequence of these publications various concepts
have been developed and subsequently presented as fact—
such as “carbon dioxide is the primary anode product”—
even though publications have acknowledged that a low
current densities carbon monoxide can be the dominant
product. The presence of the carbon monoxide is generally
attributed to generation by Eqs. 6 and 7 of Table 1. Devia-
tion from Tafel behaviour at high current densities has been
solely attributed to concentration polarisation through
depletion of the interfacial alumina concentration, even
though the current voltage curve does not exhibit the clas-
sical shape for a limiting current. In mathematical models the
current density associated with the transition to fluorocarbon
co-evolution when under constant current control the
DH Einitiation ¼ DG =6F EIsothermal ¼ DH =6F Q deficit at g V
kJ/mol Volts Visothermal kJ
Al2O3
1350.9 1.074 2.333 729.4–580* g
1098.6 1.191 1.890 477.1–580* g
1525.8 1.778 2.636 904.3–58* g
167.8
−846.4
1433.7 1.845 2.476
92.0
Role of Heat Transfer and Interfacial Phenomena …
“critical current density” at which an anode effect is initiated
has been interpreted as being synonymous with the limiting
current.
Within the combined studies and conclusions there are
several inconsistencies, such as:
– Why there is a transition at very low current densities
from CO evolution to CO2 co-evolution even though the
same oxy-anion is involved?
– Why does the CO2 readily react chemically with carbon
to evolve CO whereas its formation electrochemically is
considered to be inhibited?
– Why during an anode effect, does the CO content of the
cell gas dominate over CO2 [3, 9]?
In reviewing the past literature, it also becomes evident
there has also been mechanistic contributors ignored. For
example the role of interfacial heat transfer has not been
considered, nor has the role of the possibility of full or partial
passivation of the anode surface as a contributor to the anode
polarisation. The persistent use of the critical current density
(CCD) as an apparent measure of the limiting current is also
erroneous as the phenomena that generates the CCD is a
consequence of change in electrode reaction involving dif-
ferent anions. The coevolution of CF4 at normal operating
voltages leading to the “background PFC’s” which simul-
taneously bring about an increase in CO formation [11, 12]
is also inconsistent with existing mechanistic interpretations.
The electrode potential at which the transition to CF4
coevolution occurs is significantly below that necessary for
the normally assumed anode effect reaction as given by the
equation
4=3 Na3 AlF6 ð1Þ þ C ¼ 4=3 Al þ CF4 ðgÞ þ 4 NaF(1) ð10Þ
which is predicted to initiate at approximately 2.54 V.
Consequently it is timely to re-analyse the interpretation
of the anodic processes. This paper focuses on the electro-
chemically induced formation mechanisms for CO and CO2
gases, whereas the co-evolution of fluorocarbons is dealt
with elsewhere [10].
Experimental Results of Relevant Studies
The data presented below is a combination of previously
unpublished research results both linked with publications
and previously retained for sensitive reasons, and a
re-examination of results previously presented—especially
in regard to the heat transfer conditions. In comparison with
smelter cells the laboratory cells have quite different control
and heat transfer conditions existing during experimentation
because of the methodology of heating (external versus
internal) and design conditions. These include the smaller
661
size of test electrodes which lower heat loss rate, larger
electrolyte volume per unit electrode area, and much higher
superheat. All of these change the interfacial heat transfer
and cell conditions.
Four different laboratory and plant studies are included.
These are (a) measurement of the changes in interfacial
anode potential as a function of alumina concentration and
current density when determined under “power control”,
(b) both plant and laboratory studies of the anode gas
composition changes with different heat transfer conditions,
(c) an investigation of the role played by anode baking has
on the gas composition at different current densities.
Anode Overpotential Measurements & Results
The apparatus developed for these studies has been descri-
bed in detail elsewhere [6]. Key features included using a
boron nitride encased CO/CO2 reference electrode with a
Luggin capillary positioned against the working anode
electrode without interfering with the current flux field. The
working electrode of approximately 1.25 cm2 surface area
was high purity graphite encased in boron nitride giving a
vertically oriented surface enabling free gas release. An
isolated voltage sensing probe connecting to the insulated
electrode ensured absence of ohmic contributions to the
voltage associated with the resistance of electrolyte and the
electronically conducting circuitry.
An adjustable DC power supply was connected to the
cell through a high resistance variable rheostat. The
combination of the adjustable voltage and the rheostat in
series with the cells enabled measurements to be con-
ducted under a pseudo “power control” mode whereby
for each setting change both current and total cell voltage
also changed. The resulting current and anode potential
change for each setting were recorded on an XY recorder
fitted with a logarithmic converter unit for the current after
each incremental change in the power applied to the
externally heated cell. The standard procedure was to
slowly increase the current by reducing the external
resistance and simultaneously record the trace. After each
increment there was a pause to ensure steady state con-
ditions were achieved.
Care was taken to avoid introduction of any impurities,
with handpicked Greenland cryolite being used as the base
solvent, and the highest purity grades of LiF, AlF3, CaF2,
and Al2O3 being used after drying to ensure absence of any
moisture. As an added crosscheck, the electrolyte was also
subject to pre-electrolysis using an auxiliary electrode.
A typical curve resulting from increasing the applied
power to the cell and subsequently reducing it are presented
in Fig. 1, for a solvent electrolyte of Na3AlF6 + 8.5% CaF2
containing 9.2 wt% of dissolved alumina at 982 °C.
662 M.M.R. Dorreen et al.

Other curves with different solvents also show similar

Fig. 1 The anode overpotential measurements for increasing and
decreasing current for a solvent electrolyte of Na3AlF6 + 8.5% CaF2
containing 9.2 wt% of dissolved alumina at 982 °C
trends and hysteresis with the inflection diminishing as the
temperature increased, but always being more pronounced
for electrodes that had no prior electrolysis.
Electrode polarisation measurements recorded at 1012 °C
at higher current densities where more classical deviation
from the apparent Tafel behaviour due to concentration or
surface coverage effects is to be expected is presented in
Fig. 3 for a range of alumina concentrations. In generating
each curve the power input to the cell was increased slowly
with pauses at approximately 0.5 V increments by varying
an external resistance interfaced to the DC power supply.
The power increases continued until an anode effect occur-
red, the anode effect being indicated by the dashed line and
characterised by wildly swinging voltages and current as a
consequence of the power constraints.
The magnitude of the apparent overpotential exceeds the
voltage increase expected for an AE according to Eq. 1.
Based on the experimental conditions and measurement
procedure these recorded “overpotential” curves can include

Fig. 2 The temperature dependence of anode overpotential in an

equimolar solvent of Na3AlF6 + Li3AlF6 electrolyte saturated with
alumina

This over potential curve shows a “hysteresis” which was

commonly observed for either new electrodes having their
first electrolysis cycle, or for the same electrode after a
significant pause at the rest or reversible potential. It is noted
that the decreasing current curve tends towards a single
electrode process Tafel behaviour but the curves invariably
showed a small deviation in the current density range 0.05–
0.1 A/cm2 as can be seen from careful examination.
Figure 2 presents curves at two temperatures when using
conditioned electrodes in an equimolar solvent of Na3AlF6 +
Li3AlF6 electrolyte saturated with alumina. These curves
show a similar but less distinct inflection occurring at a
higher current density as the temperature is increased.
Superimposed on part of these curves is the Tafel curve
originally interpreted when assuming the data points that
generated the deviation was experimental error due to trace Fig. 3 Anode overpotential measurements in molten cryolite at 1012 °C
impurity which is surprising in view of the care taken to as a function of alumina concentration at high current densities under
eliminate such impurities. voltage constrained power control
Role of Heat Transfer and Interfacial Phenomena …
an ohmic polarisation contribution at the electrode inter-
face if a resistive intermediate layer is formed. Such resis-
tance would reflect surface coverage.
It is clear that the alumina concentration in the electrolyte
also plays a part in the increase in anode potential, even
though none of the curves progress to a classical limiting
current.
Based on more recent information [10, 11] at higher
overpotential when co-evolution of PFC’s initiate, the cur-
rent decreases and this is consistent with an increasing sur-
face coverage due to a reaction intermediate product existing
before release of the final product. Presumably this is formed
from the fluoride anion discharge. The trends in the curves
are consistent with this change.
Results from Laboratory Studies of Gaseous
Anode Products
As part of an independent study of parameters influencing
current efficiency [12] an oxygen balance approach was
adopted using an apparatus designed and operated to min-
imise secondary reactions of CO2 electrochemically formed
in the cell by screening the cathodic crucible sidewalls and
emergent part of the anode with boron nitride as illustrated in
Fig. 4. A well baked plant anode specimen was used as the
anode with a downward facing, horizontally oriented elec-
trode area of approximately 70 cm−2. This was encased in a
200 mm OD sealed Inconel can enabling all gases released
Fig. 4 The 50–100A laboratory cell arrangement for quantitative
collection and analysis of anode gases
663
from the cell to be captured and transported directly to a gas
analyser via a controlled but fast flowing argon cover gas,
thus enabling a quantitative mass balance of all elements and
gaseous components.
The experimental procedure involved electrochemical
depletion of a fixed mass of alumina until an anode effect
occurred.
Figure 5 presents the change in the CO/CO2 ratio during
the electrochemical depletion of the alumina at 1.1 Acm−2
from the starting concentration of 6.0 wt% Al2O3 in a sol-
vent giving a liquidus temperature of 959 °C for the solu-
tion. Because of the size of the container the cell temperature
changes during electrolysis because of the resistive heating
during the electrolysis changed the temperature experiment.
This increased the superheat of the electrolyte significantly
from the starting value of 14 °C as shown in Fig. 5.
After the first few minutes of the measurement sequence,
and continuing until just before the anode effect, the oxygen
balance gave a constant current efficiency of 84.5 ± 0.5%.
However the temperature versus time trace displayed a
steady increase in the proportion of carbon monoxide.
During this period the superheat increased from its initial
value of 14 °C to more than 20 °C and therefore there would
be an increase in the driving force for heat transfer from the
electrolyte to the electrode.
It is interesting to note that if the current efficiency were
calculated from the CO to CO2 ratio using the Pearson and
Waddington equation the electrolysis would have started at
less than 80% and steadily decreased to less than 70%.
However the oxygen balance approach is rigorous because
there are no other sources for the oxygen measured, while
the steady increase in rate of evolution of CO indicates other
causes. A more substantial increase in CO evolution at the
expense of the rate of evolution of CO2 occurred in the last
10 min of the electrochemical depletion.
Fig. 5 The trends in both temperature and CO/CO2 ratio as the
alumina concentration is electrochemically depleted in the laboratory
cell
664
Fig. 6 The variation in the ratio of CO/CO2 as a function of current
density for plant anode samples with different inherent reactivity
A second sequence of gas analysis studies has been
conducted under conditions of constant alumina concentra-
tion, but using anode’s produced with varying heat treatment
conditions and a slightly modified experimental arrangement
as has been described in detail elsewhere [13]. This study
was to enable assessment of the role of the carbon structure
as a consequence of heat treatment has on the anode gas
composition. Each specimen was characterised by the stan-
dard ISO-N804 method for the carbon dioxide reactivity
residue (RR) method prior to electrolysis. However the
results presented are expressed as reactivity calculated by the
formula (100- RR). The experiments were carried out in a
standard industrial electrolyte saturated with alumina at
975°C, thus having a high superheat. The experimental
procedure was to set the operating current density to deter-
mine the steady state gas composition as represented by the
ratio of CO–CO2. Then the current was stepped to a new
current density. A sequence of the results obtained is pre-
sented in Fig. 6.
Figure 6 shows that even for the well baked low reac-
tivity carbon anode there is a dramatic increase in the rate of
generation of CO at current densities below 0.15 Acm−2.
This increase can only be explained by an electrochemical
contribution with direct formation of CO rather than through
back reaction with CO2. The increase in CO with anode
reactivity may have a significant contribution from the
higher real surface area of the under baked carbon or the
more disoriented structure of the graphite crystallites.
Plant Studies of Gas Evolution
As described elsewhere [3] samples of the gas being evolved
from anodes of operating cells during electrochemical
depletion of the dissolved alumina concentration have also
M.M.R. Dorreen et al.
Fig. 7 The trend in CO/CO2 ratio before and after AE’s in three
different operating cells
been collected and analysed at various time intervals during
normal operation and through anode effects for three well
operated smelting cells. The gas compositions showed
matching trends to those described for the above laboratory
study. Similar increases in carbon monoxide during anode
effects have been reported by Holliday and Henry [9] who
also made special mention of the fact that the carbon
monoxide concentration increased several minutes before
the anode effect occurred. (Fig. 7).
In all the gas evolution studies, whenever there was an
increase in anode potential, and hence an enhancement in
heat transfers, there was an accompanying increase in carbon
monoxide concentration.
Discussion of Results
As noted in the introduction heat transfer was not included
as a consideration in earlier mechanisms proposed and
therefore we have re-examined mechanisms in an attempt to
resolve the anomalies highlighted, and to also give more
consistent conformity with the data trends presented here.
It is generally accepted that alumina dissolves by an
endothermic process to form a complex, and numerous
reactions and resulting ionic species have been proposed
such as:
Na3 AlF6 ðliquidÞ þ Al2 O3 ðsolidÞ , 3Na AlOF2 ð11Þ
or
2Na3 AlF6 ðliquidÞ þ 2Al2 O3 ðsolidÞ , 3Na2 Al2 O2 F4 ð12Þ
Hence the oxide anion exists in the molten electrolyte as a
complex such as AlOF2− or Al2O2F42−. Irrespective of the
form they will be in some dissociation equilibria but for
convenience the mechanism development we work on the
basis of it being AlOF2−.
Role of Heat Transfer and Interfacial Phenomena …
The sequence of experimental results presented here gives
strong evidence towards a significant direct electrochemical
formation of CO with a combination of the carbon
structure/reactivity and heat transfer conditions playing an
important role in determining the resulting proportions evolved.
The consistent increase in the proportion of CO evolved
for experiments with increased heat transfer rates indicates
this can be the rate limiting feature for CO formation.
Furthermore since the same anion is involved for the formation
of both CO and CO2 and some polarisation of the CO evolution
reaction occurs at very low current densities as a consequence
of surface coverage with the reaction intermediate appears to
also play a part.
The anode overpotential results demonstrate there is
clearly a change in the kinetics of the electrode processes
(and probably anode product) soon after the potential
achieves the reversible value expected for CO2 formation.
There are clear indications the second process (presumably
CO2 formation) obeys Tafel’s law before some other form of
reaction rate limitation cuts in. As discussed in the mecha-
nisms proposed below, within that Tafel zone the kinetics of
the reaction can be controlled by a charge transfer step but
would involve the same anion as for CO formation.
Accordingly the following two generalized mechanisms,
operating independently or in parallel, are proposed.
For CO(g) Formation
The following two steps would be involved in the reaction
mechanism.
AlOF þ
2 þ xC $ Cx O þ 2e þ AlF2 ðStep1Þ
Cx O þ QCO ! COðgÞ þ ðx  1ÞC ðStep2Þ
where QCO is the magnitude of heat to be transferred beyond
that provided through the polarisation.
If the first step is rate limiting Tafel behaviour would be
expected, and the slope of the semi-logarithmic overpotential
curve (dη/dln i) correspond to RT/2bF where R is the uni-
versal gas constant, T the absolute temperature, F is faradays
constant and b the symmetry factor for the activation energy
which is expected to be approximately 0.5.
However no linear portion is evident prior to the second
process cutting in, thus supporting the second step being rate
determining. Consequently there would be a strong influence
from the heat transfer rate across the electrode interface, and
hence the driving temperature gradient.
In contrast the rate of Step 2 could be controlled by either
the heat transfer or the bond rapture of the carbon atom from
its stable crystal structure. In the latter case this would lead
to an increased surface coverage of the intermediate as the
665
current is increased. The rate of the latter would decrease
with heat treatment and hence the more graphitic the struc-
ture as has been observed in the data presented in Fig. 6.
However at higher current densities, and hence for higher
evolution rate, heat transfer could become dominant.
For CO2 Formation
(g)
The following three steps would be involved with the first
step being the same as the first step for carbon monoxide
formation:
AlOF þ
2 þ x C $ Cx O þ 2e þ AlF2 ðStep1aÞ
AlOF þ
2 þ xC $ OCx O þ 2e þ AlF2 ðStep2aÞ
OCx O þ QCO2 ! CO2 ðgÞ þ ðx  1ÞC ðStep3aÞ
where QCO2 is the magnitude of heat to be transferred
beyond that provided through the polarisation.
For the three illustrated polarization curves in Figs. 1 and
2 the Tafel slopes beyond the small limited polarisation
inflection give a symmetry factor of 0.5 ± 0.03 when Step
1a is assumed to be rate determining, whereas the theoretical
slopes for Step 2a—(RT/2(1 + b)F—does not give a real-
istic fit. The curvature at the high current densities is likely
to have a contribution from concentration polarisation due to
depletion of the oxide anion in the electrolyte, and/or
build-up of the anode surface reaction intermediate accord-
ing to Step 2a and heat transfer.
Figure 8 depicts the scenario for the possible mechanisms
based on an ordered graphitic structure of carbon.
The relatively fast discharge of an oxy-anion on the
surface as is evident from the Tafel slope during carbon
dioxide formation, indicates that a high degree of surface
coverage could exist at the electrode interface from the
polarisation when CO is the only product. However for the
gas release it requires the residual entropic energy and rup-
ture of the relatively stable C–C bonding of the graphitic
structure as highlighted by the dashed oval shape, and this
step is likely to require an activation energy.
By contrast the discharge of the second oxy-anion that is
attached to the same carbon atom as depicted on the
right-hand side would lead to a structure that is readily
released.
Heat Transfer and the Proportion of Gases
The gas analysis results clearly demonstrate that when the
magnitude of the energy required for completion of reaction
increased by either raising the superheat or increasing the
666
Fig. 8 Depicting the potential
surface coverage and reaction
intermediate associated with CO
formation (left hand side) and the
pre-release intermediate for CO2
on the right-hand side
anode potential the proportion of carbon monoxide in the
cell gases increase.
The gap between the energy provided by the anode
electrode potential gradient and that required by the ther-
mochemistry of the reactions diminishes as the anode
potential increased.
Using the anode overpotential curves and Table 1 rela-
tionships the actual production rate of the gases can be
predicted. Therefore we can estimate the required interfacial
heat flux required for completion of the reactions at different
electrode potential levels. The calculated heat flux for pro-
ducing either CO or CO2 is presented in Fig. 9.
These curves show that while the flux requirements are
not substantial at potential below carbon dioxide evolution,
Fig. 9 Interfacial heat flux requirements to satisfy thermochemistry for
pure gas evolution at the current densities indicated by the polarisation
curve at 967 °C
M.M.R. Dorreen et al.
it would soon become quite substantial if CO continued as a
dominant product.
In a situation where there is competition for the heat flux
between both gases, the requirements for CO2 would be
more easily satisfied—thus the higher proportion of this gas.
It should be noted that the typical heat flux at sidewalls of
smelting cells is about 6 kWh m−2. Conditions that deter-
mine the heat flux at the anode would be similar. The dif-
ference being the electrode interfacial heat flux must also
satisfy some of the cell top heat losses, reducing the amount
available for reactions.
The gas analysis data of this study highlights that the ratio
of carbon monoxide to carbon dioxide changes with current
density and the associated interfacial electrochemical
potentials.
By using typical compositions of cell gases analysed in
both the plant studies and also the laboratory cells such as
illustrated by the well baked anodes of Fig. 6, we can also
Fig. 10 Estimates of the reaction heat fluxes for typical anode gases
evolved cells as a function of anode potential
Role of Heat Transfer and Interfacial Phenomena …
estimate the heat flux required to satisfy sustaining both
reactions in the proportions expected. This analysis is pre-
sented in Fig. 10.
The Transition to Co-evolution of PFCs
The data presented in Fig. 3 presents an excellent analogy to
the situation that exists as an individual anode in the modern
smelters cell, since cell voltage changes for each anode are
constrained by the parallel circuitry that exists between the
anode beam and the metal pad for each anode. However the
current can be redistributed to the other anodes.
The apparent anode potential increases to values that
exceed that necessary to evolve PFC’s and thus transition to
an anode effect without the constraint. However the mea-
surement technique would incorporate the ohmic resistance
voltage drop of any surface film formed on the anode sur-
face. Although many consider that an anode effect is due to
de-wetting phenomena on the anode surface both Calandra
et al. [14] and Dorreen et al. [10] have clearly demonstrated
that a highly resistive passivating film is formed on the
anode during an anode effect. Therefore as this builds up it
would increase the resistance and hence the “ohmic over-
potential” contribution. This would then provide the extra
heat at the interface needed to complete the energy transfer
for gas release—which is higher when PFCs are coevolved.
This further emphasises the importance of anode interfacial
heat transfer.
Conclusions
It is clear that CO is electrochemically coevolved in alu-
minium smelting cells, but the kinetic rate of its evolution is
influenced by the interfacial heat transfer. Since the energy
required for the equivalent amount of CO2 to be released is
much less and hence will dominate when both reactions are
enabled.
Based on this current efficiencies calculated according to
any equation based on the proportions of gases can be quite
unreliable.
667
However the correlation is also present warnings on
limitations in reducing superheat in order to lower heat loss
and therefore energy consumption, especially when operat-
ing at high current densities.
References
1. T.G. Pearson, J. Waddington, Discuss. Faraday Soc. 1, p307
(1947)
2. E.A. Hollingshead and Braunwarth, in Proceedings AIME Inter-
national Symposium on Aluminium, vol. 2, pp. 31–50, 1962
3. A.T. Tabereaux, N.E. Richards and C.E. Satchel, Composition of
reduction cell gas during normal conditions and anode effects.
Light Met. 325–333 (1995)
4. H. Vogt, Heat transfer in boiling and mass transfer in gas evolution
at the electrode’s the analogy and its limits. Int. J. Heat Mass
Transf. 59, 191–197 (2013)
5. W.E. Haupin, J Electrochem. Soc. 103, 174 (1956)
6. N.E. Richards, and B.J. Welch, Anodic overpotentials and
mechanisms of the anode process on carbon in cryolite-alumina
electrolytes, in Proceedings 1st Australian Conference on Elec-
trochemistry, ed. by Gutmann and Friend (Pergaman Press),
pp. 901–922 (1964)
7. J. Thonstad, Electrochim. Acta 15, 1569 (1970)
8. E.W. Dewing, E.T. van der Kouwe, J. Electrochem. Soc. 122, 358
(1975)
9. R.D. Holliday and J.J. Henry, Industrial & Engineering Chemistry.
31, 1289–1292 (1959)
10. M.M.R. Dorreen, M.M.Hyland, R.G. Haverkamp, J.B. Metson, Ali
Jassim, B.J. Welch &. A.T. Tabereaux, Co-evolution of carbon
oxides and fluorides during the electrowinning of aluminium with
molten NaF-AlF3-CaF2-Al2O3 electrolytes. Light Met. (2017 at
press)
11. A. Jassim, S. Akhmetov, B.J. Welch, M. Skyllas-Kazacos, Jie Bao,
& Yuchen Yao, Studies of background PFC emissions in
Hall-Heroult cells using online anode current signals. Light Met.
546–550 (2015)
12. M.M.R. Dorreen, M.M. Hyland, and B.J Welch, An improved
method for current efficiency determination in a laboratory
aluminium cell. Light Met. 1189–1193 (1997)
13. S.M. Hume, M.R. Utley, B.J. Welch, R.C. Perruchoud, The
influence of low current densities on anode performance. Light
Met. 1992, 687–692 (1992)
14. A.J. Calandra, C.E. Castellano, C.M. Ferro & O. Cobo, Experi-
mental and Theoretical analysis of the Anode Effect in Industrial
cells. Light Met. 345–358 (1982)
 Part XVI
Aluminum Reduction Technology:
Modelling and Cell Design
 Improving the Understanding of Busbar
Design and Cell MHD Performance

Alexander Arkhipov, Abdalla Alzarooni, Amal Al Jasmi,

and Vinko Potocnik

Abstract
Good busbar design is of paramount importance for aluminium reduction cell performance.
Busbar design impacts cell magnetohydrodynamic (MHD) stability, without which it is
difficult to achieve high current efficiency and low energy consumption, since instabilities
enhance the rate of back reaction and make pot control more difficult. Many aspects of
busbar design and MHD stability are still grey areas where cell designers do not have full
confidence because MHD criteria are still rather qualitative. EGA has developed cell design
capabilities, including busbar design. During the last six years, EGA has developed about
ten busbar designs for new and retrofit potlines. In some cases, the constraints led to
sub-optimal busbar design for cell stability in practice. This experience enhanced our
understanding of busbar design, MHD modelling and measurements, which we share in this
paper. We also discuss criteria for busbar temperature, current density and vertical magnetic
field distribution.

Keywords
Cell design Aluminium electrolysis cells MHD Busbar design

Introduction Many articles have been written on busbar design and

It is well known that busbar design is one of the most
important aspects of cell design since it has great impact on
cell MHD stability. MHD instabilities are defined as oscil-
lations of metal-bath interface, driven by electromagnetic
forces. They increase the rate of back reaction leading to
current efficiency loss and also make alumina-feeding con-
trol difficult.
MHD of aluminium reduction cells is still not a very
precise science and many aspects of busbar design are grey
areas where designers have to use step-by-step experience
based on past designs.
A. Arkhipov (&)
A. Alzarooni
A.A. Jasmi
V. Potocnik
Emirates Global Aluminium (EGA), Jebel Ali Operations,
PO Box 3627 Dubai, UAE
e-mail: arkhipov@dubal.ae
modelling, but not many have discussed practical aspects
and industrial experience of different busbar designs.
EGA is very active in smelter expansions as well as in
upgrading existing technologies, aiming to achieve greater
production and lower specific energy consumption. This has
given the EGA modelling team a great opportunity to
implement many busbar designs in the past few years. Some
of these are new designs such as DX + , DX + Ultra and DZ
Technologies; and others are upgrades of old technologies,
such as D18 + and D20 + Technologies. During the last six
years, EGA has developed (modelled and engineered) about
ten busbar designs for new and retrofit potlines. Seven of
these have been built and tested in practice; another two will
hopefully be tested in the future. The experience gained
from industrial tests increased our understanding of busbar
design and its limits. In this paper we will not focus on the
modelling techniques, but rather discuss our observations on
how the busbar designed by modelling performed in
practice.

© The Minerals, Metals & Materials Society 2017 671

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_82
672
MHD modelling and representation of various vectors,—
such as electrical current density, magnetic field, electro-
magnetic force and metal and bath velocities—require a
coordinate system, which is defined in this paper with:
• x—longitudinal direction,
• y—transverse direction in the sense of potline current,
• z—vertical direction upwards,
• The centre in the middle of the cell on the top of cathode
carbon block.
The discussion in this paper is limited to MHD modelling
and busbar design with MHD-VALDIS software package,
since it calculates simultaneously all the MHD parameters
discussed here [1]. Metal velocity patterns have been shown
earlier [2] and will not be discussed here since the previously
proposed criteria are used [3]: Preference for small veloci-
ties, small circulation pools, symmetric pools with respect to
the transverse axis of the cell.
The following MHD modelling parameters and busbar
characteristics will be discussed:
1. Collector bar current distribution,
2. Busbar temperature and current density,
3. Vertical magnetic field influence on MHD behaviour of
the cell,
4. Metal-bath interface deformation (metal heave).
Collector Bar Current Distribution
Ideally, current through each collector bar should be the
same. In reality this cannot be achieved because it is not
practical to create an individual equal-resistance path from
each collector bar to the equipotential point between
upstream (US) and downstream (DS) busbars. The difference
in currents between collector bars generates horizontal
Fig. 1 Narrow range of collector
bar currents in low amperage cell
(left), compared to wider range in
high amperage cell (right). NC is
collector bar number
A. Arkhipov et al.
currents in the metal pad. The difference between the US and
DS collector bar currents generates transverse current, Jy,
across the longitudinal axis of the cell. The difference
between collector bars on one side of the cell (US or DS)
generates longitudinal currents, Jx. As known, electromag-
netic (Lorentz) force is generated by vector product of cur-
rent density J and magnetic induction B:
F¼JB ð1Þ
The most significant component of the magnetic field for
cell stability is Bz because it creates the wave-driving force
with horizontal currents Jx and Jy, which are generated by
the busbar design, pot operation (such as anode change) and
by the waves. Jy and Bz create longitudinal force, Fx, which
is the most disturbing. From this point of view, the balance
between the US and DS collector bar currents should be very
important. Reference [4] proposes that US and DS partition
should be within the range of 48–52% and additionally, that
the coefficient of variation (COV) of all collector bar cur-
rents should not be greater than 10%.
In the past, EGA criteria for collector bar current distri-
bution as designed were stricter than mentioned above:
US/DS current partition was required to be within 49%–51%
and the difference between maximum and minimum current
not greater than 1 kA. These criteria were easily achieved in
the past for D18 + Technology or D20 + Technology cells,
which operate at amperage up to 270 kA (Fig. 1).
Nowadays, it is more and more challenging to satisfy
these criteria in high amperage, low energy cells due to a
combination of factors: Low resistance graphitised cathode
blocks, low resistance collector bar design and much longer
cells. Low resistance of the cathode assembly reduces its role
as an equaliser of collector bar currents and more precise
busbar design is required to achieve uniform collector bar
current. At the same time, there may be more separate paths
from collector bars to equipotential points, but cell–to-cell
distance has to be small for better economics, which limits
Improving the Understanding of Busbar Design and Cell MHD … 673

Table 1 Impact of cell design on Previous cell New cell Consequences for uniformity of collector bars current
collector bar current uniformity generation generation
Amperage, 200–300 400–700 -
kA
Length, m 8–10 14– > 20 Longer path from US side,
more collector bars ->
more separate paths required - > more space between cells
required
Width, m 4.3–4.6 4.8–5 Wider cell at same cell-to-cell distance - > reduces space
Cell-to-cell 6–6.1 6–6.3 between cells - > less separate paths
distance, m
Cathode Amorphous, Graphitized Lower cathode assembly resistance - > higher current
blocks graphitic variation - > more separate path required
material
Collector bar Steel Copper Lower resistance - > higher current variation - > more
design inserts separate path required

the space available for busbar paths (Table 1). This issue can
be avoided or minimized by using busbar design with, so
called, External Compensation Current (ECC), Combined
Compensation Current (CCC) or Reversed Compensation
Current [5]. However ECC and CCC have big drawback
since they need external compensation loops. RCC design is
only at the concept stage and needs more complete detailed
study. These considerations led to shifting the US/DS busbar
equipotential point from the base of the risers in DX Tech-
nology and DX + Technology to the anode beam in DX +
Ultra Technology, using so-called “split” anode risers [6].
The collector bar currents on each side of the cell are also
determined by local equipotential points as shown in Fig. 2.
A larger number of collector bars, connected to the same
equipotential point gives a larger difference between the
maximum and minimum collector bar currents.
Taking into account the factors described above, more
tolerant criteria for collector bar current distribution were
used for the busbar design of new high amperage, low
energy cells; but these are still stricter than mentioned in [4].
Even though the difference between the maximum and
Equipotential
point for US and
DS collector
Equipotential
points for US
collector bars
Fig. 2 Equipotential point for different collector bars
minimum collector bar current was 2 kA, the US to DS
current partition was nevertheless close to 50% US and 50%
DS (Fig. 1).
As the main point of interest is the horizontal current in
the metal pad, the criterion for the difference between col-
lector bar currents has to be linked with target metal height
and metal heave. Higher target metal height gives lower
horizontal current densities in the metal pad since the current
density is inversely proportional to the metal height.
Metal-bath interface deformation decreases horizontal cur-
rents at locations of metal elevation and increases them at
locations of metal depression. Figure 3 illustrates the dif-
ference in horizontal currents calculated with flat and
deformed interfaces. As seen from these modelling results,
the interface deformation increases the maximum horizontal
current densities Jx and Jy considerably. Jx is mostly gen-
erated by unequal currents in the collector bars. In the case
shown, it is 3900 A/cm2 for flat metal pad and 5500 A/m2
for deformed metal pad. This is much smaller than the
transverse and vertical current density and does not con-
tribute substantially to MHD behaviour of the cell.
The metal pad thickness is also locally affected by the
cathode heave since it is larger in the centre of the cell,
Therefore the impact is maximum in the centre and negli-
gible close to the cell ends. We believe that the cathode
heave should reduce the impact of the metal heave on the
current density because both are higher close to the centre.
However, a study [7] has shown a negative impact of the
cathode heave on MHD stability. Probably the impact
depends on the shape of the metal heave.
MHD-VALDIS uses the current densities from deformed
bath-metal interface for its final steady state results and for
MHD stability calculations. Therefore, the accuracy of these
results depends on the accuracy of the interface calculation,
which seems to be reasonable since it has been validated [1].
674
a) Metal-bath interface deformation
b) Max Jx = 3900 A/m2
c) Max Jx = 5500 A/m2
d) Max Jy = 10400 A/m2
e) Max Jy = 11000 A/m2
Fig. 3 Impact of metal heave on horizontal currents inside the liquid
aluminium for average metal height of 20 cm. b and d are for flat
metal-bath interface and c and e are for deformed interface.
Busbar Current Density and Temperature
Very often developers of cell technology are asked about the
maximum allowed current density and temperature in the
busbars. Busbar temperature depends on busbar current
density and busbar cooling conditions. The cooling is by
convection and radiation, which are considerably affected by
the proximity of the potshell and by nearby busbars. Short
busbar sections are also affected by axial heat transfer in the
busbars. Maximum design busbar current density is typically
80 A/cm2, but it may be 100 A/cm2 in retrofits and due to
amperage increase. It can be greater in short busbars if they
A. Arkhipov et al.
are connected to larger busbars with lower current density.
Mathematical models that comprise full busbar systems
calculate the busbar temperature automatically. The accuracy
depends on how much detail of the ambient boundary con-
ditions is specified, specifically ambient temperature. In
principle, these should be adjustable locally if the software
has this capability; otherwise an average for all busbars has
to be used. ANSYS accepts local ambient temperatures but
MHD-VALDIS does not; the former will give more accurate
busbar temperatures than the latter if the modeller takes the
time to enter the local boundary conditions, which is rarely
the case. At EGA, extensive model validations of busbar
temperature and current distribution have been made for
both software packages, therefore the accuracy of model
predictions is known. The model predictions of busbar
temperature are quite accurate. Even using only one average
ambient temperature, the maximum difference between cal-
culated and average busbar temperature is within ± 20 °C,
but the typical difference in the vast majority of the busbars
is within a few degrees Celsius only.
In EGA busbar design, the most often used maximum
safe design busbar temperature is 200 °C. This is in agree-
ment with [4], whereas [8] mentions 215 °C. The main
reasons for this limit are:
• Softening of aluminium (yield strength at 200 °C is
about 70% of the strength at 20 °C [9]; at 260 °C it is
50%), which can lead to excessive busbar deformation—
even by their own weight if the busbars are not well
supported,
• Electrical insulation resistance under busbars, which
decreases rapidly with temperature and may not be ade-
quate at temperatures above 200 °C.
• Mechanical resistance of insulation below busbars, which
in some cases has been crushed at high busbar temper-
atures caused by amperage increase [8].
To operate busbars at higher temperature limits, specific
solutions need to be found to take care of these constraints. If
busbars are designed with proper expansion flexibles and
busbar supports, the busbar deformation and expansion is
not an issue. For busbar insulation, wherever an epoxy based
material is used, the degradation of the insulation resistance
can be minimised by interposing a high temperature indus-
trial laminate plate between the epoxy and the busbar or
insulate the busbar support columns at lower level where the
temperature is lower. Our tests have shown that mechani-
cally epoxy based insulation can sustain temperatures up to
250 °C. At 200 °C it still provides more than 50% of the
strength guaranteed by suppliers at room temperature.
Improving the Understanding of Busbar Design and Cell MHD … 675

Vertical Magnetic Field Component (Bz) 0.100

MHD Noise, V
0.090
0.080
As mentioned earlier, the main impact on cell stability comes 0.070
from the vertical component of magnetic field (Bz), which 0.060

Noise, V
0.050
interacts with transverse horizontal current (Jy) and creates 0.040
0.030
longitudinal Lorentz force (Fx). There are many publications 0.020
about MHD stability criteria and what Bz should be. For 0.010
0.000
example in [4] the authors state that in modern design
approach Bz should be low (typically targeting maximum Week # of year 2014

values of ± 1.5 mT) and balanced (having values of equal

and opposite sign) within each quadrant of the cell. Urata
wrote [10] that Bz gradient between cell corners has to be
small. These Bz characteristics are difficult to achieve and
moreover, the reduction of absolute maximum Bz may
increase other magnetic field components, usually the
transverse component (By). An increase of By can lead to
other negative consequences such as higher metal heave.
However, a compromise can be found. A recent Chinese
modelling study showed that both components can be made
small. According to the study, the four Chinese 400 kA cell
technologies have maximum Bz and By from 3.3 mT to
4.9 mT, the average absolute Bz from 0.4 mT to 2 mT and
By from 0.5 mT to 1 mT [11].
Our experience has shown that absolute maximum Bz can
be higher (as high as 8 mT) than above but the cell can still
have very good MHD stability and performance with current
efficiency of 95%. It seems that Bz distribution has a much
more important role on MHD stability than absolute maxi-
mum Bz value, where the main goal is to obtain a distri-
bution of electromagnetic forces in the cell that cancel each
other by cell quadrant as presented in [3] based on [12]. This
requires Bz anti-symmetry with respect to cell centre. Our
experience confirms that the closer the Bz distribution to
anti-symmetry the more stable is the cell.
Another criterion, in addition to anti-symmetry of Bz
distribution, was mentioned in [3] and is based on patent of
Chaffy and others [13]. It requires that the quadratic average
of the vertical magnetic field component over the whole
metal area be <1 mT. However, our experience shows MHD
stability does not correlate with quadratic average value of
Bz at all.
Table 2 shows one case study of cell stability before and
after modification where the impact of the quadratic average
is shown not to be important but asymmetry of Bz is
Fig. 4 Weekly average of MHD noise before and after busbar
modification in the case study. (Orange bar indicates the week when
the busbar modification was made) (Color figure online)
(Fig. 4). MHD-VALDIS software also predicted that Case
study 2 is much more stable than Case study 1 design.
Another example is the design of the original CD200 cell,
built in 1991 [14]. The original models were made by
COMALCO and were no longer available. For this study
performed for software validation, a model of the original
and a model of the improved busbars were built, using
MHD-VALDIS as the original drawings and reports are still
available. The improved design is very similar to one used in
Potlines 5 and 6 at EGA Jebel Ali. The same conclusions
were found as originally: The original design was unstable
even with 2 cm higher ACD than the improved and the
improved design was stable.
Analysis of Bz has proved that it is much more important
to have maximum anti-symmetric Bz distribution in the cell
rather than low absolute value of Bz (Table 3). In spite of the
fact that for the improved design the quadratic average of Bz
and maximum absolute Bz are lower at the original amper-
age (190 kA), the main contributor to MHD stability is still
very good anti-symmetry of Bz. The improved CD200
Technology had very similar busbar design to D20 Tech-
nology, which operates at 270 kA now. At this much higher
amperage, D20 Technology has, of course, higher maximum
absolute Bz value.
Metal Heave
In 1992, LaCamera [15] in his overview already described
some trials that had shown no correlation between metal
heave and stability of the cell. Our experience shows the

Table 2 Case study of MHD Max absolute. Bz Heave (Max Quadratic Antisymmetry MHD
characteristics US/DS, mT —Min), cm average of Bz, of Bz stability
mT
Case study 1, before 5.9/6.1 12.1 1.97 Poor Poor
modification
Case study 2, after 7.7/4.4 14.8 1.94 Good Good
modification
676 A. Arkhipov et al.

Table 3 Case study of MHD Max absolute. Bz Heave (Max— Quadratic average Antisym-metry MHD
characteristics US/DS, mT Min), cm of Bz, mT of Bz stability
CD200 2.2/3.8 5.0 1.95 Very bad Poor
original
CD200 2.9/2.9 5.5 1.04 Very good Good
improved
D20 at 4.7/4.3 11.9 1.51 Very good Good
270 kA

Fig. 5 Impact of anode setting (a) (b)

on metal-bath interface shape
change: a All anodes have normal
currents; b Two anodes in US
duct end corner are changed;
c Interface deflection below the
centre of each anode with respect
to the steady state interface on DS
side; d On US side

(c) (d)
Metal deformation below DS anodes Metal deformation below US anodes
0.05 0.05
Deformation wrt (m)

0.04 0.04

Deformation wrt (m)

0.03 AC: None AC: 9 & 10 0.03
0.02 0.02
0.01 0.01
0 0
-0.01 11 12 13 14 15 16 17 18 19 20 10 9 8 7 6 5 4 3 2 1 -0.01
-0.02 -0.02
-0.03 -0.03
-0.04 AC: None AC: 9 & 10 -0.04
-0.05 -0.05
Anode No. Anode No.

same; Metal heave is much less important for cell stability
than distribution of the vertical component of the magnetic
field. As shown in Table 2, the cell with the flatter
metal-bath interface had poorer MHD stability. Our calcu-
lations show that lower heave gives some improvements in
stability only when the distribution of Bz is already good. It
is, of course, desirable to have lower metal heave due to its
negative impact on operation for the following reasons:
1. Metal heave creates uneven distribution of bath volume
along the cell length therefore it can have negative
impact on alumina distribution in the locations of high
metal heave.
2. Higher metal heave in the cell, leads to higher metal-bath
interface change during and just after anode change.
3. In cases of power outage, high metal heave can create a
problem if full amperage is not restored quickly.
4. High metal heave makes amperage modulation more
difficult.
The negative impact of metal heave on MHD perfor-
mance during and just after anode change (when anode is
drawing low current) is due to the following: After a new
anode is set into the cell, the change in metal surface shape
can be so high that it short-circuits other anodes. Figure 5
illustrates how metal heave changes after corner anode set-
tings. As can be seen from the graph, the maximum
depression of interface with respect to steady state case is
3.3 cm and the maximum rise 1.4 cm. Taking into account
that cells operate with ACD of about 3 cm, such change in
interface shape induces significant change in uniformity of
anodes current distribution and may lead to instability until
the new anodes start picking up sufficient current.
The negative impact of high metal heave following a
power outage can be significant. During normal operation,
anodes are consumed and take the shape of the metal-bath
interface. When amperage is reduced, Lorentz forces in the
metal and bath also reduce which results in lower metal
heave (Fig. 6). In cases of power outage, the Lorentz forces
vanish altogether and the bath-metal interface becomes flat.
The metal in the central part of the cell goes down and the
metal at the corners goes up—which immerses the corner
anodes into the metal. When the power is restored, most of
the current flows through the corner anodes. This generates
excessive heat in these anodes and cell instability. The
temperature of the corner anodes and anode yoke increases
Improving the Understanding of Busbar Design and Cell MHD … 677

Fig. 6 Model predicted Metal Deformation below DS anodes Metal Deformation below US anodes
metal-bath interface deformation
at different amperages 0.04 0.04
0.03 0.03

Deformation (m)
0.02 0.02

Deformation (m)
0.01 0.01
0.00 0.00
10 9 8 7 6 5 4 3 2 1 -0.01
-0.01 11 12 13 14 15 16 17 18 19 20
-0.02 -0.02
-0.03
-0.03
-0.04
-0.04 Anode No.
Anode No.
50 100 150 50 100 150
200 235 200 235

and the transition joint may fail. Modelling in ANSYS has
shown that if half of the potline current goes only through
the corner anodes, the transition joint temperature reaches
500 °C (maximum limit) in less than 30 min. To avoid
transition joint failures, the amperage has to be increased as
fast as possible to a minimum at which the metal heave is
sufficient to free the corner anodes of the short circuit to the
metal pad.
In cases of power modulation or temporary reduction of
potline current, cell design with high metal heave will give
less freedom on how much the amperage can be reduced
without causing short circuiting of corner anodes and cell
instability.
Conclusions
During recent years, EGA has gained substantial experience
in busbar design with many cell technology development
projects for greenfield smelter expansions and for existing
cell technology modernisation. Excellent practical results
have proven that the modelling and design capabilities are
sound and reliable and can be used for future cell technology
projects to create new more efficient busbar designs. The
generally known MHD design criteria have been validated
refined and updated for EGA cell technologies.
References
1. V. Bojarevics and K. Pericleous, Solutions for metal-bath inter-
face. Light Met. 569–574 (2009)
2. A. Alzarooni, L. Mishra, M. Bastaki, A. Al Jasmi, A. Arkhipov
and V. Potocnik, Mathematical model validation of aluminum
electrolysis cells at DUBAL. Light Met. 597–602 (2013)
3. Vinko Potocnik, Principles of MHD design of aluminum electrol-
ysis cell. Light Met. 1187–1193 (1992)
4. A. Kjar, J. Keniry and D. Severo, Evolution of busbar design for
aluminium reduction cells, 8th Australasian Aluminium Smelting
Technology Conference, Yepoon, Australia, 3—8 October 2004.
Paper 5.07
5. M. Dupuis, A new aluminium electrolysis cell busbar network
concept, in Proceedings of 33rd International ICSOBA Confer-
ence, pp. 699–708 (2015)
6. A. Al Zarouni, A. Alzarooni, N. Ahli, S. Akhmetov, A. Arkhipov,
DX + ultra—EGA high productivity, low energy cell technology,
Light Met. (2017)
7. M. Dupuis, V. Bojarevics and D. Richard, Impact of the vertical
potshell deformation on the MHD cell stability behavior of a
500 kA aluminum electrolysis cell. Light Met. 412–409 (2014)
8. A.F. Schneider, D. Richard and O. Charette, Impact of Amperage
Creep on Potroom Busbars and electrical insulation:
thermal-electrical aspects. Light Met. 525–530 (2011)
9. A.F. Schneider, D. Richard and O. Charette, Impact of Amperage
Creep on Potroom Busbars: thermal-mechanical aspects. Light
Met. 899–904 (2012)
10. N. Urata, Wave mode coupling and instability in the internal wave
in aluminum reduction cell. Light Met. 455–460 (2005)
11. Ding Ji-lin, Li Jie, Xu Zhang Hong-liang, Yang Shuai Yu-jie, Liu
Ye-xiang, Comparison of structure and physical fields in 400 kA
aluminum reduction cells. J. Cent. South Univ. 21, 4097–4103
(2014)
12. P. Morel, J.P. Dugois, Process of reduction of magnetic distur-
bances in high amperage electrolysis cell potlines. Canadian Patent
no 1 120 422 (1982) (in French), also British Patent Aplication GB
2 021 647 (1979)
13. J. Chaffy, B. Langon, M. Leroy, Device for Connection between
very high intensity electrolysis cells for production aluminum. U.
S. Patent 4 713 161 (December 15, 1987)
14. G.P. Bearne, M. Dunn, M. Roberts and Y. Mohammed, The
CD200 Project—The Development of a 200 kA cell design from
concept to implementation. Light Met. 243–245 (1997)
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namics in the Hall-Heroult process, an overview. Light Met. 1179–
1186 (1991)
 LES Turbulence Modeling Approach for Molten
Aluminium and Electrolyte Flow in Aluminum
Electrolysis Cell

Mounir Baiteche, Seyed Mohammad Taghavi, Donald Ziegler,

and Mario Fafard

Abstract
In a Hall-Héroult electrolysis cell for aluminum production, understanding hydrodynamic
phenomena induced by the magnetic field is very important for process stability and
performance. The mathematical modeling of the flow of liquid aluminum and the
electrolytic bath under operational conditions involves solving two systems of equations for
two immiscible stratified fluids where the movement is primarily due to the anodic bubles
and the electromagnetic forces. Because of the flow recirculation, dissimilar cell length
scales in three directions and the magnetic field effects, the turbulence estimation for flow
modeling is not straightforward. In this study, numerical simulations are conducted in order
to investigate the applicability of Large Eddy Simulation turbulence models to adequately
represent the magnetohydrodynamic turbulence in the electrolysis cell.

Keywords
Stratified fluids


Hall-Héroult electrolysis cell Turbulence model Magnetohydro-
dynamic Large eddy simulation

Introduction dimensions of the order of several meters long by a few

Primary aluminum is produced at industrial scale by the
Hall-Héroult process. The alumina is dissolved in an elec-
trolytic bath. When passing a very high intensity electric
current, the alumina is reduced and metallic aluminum is
produced. This reaction consumes a large amount of electric
energy, theoretically, 6.35 kWh/kg aluminum. In practice,
more than twice this amount of energy is consumed due to
necessary engineering compromises in the cells [1].
Aluminum and the bath at high temperature, of the order
of 960 °C, are in liquid form and are completely stratified.
Aluminum is denser and rests at the bottom of the cell. At
the industrial scale, the fluid layers are of large horizontal
M. Baiteche (&)
S.M. Taghavi
M. Fafard
Aluminium Research Centre REGAL, Laval University, 1065,
avenue de la Médecine, Québec, QC G1V 0A6, Canada
e-mail: mounir.baiteche.1@ulaval.ca
D. Ziegler
Alcoa Primary Metals, Alcoa Technical Center, 100 Technical
Drive, New Kensington, PA 15069-0001, USA
meters wide, but only tens of centimeters in height [2].
The induced movement of the liquid metal and bath
through the magnetic field generates an electromotive force
which can alter both the imposed current distribution and the
magnetic field. The fluids are therefore subject to a resultant
electromagnetic force on the one hand produced by the
current passing in the conductor bus and the other generated
by the movement of fluid in the cell [3]. The flow must be
designed and controlled for efficient operation of the elec-
trolytic cell. At one level, the flow is necessary and very
important for optimum operation. It allows the dissolution
and distribution of alumina in the bath and the removal of
heat from the anode-cathode space [4, 5]. However, an
excessive level of flow can alter the electrolysis process by
causing deformation of the interface between the bath and
the liquid aluminum resulting in non-uniformity of the
electric current due to the variation of the distance between
the liquid aluminum and the anodes (Anode Cathode Dis-
tance or ACD) [6]. In extreme cases, this interface

© The Minerals, Metals & Materials Society 2017 679

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_83
680
deformation risks short-circuiting where the surface of the
liquid metal touches the anodes [7]. This behavior must be
avoided as it is a complete loss of current efficiency and may
damage the cell.
A first estimate of the Reynolds number using the cor-
relation provided by Haupin [8] and Severo et al. [9] gives
values of Re  104 which shows that the flow is turbulent,
although probably not fully developed. However, the tur-
bulence situation is very complex: The geometric scale of
the cell is different in the three directions; the shape of the
cell is difficult to represent accurately due to the solidifica-
tion of cryolite on the perimeter of the cell and wear of the
cathode blocks; the velocity is not very high, and the flow is
swirling and strongly stratified due to the two liquids and the
layer of bubbles below the anodes [10, 11].
The purpose of this study is to solve the problem of two
stratified fluids (liquid aluminum and cryolite bath). These
two fluids are in a 3D geometry similar to that of an elec-
trolytic cell. The arrangement of anodes is faithfully repre-
sented in a generic cell plan. Figure 1 shows a schematic
view of the cell representing the volume of the fluid in the
model with all the details of the positioning of anodes and
the spaces between the anodes, which have an important
influence on the flow.
Several studies in the literature deal with the modeling of
fluid flow in the electrolytic cell under different conditions.
In the most common models a time independent solution is
proposed for the two fluids’ velocity fields. These studies
attempt to show that a given magnetic field distribution
provides an established flow regime and also provides the
shape and position of the interface between the bath and the
aluminium pad, e.g. Severo et al. [12]. This type of model
allows, among other things, to study the heat and mass
transfer coefficient between the fluid and the walls of the cell
for heat and mass balance studies and the ledge formation
Fig. 1 Schematic view of
simulated volume of electrolysis
cell
M. Baiteche et al.
[13], but cannot predict possible vortex oscillation in the
fluids.
Other authors have established simpler models by pro-
viding solutions to determine the peaks of the interface
between bath and aluminum and wave displacement [14].
These works demonstrated several aspects of the effect of
magnetic field on the flow in the cell but retain rather simple
representations of the turbulence.
Other more complex works have reported simulation of
the pseudo-transient flow of the two fluids in the cell. Lan-
glois et al. [15] used an approximation of eddy viscosity to
simulate the flow while modeling thermo-electrical phe-
nomena. Some of these works use common turbulence
modeling approaches even if they are not suitable for this
application. The use of RANS models such as k-e are not
recommended for fluid flows as those appearing in the cell
due to anisotropic turbulence [16], as the shape of the
enclosure, flow type (buoyant) and swirling and recirculation
are not suitable to be represented by such a model.
Mathematical models for calculating the magnetic con-
ditions to which the cell is subjected are available in the
literature. Several studies carried out with finite element or
other approaches are presented for computing the resultant
magnetic forces in the cell [7, 17]. The present study uses
magnetic field and current distributions obtained by an
in-house code at Alcoa. These conditions are used to
determine the base body force distribution to which the
fluids are subjected.
In the present study, we use Large Eddy Simulation
(LES) [18] in transient mode. Various simulations were
performed and the results are presented in this article.
Despite not yet having experimental data to validate the
model results, numerical experimentation was done by
comparing results from different simulations to see the effect
of the mathematical model parameters on the results.
LES Turbulence Modeling Approach for Molten Aluminium …
Mathematical Model Description
The model consists of solving the transient 3D momentum
equations of the fluid in the geometry shown above. The
model is constructed with ANSYS-WORKBENCH [19].
Figure 2 shows the model organigram applied to the fluid
in the electrolytic cell. The equations of momentum are
discretized in a homogeneous schema for the two fluids. This
approach solves a bulk velocity field for the two fluids with
consideration of the respective density and viscosity for each
phase (aluminum or bath) in the part of the volume which is
occupied by this phase. This approach is commonly used
in situations where the stratification state of immiscible
fluids is not affected by the flow.
The physical properties of the two fluids were chosen to
correspond to a temperature of 960 °C [20]. The free surface
model was applied to the domain where the effect of gravity
is considered with a reference density for the two-phase
system which is that of the less dense fluid, namely the bath.
This condition can specify to the model the stratification
condition. Atmospheric pressure was applied to the free
surface over the volume occupied by the bath.
The equation system is implemented and solved using the
ANSYS-CFX software, which is based on the finite volume
method for solving computational fluid dynamics problems.
The solution is obtained in a transient implicit Euler scheme of
Fig. 2 Organigram of the model
681
the second order. The spatial discretization of the domain is
made beforehand and is not subsequently adapted. The
appropriate mesh density was verified by the independence of
the solution of the velocity field relative to the size of the mesh.
A fairly small time step was chosen (about 0.1 s) to see
changes in the flow field at very short intervals. This feature of
the model allows us to follow the interface and its deformation
due to fluctuation of the velocity field in more detail.
Magnetic Field Assumptions
The current density distribution was calculated using a finite
element method and verified against measured collector bar
currents. The magnetic field was calculated from the current
density distribution, taking into account the effects of the
steel parts of the cell, and verified against field measure-
ments. From these results, the Lorentz force was calculated
and applied as a source of momentum in the governing
equations. The calculated input magnetic field was devel-
oped without reference to changes caused by the fluid
motion. This approach was considered first to simplify the
system of equations to be solved and to test the simulation
methods of turbulence.
Figures 3 show contours of the magnetic induction
magnitude in the electrolytic cell.
682
Fig. 3 Magnetic field contours in the cell domain
Metal/Bath Interface Tracking
The initial conditions with which the model starts are a static
state where the Volume Of Fluids method (VOF) is used to
specify the volume occupied by each phase. An interface
between the two fluids is then set at the mesh volumes with a
fraction of 50% of volume occupied by each of the fluids. As
a new velocity field is calculated, the interface moves
according to the movement of the volume fractions of each
phase. This method is very compatible with the approach
used to calculate a bulk velocity field for the two fluids.
Turbulence Model Consideration
The turbulence model chosen is that of the Large Eddy
Simulation (LES). Several approaches exist for this model,
are cited in the literature and are available in ANSYS-CFX.
Three types of this model were tested in this study:
LES-Smagorinsky [21], LES-Wall [22] and Dynamic LES
model [23, 24]. Technically, simulations with LES are car-
ried out by the separation between large and small scales of
the eddies using a filter which is an algebraic equation to
calculate the eddy viscosity [16]. The transient terms of the
Navier-Stokes equations are filtered in the domain according
to the small eddies that the filter or the mesh size allows to
solve. This approach enables the taking into account of the
small eddy’s Sub-Grid Scale viscosity, and this without
being constrained to have mesh smaller than the smallest
eddies resolved in the transient simulation. The different
results of the velocity fields are compared in order to test
their sensitivity to the details of the LES approach. The LES
model results are compared to the more common is k-e
turbulence model.
M. Baiteche et al.
The three versions of the LES approach are very similar,
with small differences that have minor effects on the results.
The first method is LES Smagorinsky. This model uses an
algebraic equation that separates the turbulent viscosity in
two parts. The first is the viscosity due to the fluctuation of
the velocity field at scales larger than the filter and the
second is called Sub-Grid Scale which is estimated for the
smallest scales or under the filter value. For LES models, an
eddy viscosity is calculated according to a characteristic
1
length which depends on the geometry ðVolune3 Þ and a
constant coefficient varying from 0.1 to 0.2. For the
Smagorinsky model the coefficient chosen is 0.1, which is
the recommended value for numerical stability [16]. The
added characteristic of the LES-Wall model is the ability to
neglect areas of the boundary layer near the wall where the
flow is laminar but which is able to reproduce the transition
between laminar and turbulent far from the walls. This is
done using the distance from the boundary. The LES
Dynamic model has the ability to calculate the Sub-Grid
Scale viscosity considering a dynamic coefficient which is
calculated based on the velocity field of the large scales.
However, the value of the coefficient should not exceed 0.4.
It is reported in the literature that this approach is more
accurate but requires more computing resources [25].
Results and Discussions
The model provides detailed results on the velocity field in
the two fluids. Figure 4a shows velocity field across the cell
at the mid-height of the liquid aluminum pad. This prelim-
inary result shows a succession of vortices of various sizes.
These profiles can be obtained with different turbulence
simulation methods. This velocity distribution is comparable
to that presented in literature [15, 26] and it justifies, as it is
suggested, the use of LES type turbulence models. This flow
pattern is describable faithfully by this kind of approach
where RANS type models are not very suitable because of
the geometry characteristics and the nature of flow with large
scale flapping of a shear layer [27].
The interface between the bath and the liquid aluminum is
important to define at each time step in order to see the
impact of the velocity field on the distance between the
anodes and the cathode (the upper surface of the liquid
aluminum). The model calculates the elevation of the
interface as shown in Fig. 4b.
To verify mesh independence, the flow fields with three
different mesh sizes were obtained and compared to see the
impact of the mesh, as shown in Fig. 5. The main difference
of the three meshes is the characteristic size of the elemen-
tary volumes and the location of the refinement of the mesh
LES Turbulence Modeling Approach for Molten Aluminium …
Fig. 4 a Velocity vectors of liquid aluminum in the cell. b Height of the interface between the bath and the liquid aluminum
Fig. 5 Different meshes tested for the model of the cell: a coarse mesh, b refined mesh on the walls and c refined mesh at the interface
near the walls or in the volume where the interface can be
located.
The results of this comparison are presented in Fig. 6a, b,
c. Velocity profiles were compared on the line sections AA,
BB and CC of Fig. 4a. Comparison of velocity profiles on
the three lines at mid-height of the aluminum pad shows a
slight sensitivity of the solution to the mesh size. These
velocity profiles were obtained at four minutes of physical
time. Another significant output is the interface position; the
case using a refined mesh near the interface gives a smoother
representation.
The simulations were done for 10 min. Up to 4 min of
physical time, there is formation of different vortexes over
the cell, after which the flow is nearly stable. Two main
vortices are observed on both sides and seem to be stable
through the end of the simulated period. However, a set of
smaller vortexes of different sizes in the center of the cell are
683
slightly fluctuating with time. The length scale of these
vortices is substantially large but remains smaller than the
big main ones. The big vortices seem stable probably due to
the assumption that the magnetic field and current density
don’t vary during the simulation which should change
according to the interface deformation. Another point which
should be mentioned is the calibration of the filter for the
LES models. An appropriate values should be investigated
as suitable data becomes available.
At 4 min the results were compared. The three LES
models were compared with RANS model (Reynolds
Average Navier-Stokes, k-e). All the simulations were per-
formed under the same conditions and on the same mesh.
Figure 7 shows the velocity contours at mid-height of the
aluminum pad. A slight difference is observed at the con-
tours on the velocity distribution in the use of k-e and LES
models.
684
Fig. 6 Velocity profiles for different mesh size: a section AA b section BB and c CC section
Fig. 7 Velocity profiles
contours: a k-epsilon model and
b LES model
A more detailed analysis was conducted to see the dif-
ference in the velocity fields calculated in the cell with the
three LES approaches and k-e model. The comparative
results were extracted along indicator lines 1–6 in Fig. 7.
The lines cross the mid-height of the liquid aluminum pad.
The results shown in Figs. 8 and 9 respectively show the
velocity profiles comparison of line 1–3 and 4–6. Another
difference is that computational time for the RANS k-e
turbulence model is higher than with the LES models. In the
k-e model, the eddy dissipation rate and the kinetic energy of
turbulence are calculated with separate partial differential
equations, increasing the number of equations to solve. This
makes the computational requirements higher. The LES
M. Baiteche et al.
models require also long time because they are attempting to
solve the large turbulence eddies at the same time with
velocity field fluctuation. Between the three LES models, the
dynamic model takes a longer time because of the estimation
of the eddy viscosity coefficient instead of considering a
constant value.
Figure 10 shows the turbulence kinetic energy fluctua-
tions at each time step for the two turbulence approaches;
LES Smagorinsky and k-e. The values were calculated at a
position where the small eddies are fluctuating to quantify
the turbulence energy in the same way for both models.
Figure 10a compares the kinetic turbulence energy for
k-e with the sub-grid scale energy for LES model.
LES Turbulence Modeling Approach for Molten Aluminium … 685

Fig. 8 Velocity profiles in liquid aluminum for different turbulence models: a line 1, b line 2 and c line 3

Fig. 9 Velocity profiles in liquid aluminum for different turbulence models: a line 4, b line 5 and c line 6

Fig. 10 Turbulence energy Turbulence Kinetic Energy for k-ε

Smagorinsky
fluctuation for RANS and LES Sub-grid scale energy for LES (a) 4.0E-02
k-ε
(b)
2.5E-03
Total turbulence energy [J kg^-1]

models
3.5E-02
Turbulence energy []J kg^-1

2.0E-03 3.0E-02

2.5E-02
1.5E-03
2.0E-02

1.0E-03 1.5E-02

1.0E-02
5.0E-04
5.0E-03

0.0E+00 0.0E+00
0 100 200 300 400 500 600 0 100 200 300 400 500 600

Time [s] Time [s]

The fluctuations for k-e is random and lower compared to Conclusions

the LES model. Figure 10b compares the total turbulence
energy for both models. After the flow stabilisation observed Turbulent flow in the electrolysis cell is constituted of a
after four minutes, the turbulence kinetic energy is quite series of vortices of several scales of magnitude. To repre-
different for both models. LES Smagorinsky appear to be sent the small eddies and see their effects on the overall flow
higher and periodic while k-e seems random. These results requires choosing the turbulence model that seems the most
prove that the two modeling approaches are different. appropriate. From this study, it appears that Large Eddy
Experimental investigations are necessary to choose the Simulation models seem to give a good representation of
adequate model. different sizes of vortices in the fluid domains. Flow near the
686
walls in the electrolysis cell are as important as the flow over
entire fluids volume. The formation of the cryolite crust and
the overall heat balance of the cell depends on this criterion.
The use of LES models showed good flow description with
less computational time. Experiments and measurement of
the flow in the cell will help to perform a parametric study
and choose an appropriate filtering parameter for the LES
models.
Acknowledgements The authors acknowledge the technical and
financial support from NSERC, ALCOA, FQRNT and Laval
University.
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 MHD of Large Scale Liquid Metal Batteries

Valdis Bojarevics and Andrejs Tucs

Abstract
Liquid metal batteries are candidates for large-scale energy storage in a national energy
grid. The attraction of the liquid batteries lies in the fast kinetics at liquid metal-electrolyte
interfaces, simple assembly and recycling, while the major difficulties to implementation
are their sensitivity to liquid motion and operation at elevated temperatures. The concept of
liquid metal battery bears a close similarity to aluminium electrolytic production cells. The
two liquid layer magnetohydrodynamic effects can be projected to the three liquid layer
self-segregated structure of the batteries. The trend for commercial electrolysis cells is to
increase their size instead of operating a large number of parallel small ones. Our aim is to
develop a numerical model for the three density-stratified electrically conductive liquid
layers using 3D and shallow layer approximation accounting for specific magnetohydro-
dynamic effects during periods of battery charge/discharge. A possibility to reuse
infrastructure of an old aluminium electrolysis potline for a large scale liquid batteries
facility is discussed.

Keywords
Liquid metal batteries Interface instability MHD mixing

Introduction components enables simpler, lower-cost cell fabrication and

Liquid Metal Batteries (LMB) are attracting a growing
interest due to ultrafast charge-transfer kinetics at liquid
electrode-electrolyte interfaces, efficient mass transport of
reactants and products by means of convection and liquid
diffusion, high cycling capability, and relatively low ohmic
losses in highly conductive molten metals (106 S/m) and salt
electrolytes (up to 300 S/m) [1–5]. The LMBs operate at
relatively high voltage efficiency and high current density;
such characteristics are vital for practical implementation as
large-scale energy storage facilities in a national energy grid.
LMBs also have advantage of being low cost because many
of the candidate electrode materials are earth-abundant [1].
Density driven natural self-segregation of the active liquid
V. Bojarevics (&)
A. Tucs
University of Greenwich, London, SE10 9LS, UK
e-mail: v.bojarevics@gre.ac.uk
recycling if compared to conventional batteries. Important
features of the liquid only cells are the continuous renewal of
the liquid metal electrodes upon charge-discharge cycling, as
well as their insensitivity to micro-structural degradation
mechanisms, which are a major limitation to the majority of
solid battery types. A key parameter for practical operation
of LMB is the cell operating temperature determined by the
melting temperatures of the constituents (see the data in [1]
for typical candidate metals). Lower cell operating temper-
ature decreases impact of corrosion and self-discharge
effects, at the same time simplifying sealing and thermal
management. In general, the use of pure metals is not
mandatory, the electrodes may be composed from alloys
with electrical characteristics similar to pure metals, but with
reduced melting/operating temperatures which, in turn, can
improve performance over longer lifetime [3, 4].
Major drawback of LMBs is their operation sensitivity to
liquid motion (caused mainly by electromagnetic forces)

© The Minerals, Metals & Materials Society 2017 687

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_84
688
which potentially may lead to the top and bottom liquid
electrode short-circuiting, accompanied by electrochemical
and thermal problems [1, 5]. A very similar destabilization
mechanism is observed in Hall-Héroult (H.H.) cells, where
the liquid aluminium and electrolyte thicknesses are care-
fully adjusted and controlled for stable and efficient tech-
nological process. Interface instabilities are well-known
phenomena in H.H. cells [6–9]. These instabilities result
from interaction of the electric currents with a background
magnetic field generated by the current supply lines in
combination with self- induced magnetic field of the current
in the cell. A gravity wave perturbation of a length scale
comparable to the cell horizontal dimension may develop
into a resonant ‘rotating’ or sloshing motion of the liquid
aluminium [7–9]. In order to prevent the electromagnetically
driven long wave instabilities, the horizontal component of
electric current in the cell has to be kept below a critical
value, the vertical component of magnetic field should be
highly optimized, and the electrolyte layer thickness should
not be less than certain critical limit (about 4 cm). These
requirements lead to a typical commercial cell total voltage
of about 4 V, of which 1.5–1.7 V are due to the ohmic
resistance of electrolyte layer, directly converted to Joule
heat. Part of this heat is useful to maintain the cell contents
in liquid state, however a reduction of the electrolyte
thickness even by few millimeters gives huge savings for the
large scale production electricity costs.
In the case of LMB the maximum thickness of the
electrolyte layer is limited by the requirement that the
voltage loss in the electrolyte must not exceed a significant
portion of the available thermodynamic driving force (open
circuit voltage) [1]. For the relevant combination of metals
and salts, this means the electrolyte thickness should not
exceed a few centimeters. A thinner electrolyte layer would
mean less irreversible voltage loss and faster kinetics for
ionic mass transport. The commercial development of H.H.
cells demonstrates a trend to increase size of the cells
instead of operating a large number of parallel smaller ones,
therefore we could assume the same tendency for the
practical large scale LMB cells with large horizontal surface
area and a small depth of the electrolyte and liquid metal
electrodes. For these conditions, a careful stability analysis
of the LMB liquid interfaces becomes imperative. The
mathematical model in this paper follows our previous
modelling experience with commercial large-scale H.H.
cells [6–9].
Mathematical Models
Let us consider the electrically conducting liquid volume
consisting of three materials stratified due to their density in
layers (see the Fig. 1 for notation to be used in this paper)
V. Bojarevics and A. Tucs
Fig. 1 Schematic representation and notation for the LMB model
under conditions of applied electric current from an external
circuit (charge/discharge).
The problem can be solved by means of spectral
algorithm based on Fourier and Chebyshev polynomial
expansion:
j ¼ ri ru; Dui ¼ 0; x 2 ð0; Lx Þ;


y 2 0; Ly ; z 2 ðHi1 ; Hi Þ; i ¼ 1; 2; 3 ð1Þ
M;N X
X P
ui ðx; y; zÞ ¼ aðmnp
iÞ
Tp ðzÞ cosðmpx=Lx Þ cosðnpy=Ly Þ;
m;n¼0 p¼0
ð2Þ
The advantage of using the expansion (2) is that it sat-
isfies the condition of insulating side-walls, while the given
collector currents are imposed at the top and bottom elec-
trode areas at z = H0 and z = H3. The magnetic field (from
the currents in the cell and the supply lines) is computed
numerically using the Biot-Savart law for the volume current
distribution. The respective electromagnetic force distribu-
tion is recomputed at each time step when the interfaces H1
and H2 are deformed according to the hydrodynamic wave
model. The wave model for the three coupled layers can be
represented efficiently using the small wave amplitude A and
the shallow layer approximation after introducing the fol-
lowing non-dimensional parameters:


e ¼ A=h1  1; d ¼ h1 =Lx ; Ek ¼ IB0 = L2x qk ged ; ð3Þ
where the electromagnetic interaction terms are scaled by the
total current I and the typical magnetic field B0, relative to
the gravitational restoring forces qg arising for the small
amplitude waves in a shallow layer [6].
In the shallow layer approximation, taking into account
the effects of hydrodynamic damping at the bottom and top
solid walls (terms with the coefficients kf1 and kf3) [7, 10],
MHD of Large Scale Liquid Metal Batteries 689

the two coupled interface dynamics are determined by

solving the equations:
 
q1 q2 q kf 1 q
þ @tt H1 þ 2 @t H1  2 @tt H2
h1 h2 h1 h2
ð4Þ
¼ ðq1  q2 Þg@jj H1  E1 @i Fi1 þ E2 @i Fi2



 e q1 @j Uk1 @k Uj1  q2 @j Uk2 @k Uj2 ;
 
q2 q3 q kf 3 q
þ @tt H2 þ 3 @t H2  2 @tt H1
h2 h3 h3 h2
ð5Þ
¼ ðq2  q3 Þ@jj H2  E2 @i Fi2 þ E3 @i Fi3 Fig. 2 The simple electric current supply collectors for a short series


 of cells
 e q2 @j Uk2 @k Uj2  q3 @j Uk3 @k Uj3 ;

@n H1 ¼ ðFn1  Fn2 Þ=½ðq1  q2 Þg; ð6Þ

@n H2 ¼ ðFn2  Fn3 Þ=½ðq2  q3 Þg: ð7Þ

The boundary conditions (6), (7) correspond to the zero
velocity condition at the side walls. The horizontal velocity
components Uk (k = 1, 2) are computed from the full
Navier-Stokes equation in the shallow layer approximation
obtained after the depth averaging procedure [6, 8].

Numerical Solution Examples for Mg/Sb Fig. 3 3D solution for the electric current distribution in 3 liquid
layers
Battery

Simple Collector Cell
A selection of computed results for the time dependent flow
and interface wave development is presented for the case of
magnesium/antimony battery. This type of battery is rela-
tively safe to realize in laboratory, and was used successfully
in the small scale experiments [2], however more efficient
combinations of the metals are in principle available [3, 4].
The electrolyte density q2 = 1715 kg/m3 in this case is close
to the liquid magnesium density q3 = 1584 kg/m3, making
this a critical challenge to stabilize the wave motion after a
small amplitude A = 0.005 m gravity wave of the longitu-
dinal mode (1, 0) perturbation applied as the initial distur-
bance. The bottom metal layer of liquid antimony Sb is
the liquid depends on the full path of the electric current
including the surrounding cells and the return current line.
The computed electromagnetic force is sensitive to the
magnetic field details and leads to skewed non-symmetric
horizontal flow pattern shown in the Fig. 3 for the bottom
metal case. A symmetric vortex pattern can be obtained if
ignoring the return current line. This observation serves as a
hint why in the experimental LMB cell described in [11] the
measured flow was highly non-symmetric even in a small
scale liquid metal cell (Fig. 4).
Velocity
0.2
2 Vm: 0.002 0.046 0.09 0.134
y (m)

expected to be easier to stabilize due to the higher density

q1 = 6483 kg/m3. The first attempts of modelling use simple
1
electric collectors at the top and bottom of the cell (Fig. 2).
The cell of 8 by 3.6 m horizontal cavity contains 20 cm of
liquid Sb, 20 cm of liquid Mg, and 5 or 8 cm of the liquid 0
electrolyte. The electric current I = 100 kA is supplied by a
single central collector from the top and removed at a single -1
collector at the bottom (Fig. 2). The computed 3D current
distribution for this case is shown in the Fig. 3, demon- -2
-4 -3 -2 -1 0 1 2 3 4
x (m)
strating the presence of high horizontal current density in the
metallic electrode layers and almost purely vertical current in Fig. 4 The non-symmetric velocity field in the bottom layer due to the
the electrolyte. The distribution of the total magnetic field in return circuit effect
690 V. Bojarevics and A. Tucs

Magnetically Optimized Cell

In the previous example of the single collector the cell could

be stabilized only at relatively high electrolyte thickness (5
or 8 cm), meaning that the ohmic voltage drop at the 100 kA
charge current is far exceeding the thermodynamic EDS
available for the Mg/Sn battery in the discharge period
(about 0.4 V [2]). It would be possible to operate this battery
at significantly lower current and a low efficiency.
An improvement of efficiency (by reducing the thickness
Fig. 5 The final stable oscillating interface between the top metal of the electrolyte layer) can be achieved by optimizing the
(Mg) and the electrolyte for I = 100 kA and the electrolyte thickness of current supply bus bar path in such a way that the vertical
8 cm
magnetic field is reduced in magnitude and its distribution
optimized to avoid the MHD wave instability. The com-
The long term simulation of the wave dynamics with the
mercial aluminium electrolysis cells were developed fol-
fully coupled electromagnetic interaction demonstrates that
lowing such stringent guidelines. Hence, we attempted to
the bottom heavier metal interface is very stable to the
reuse one of the existing optimized bus bar configurations
perturbation effects, while the top metal interface is easily
for the case of 3 liquid layers filling the cell cavity.
destabilized, leading to the wave amplitude growth and the
The commercial Trimet 180 kA cell series are used for
development of the rotating wave instability [7]. In the case
these simulations. The configuration is shown in the Fig. 8.
of the simple single current collectors the response can be
In this case the electric current in the liquid layers has less of
stabilized by reducing the magnitude of the total current I
the horizontal component, particularly in the longer dimen-
(from 100 to 75 kA) or by increasing the electrolyte thick-
sion ‘x’, Fig. 9. From the figure we can see that the 0.65 V
ness from 5 to 8 cm (Fig. 5). The oscillation for the bottom
voltage drop is still too high for the 0.4 V discharge current
metal is easily damped and retains the imposed (1, 0) per-
turbation frequency, while the top metal interface is not
completely damped and continues to oscillate at the new
shifted frequency, Figs. 6 and 7.

0.004

0.002 -16 -18

-20
-12 -14
-6 -8 -10
-2 -4
0 4 2 0
6
dH (m)

12 10 8 y(m )
16 14 Z
-0.002 20 18
X
I: 1.0E+03 8.2E+03 1.5E+04
-0.004 Y

dH corner, top
-0.006 dH mid-cell, top
dH corner, bottom Return line
-0.008
200 400 600 800 1000
t (s)

Fig. 6 Oscillation patterns for top and bottom metal/electrolyte Fig. 8 Trimet bus bars for a series of cells used for the liquid battery
interfaces in the case of single collectors simulation

Fourier spectrum
2E-09

1.5E-09 dH corner top

Fgravity
dH corner bottom
1E-09 Fgravity

5E-10

0
0 0.05 0.1 0.15 0.2
f (Hz)

Fig. 7 The computed Fourier spectra for the oscillations of the top and
bottom metal/electrolyte interfaces in the case of single collectors Fig. 9 Electric current in Trimet cell 180 kA, 3 liquid layers
MHD of Large Scale Liquid Metal Batteries 691

driven by the battery EDS. Therefore we reduced the current

to 75 kA to see the effects on the magnetic field, shown in
the Fig. 10 to compare the optimized cell and the previous
non-optimized. Clearly the magnetic field Bz component is
much less for the commercial Trimet cell at the same value
of the total electric current. The computed interface defor-
mations become stable and smaller in magnitude after the
perturbation dies out, Figs. 11 and 12. The horizontal
velocities for the optimized cell are reduced in magnitude as
can be seen from Figs. 13, 14 and 15. Fig. 12 The interface shape at 75 kA current for the top metall
Finally we want to compare the wave stability for the two
cells. At 100 kA the simple cell was stabilized if the elec-
trolyte thickness was increased to 8 cm. In contrast the
optimized Trimet cell holding three metal layers appears to
be more stable even if reducing the electrolyte thickness to
2.5 cm (Fig. 16). The voltage drop in the electrolyte is still
too high (0.49 V) for the discharge to be feasible, however
this combination of the current and electrolyte thickness
could be used in the dynamic charging periods when the
external circuit current is subject to high fluctuation. For the

Fig. 13 The horizontal velocity at 75 kA current for the top metall

Fig. 14 The horizontal velocity at 75 kA current for the electrolyte

Fig. 10 Comparison of the magnetic field at 75 kA current for the
simple cell versus the Trimet cell

Fig. 11 The interface shape at 75 kA current for the bottom metall Fig. 15 The horizontal velocity at 75 kA current for the bottom metall
692
Fig. 16 Simple cell (100 kA, 8 cm ACD) versus Trimet cell (100 kA,
2.5 cm ACD) top metal oscillation
Fig. 17 Trimet cell (75 kA, 2 cm ACD) top and bottom metal
oscillations
stable discharge at reasonable voltage drop of 0.29 V the
maximum current can reach 75 kA when the critical
electrolyte thickness is reduced to 2 cm. In this case the
minimum thickness of the metal layers can also be reduced
safely to 10 cm. A further reduction of the current magni-
tude to 50 kA reduces the ohmic voltage loss to 0.19 V.
The bottom metal interface is very stable, the perturbation
is damped fast while oscillating at the initial gravity wave
frequency, without any shift due to the MHD interaction.
V. Bojarevics and A. Tucs
The top metal even for the stable case of 75 kA shows the
presence of the magnetic interaction by shifting the oscilla-
tion frequencies of the two modes, which are initiated from
the single mode perturbation, as it is illustrated in the
Fig. 17.
Conclusions
The MHD model for large scale LMB demonstrates that it is
possible to design a stable to dynamic perturbation operating
cell if using the optimized bus bar configuration. The bot-
tom heavier metal layer is very stable to perturbations,
leaving the top lighter metal (Mg, Li, Ca) interface stability
as the critical step to control.
Acknowledgements A.T. acknowledges the Ph.D. scholarship
VCS-ACH-16-14 from the vice-chancellor of the University of
Greenwich.
References
1. H. Kim et al., Liquid metal batteries: past, present, and future.
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Magnesium-Antimony liquid metal battery for stationary energy
storage. J. Am. Chem. Soc. 134, 1895–1897 (2012)
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 Low Energy Consumption Cell Designs
Involving Copper Inserts and an Innovative
Busbar Network Layout

Marc Dupuis

Abstract
Two innovations presented by the authors recently at ICSOBA conferences allow to very
significantly reducing both the cathode and the busbar voltage drop (Dupuis in A new
aluminium electrolysis cell busbar network concept, 2015; Dupuis in New busbar network
concepts taking advantage of copper collector bars to reduce Busbar weight and increase
cell power efficiency, 2016). This paper combines the usage of those two innovations with
the usage of the new anode stub hole design presented at the Aluminiun of Siberia
conference (Dupuis in Presentation of a new anode stub hole design reducing the voltage
drop of the connection by 50 mV, 2016) to come up with a very low energy consumption
cell design.

Keywords
MHD cell stability Busbar design Mathematical modeling Power efficiency Copper
collector bars

Introduction Both designers clearly respected similar design guidelines

The author has been involved in the modeling of aluminium
reduction cells for the last 30 years. In 1988, he designed the
cathode of the Alcan A310 prototype cell, the first cell to
operate above 300 kA in 1989. The thermo-electric cathode
slice model he developed was presented at the 1991 ANSYS
conference [4]. Figure 6 of that paper, reproduced in Fig. 1
shows the model mesh highlighting the cell lining and pot-
shell design.
A few years later as an independent consultant, the author
developed a similar demonstration model strongly inspired
by the VAW CA300 cell design presented in JOM in 1994
[5]. The resulting thermo-electric cathode slice model that
was first presented in Fig. 12 of the 1997 CQRDA alu-
minium electrolysis course [6], is reproduced in Fig. 2.
The A310 and the CA300 cells were designed at about
the same time and operated at about the same amperage.
M. Dupuis (&)
GéniSim Inc., 3111 Alger St., Jonquière, QC G7S 2M9, Canada
e-mail: marc.dupuis@genisim.com
for the choice of the type of cathode blocks and side blocks,
the thickness of that side block, the size of the anode to side
wall distance (ASD), the location of the anode shadow, etc.
That 300 kA demonstration model typical of the early
1990s state of the art in cell design became the starting point
or base case for two styles of retrofit studies, the first one
aiming at minimizing the cell energy consumption presented
in Dupuis [6] and the second one aiming at maximizing the
cell productivity presented at the TMS 2000 conference [7].
Part of the Table 2 for a subsequent article presented in the
magazine ALUMINIUM in 2005 [8] presenting the key
design parameters and predicted operational results of those
two cell retrofits is reproduced in Table 1.
The key design changes that are allowing either the
reduction of the cell energy consumption to 12 kWh/kg or
the increase of the cell productivity by 17% are the change
of the type of cathode material from 30 to 100% graphitic
carbon block, the reduction of the anode to cathode distance
(ACD) from 5 to 4 cm and a change of the bath chemistry
(and alumina feed control logic) increasing the current effi-
ciency. Other changes are required to obtain an appropriate

© The Minerals, Metals & Materials Society 2017 693

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_85
694 M. Dupuis

Fig. 1 Alcan A310 cathode side

slice model mesh

Fig. 2 VAW CA300 inspired

cathode side slice model mesh
Low Energy Consumption Cell Designs Involving Copper Inserts … 695

Table 1 Design and predicted Base case

operational data, part of Table 2
in Dupuis [8] Amperage (kA) 300 265 350
Nb. of anodes 32 32 32
Anode size 1.6 m × 0.8 m 1.6 m × 0.8 m 1.7 m × 0.8 m
Nb. of anode studs 3 per anode 3 per anode 3 per anode
Anode stud diameter (cm) 18 16 19
Anode cover thickness (cm) 16 17.5 10
Nb. of cathode blocks 18 18 18
Cathode block length (m) 3.47 3.43 3.67
Type of cathode block HC3 HC10 HC10
Collector bar size 20 cm × 10 cm 18 cm × 10 cm 20 cm × 10 cm
Type of side block HC3 Anthracite SiC
Side block thickness (cm+) 15 15 10
ASD (cm) 35 35 30
Calcium silicate thickness (cm) 3.5 6.0 3.5
Inside potshell size 14.4 × 4.35 m 14.4 × 4.35 m 14.4 × 4.35 m
ACD (cm) 5 4.15 4
Excess AlF3 (%) 10.90 13.50 13.50
Anode drop (mV) 303 273 323
Cathode drop (mV) 285 213 292
Anode panel heat loss (kW) 240 183 284
Cathode bottom heat loss (kW) 176 132 202
Operating temperature (°C) 973.2 956.1 960.4
Liquidus superheat (°C) 6.7 2.4 6.7
Bath ledge thickness (cm) 8.66 23.5 9.09
Metal ledge thickness (cm) 4.12 9.01 4.42
Current efficiency (%) 94.00 95.70 96.10
Internal heat(kW) 628 422 713
Energy consumption (kWh/kg) 13.72 11.93 13.43

ledge thickness at a very different level of heat dissipation.
Per example, the known strategy to increase the cell pro-
ductivity is to increase the anode length, decrease the ASD
and use thin silicon carbide side walls. In addition, anode
stud diameter and collector bar size can be increased while
the anode cover thickness can be decreased.
The design strategy to decrease the cell energy con-
sumption to 12 kWh/kg is the opposite, anode stud diameter
and collector bar size can be decreased while the anode
cover thickness can be increased. What is a lot more sig-
nificant is that the cell productivity must be decreased by
12%, which explains why so far the industry have not move
in that direction despite the fact that operation at that level of
power efficiency have been reported as soon as the early
80s [9, 10].
Clearly, a cell designer cannot at the same time aim at
maximizing the cell productivity and minimizing the cell
energy consumption. This is why Rio Tinto per example has
developed and is offering both the AP60 and the APXe cells
based on the same basic platform [11].
Yet, new choice of materials and new and innovative
design ideas can always be put to contribution in order to
further increase the cell productivity or decrease the cell
energy consumption. Another tendency is to continue to
increase the cell size in order to keep reducing both the cell
OPEX and CAPEX. It is in that context that the AP60
platform replaced the AP30 platform that itself replaced the
AP18 platform [12] per example.
For one, the author have been advocating that, despite
the difficulties that have always been limiting the rate of
increase of the cells size since the beginning of the
industry, he could foresee no technical limitation that could
limit further increase of cell size in the future. It is in that
context that the author presented a 500 kA cell design in
2003 in Dupuis [13] and a 740 kA cell design in 2005 in
Dupuis [8].
696 M. Dupuis

In yet another cell retrofit demonstration study paper in
2011 [14] the author took advantage of new design inno-
vations like collector bar copper inserts, anode slots and a
new type of anode stub hole design [3] to retrofit the
500 kA cell presented in Dupuis [13] into a more productive
600 kA cell operating at about the same power efficiency.
As an intermediary step, not quite optimized in term of
thermal conditions, a 500 kA cell operating at 12.1 kWh/kg
was also developed. Table 2 presents detailed data of that
study.
New Retrofit Study Aiming at Minimizing Cell
Energy Consumption Even Further
In the past 30 years, the market conditions of high metal
value and the existence of regions of the world offering
inexpensive electrical power were favorable for new cell
designs maximizing cell productivity while maintaining
power efficiency in the 13–13.5 kWh/kg range.
The market conditions have evolved recently to a much
lower metal value and far less availability of inexpensive
electrical power. In that context, the metal production cost is
getting quite close to the metal market value and a reduction
of the energy consumption can make the difference between
operating at profit or at loss.
Technically, 12–12.5 kWh/kg have been achieved mul-
tiple times and as for operation at 13–13.5 kWh/kg range,
under the current market conditions it might well become the
preferable operational range. The next question is techni-
cally, regardless of market conditions, how much lower can
we manage to go?
Reducing the cell energy consumption means reducing
the cell voltage drop which in turn means reducing the cell
ohmic resistance. This statement assumed that at 95–96%
current efficiency, we cannot expect significant gain to come

Table 2 Design and predicted Base case

operational data, original work
presented in Dupuis and Amperage (kA) 500 500 600
Bojarevics [14] Nb. of anodes 40 48 48
Anode size 1.95 m × 0.8 m 1.95 m × 0.665 m 2.0 m × 0.665 m
Nb. of anode studs 3 per anode 4 per anode 4 per anode
Anode stud diameter (cm) 20.5 17.5 17.5
Anode cover thickness (cm) 10 10 10
Nb. of cathode blocks 24 24 24
Cathode block length (m) 4.17 4.17 4.17
Type of cathode block HC10 HC10 HC10
Collector bar size 20 cm × 10 cm 20 cm × 10 cm 20 cm × 10 cm
Type of side block SiC SiC SiC
Side block thickness (cm+) 10 10 7
ASD 30 30 28
Calcium silicate thickness (cm) 3.5 3.5 3.5
Inside potshell size 17.8 × 4.85 m 17.8 × 4.85 m 17.8 × 4.85 m
ACD (cm) 4 3.5 3.5
Excess AlF3 (%) 13.50 12.00 12.00
Anode drop (mV) 354 265 318
Cathode drop (mV) 314 87 104
Anode panel heat loss (kW) 409 420 449
Cathode bottom heat loss (kW) 273 238 240
Operating temperature (°C) 963.1 955.6 964.8
Liquidus superheat (°C) 9.4 2.6 11.8
Bath ledge thickness (cm) 6.15 29 4.76
Metal ledge thickness (cm) 2.42 26 1.07
Current efficiency (%) 95.90 96.50 96.40
Internal heat (kW) 1043 760 1140
Energy consumption (kWh/kg) 13.61 12.1 13.26
Low Energy Consumption Cell Designs Involving Copper Inserts …
from that factor. Leaving aside the bath ohmic resistance for
now, this leaves three distinct ohmic resistances to work
with: the anode, cathode and busbar resistances.
Cathode Design with Copper Collector Bars
As presented in Table 2, the intermediary cell operating at
500 kA presented in Dupuis and Bojarevics [14] was oper-
ating at 87 mV at cathode drop by using the copper collector
bars design presented in Fig. 3.
At the time, it was speculative that such a collector bar
design could be actually build, but it is no longer the case
today after Storvik AS presentation at the ISCOBA 2015
conference [15]. Furthermore, at the TMS 2016 conference
KAN-NAK advocated that copper collector bars don’t even
need to be protected by a shell of steel [16].
As first presented in Dupuis [2], what the author did not
realized in 2011 is that with the usage of copper collector
bars, 100% of the cell current can be extracted on the
downstream side without generating excessive horizontal
current in the metal pad or producing excessive cathode
voltage drop.
The results presented in Dupuis and Bojarevics [14] and
in Dupuis [2] are for a 20 cm × 10 cm copper collector bar
size. When the current is extracted all on the downstream
side of that cell running at 500 kA, the current density in the
bar doubles, and the cathode voltage drop increases from 87
to 174 mV as presented in Dupuis [2].
New results for a bigger 25 cm × 16 cm copper collector
bar are presented here. As can be seen in Fig. 4, the cathode
voltage drop is reduced back to 130 mV.
Figure 5 presents the horizontal currents in the metal pad.
They have been reduced as compared to those presented in
Fig. 2 of Dupuis [2]. Unfortunately, the center channel
copper
steel
Fig. 3 Copper collector bar design originally proposed in Dupuis and
Bojarevics [14]
697
creates a gap that prevents the total elimination of a hori-
zontal component in the metal pad current regardless of the
size of the copper collector bars used.
External Compensation Current (ECC) Busbar
Network Design
As presented in Dupuis [2], the idea of taking advantage of
copper collector bars to extract 100% of the cell current on
its downstream side came to the author as a way to reduce of
busbar weight of its own reversed compensation current
(RCC) busbar configuration.
It happens that the same idea is easily applicable to
existing ECC busbar configurations. In that case, the busbar
network is reduced to only the anode risers so it is the
preferable busbar configuration if the main goal is to mini-
mize the busbar voltage drop in order to minimize the cell
energy consumption.
Figure 6 presents the busbar network and the calculated
busbar drop of 134 mV. The busbar current density is quite
low but this is consistent with a business scenario where the
metal cost is low and the energy cost is high. Figure 7 is
presenting the vertical component of the magnetic field (Bz)
obtained while using this busbar configuration (see [2] for
more results).
Anode Design with Innovative Stub Hole
Conception
As presented in Dupuis and Bojarevics [14] and in Table 2,
when operating the cell at 500 kA using 48 anodes of
1.95 m × 0.665 m, the predicted voltage drop is 265 mV.
This already very low anode drop is in great part due to the
usage of an innovative stub hole conception. That innovative
conception was tested in a thermo-electro-mechanical
(TEM) model presented in Dupuis [17]. Figure 4 of
Dupuis and Bojarevics [14] is showing the voltage drop
prediction from that TEM model but not the new stub hole
design investigated.
That design has been presented for the first time in
Dupuis [3]. Figure 8 is presenting the original ANSYS
voltage drop figure of the TEM model testing that new stub
hole design concept.
As discussed in Dupuis [3], the aim of the new design is
to get a good contact pressure between the stub bottom
horizontal face and the anode stub hole bottom horizontal
face. This is achieved by locking the stub vertical thermal
expansion. As presented in Dupuis [3], there is more that one
way to achieve this, the final optimized shape presented in
Dupuis [3] is less costly to implement, but was developed
after [14] was written.
698 M. Dupuis

Fig. 4 Cathode voltage drop

Fig. 5 Metal pad current density

Low Energy Consumption Cell Designs Involving Copper Inserts …
Fig. 6 Busbar drop of the ECC
busbar network concept with
100% downstream side current
exit
Fig. 7 Vertical component of the
magnetic field (Bz), Fig. 10 in
Dupuis [2]
From that starting point, the author tried to further reduce
that anode voltage drop for this study. The option to add
copper insert like the one presented in Sverre Sæsbøe [15]
was investigated but the gains were disappointing. It turned
out that the best way to achieve more mV saving was to
improved the anode aspect ratio.
Figure 9 is presenting the current anode aspect ratio, each
stub is feeding a rectangular carbon section of
0.4875 m × 0.665 m, and ideally, each stub should be
feeding a square section of carbon. This is important since
699
with 4 fairly big stubs and the new stub hole design, the
biggest resistance is now in the carbon section of the anode.
For that reason, the 48 1.95 m × 0.665 m anodes have
been replaced with 64 1.95 m × 0.5 m anodes keeping the
exact same stub diameter and stub hole design in order to
avoid to go back running the TEM model. Figure 10 pre-
sents the new anode aspect ratio.
With a parametric model at your disposal, the half anode
model can be modified in no time. The same is true for the
full anode panel model. Figure 11 is presenting the initial
700 M. Dupuis

Fig. 8 Anode voltage drop from

the TEM model

Fig. 9 One of the 48

1.95 m × 0.665 m anode

Fig. 10 One of the 64

1.95 m × 0.5 m anode
Low Energy Consumption Cell Designs Involving Copper Inserts …
Fig. 11 48 anodes panel layout
Fig. 12 64 anodes panel layout
48 anodes panel layout while Fig. 12 is presenting the new
64 anodes panel layout.
The resulting anode voltage drop is presented in Fig. 13,
simply by changing the anode aspect ratio and by increasing
the number of anodes from 48 to 64, the anode voltage drop
has been reduced from 265 to 224 mV.
701
Calculation of the Resulting Cell Energy
Consumption
Several modeling tools could be used to calculate the cell
energy consumption from the above results. In Dupuis and
Bojarevics [14] the author used Dyna/Marc [18] which also
predicts the cell superheat and corresponding ledge
thickness.
So far no effort has been made to adjust the cell lining
design to the new cell operating conditions so a simple cell
voltage break down tool like Peter Entner’s CellVolt [19]
was used instead. Table 3 presents the results obtained for
the operation at 500 kA corresponding to running at
0.8 A/cm2 of anode current density.
As in Dupuis [2], the calculation was done using 3.2 cm
of ACD instead of 3.5 cm used in Dupuis and Bojarevics
[14] as since 2011, indications are that ACD have been
reduced further more in low energy consumption cell pro-
totypes. At 3.2 cm ACD, the predicted cell energy con-
sumption is calculated to be 11.2 kWh/kg.
More significantly, the cell internal heat is calculated
to be only 699 kW while the cell lining was designed to
comfortably dissipate 1140 kW with 20 cm × 10 cm size
collector bars and 192 anode stubs. Clearly a very
serious cell lining redesign work needs to be performed
as the next step. New insulating materials like the
ceramic fire board extensively used in Zhou and Dupuis
[20] will certainly need to be added to the list of lining
materials.
In order to make the new cell lining design work even
more challenging and the cell energy savings even more
impressive, Table 3 also reports results for an operation at
400 kA corresponding to running at only 0.64 A/cm2 of
anode current density. At that current density and still at
3.2 ACD, the cell is expected to produce metal using only
9.95 kWh/kg.
The corresponding cell internal heat is calculated to be
reduced to 414 kW which is only 36% of the 1140 kW
dissipated by the same cell “platform” running at 600 kA
and 13.26 kWh/kg.
702 M. Dupuis

Fig. 13 Anode voltage drop

from the TE model

Table 3 Design and predicted Base case

cell energy consumption
Amperage (kA) 500 500 400
Nb. of anodes 48 64 64
Anode size 1.95 m × 0.665 m 1.95 m × 0.5 m 1.95 m × 0.5 m
Nb. of anode studs 4 per anode 4 per anode 4 per anode
Anode stud diameter (cm) 17.5 17.5 17.5
Anode cover thickness (cm) 10 10 10
Nb. of cathode blocks 24 24 24
Cathode block length (m) 4.17 4.17 4.17
Type of cathode block HC10 HC10 HC10
Collector bar size 20 cm × 10 cm 25 cm × 16 cm 25 cm × 16 cm
Type of side block SiC SiC SiC
Side block thickness (cm+) 10 10 10
ASD (cm) 30 30 30
Calcium silicate thickness (cm) 3.5 3.5 3.5
Inside potshell size 17.8 × 4.85 m 17.8 × 4.85 m 17.8 × 4.85 m
ACD (cm) 3.5 3.2 3.2
Excess AlF3 (%) 12.00 12.00 12.00
Anode drop (mV) 265 224 179
Cathode drop (mV) 87 130 104
Busbar drop (mV) 310 134 107
Cell voltage (V) 3.89 3.59 3.20
Current efficiency (%) 95.90 95.90 95.90
Internal heat (kW) 758 699 414
Energy consumption (kWh/kg) 12.1 11.2 9.95
Low Energy Consumption Cell Designs Involving Copper Inserts …
Conclusions
Two innovations presented by the authors recently at
ICSOBA conferences allow to very significantly reducing
both the cathode and the busbar voltage drop:
– cathode design with copper collector bars extracting
100% of the cell current on its downstream side
– the usage of modified external compensation current
(ECC) busbar configuration made only of anode risers;
are combined with a third innovation presented at the
Aluminiun of Siberia conference:
– the usage of a new anode stub hole design.
As a result, a cell operating at 500 kA, 0.8 A/cm2 of
anode current density and 3.2 cm ACD is predicted to have
an energy consumption of about 11.2 kWh/kg.
The same cell platform operating at 400 kA, 0.64 A/cm2
of anode current density and 3.2 cm ACD is predicted to
have an energy consumption of about 9.95 kWh/kg.
References
1. M. Dupuis, A new aluminium electrolysis cell busbar network
concept. in Proceedings of 33rd International ICSOBA Confer-
ence, Travaux No. 44, Dubai, UAE, 29 Nov–1 Dec 2015, Paper
AL21
2. M. Dupuis, New busbar network concepts taking advantage of
copper collector bars to reduce busbar weight and increase cell
power efficiency. in Proceedings of 34th International ICSOBA
Conference, Travaux No. 45, Quebec, Canada, 2–5 Oct 2016 (to
be published)
3. M. Dupuis, Presentation of a new anode stub hole design reducing
the voltage drop of the connection by 50 mV. in VIII International
703
Congress and Exhibition “Non-Ferrous Metals and Minerals”,
Krasnoyarsk, Russia, 13–16 Sept 2016 (to be published)
4. M. Dupuis, I. Tabsh, Thermo electric coupled field analysis of
aluminum reduction cells using the ANSYS parametric design
language. in Proceeding of the ANSYS® Fifth International
Conference, vol 3. (1991), pp. 17.80–17.92
5. V.A. Kryukovski, G.A. Sirasutdinov, J. Klein, G. Peychal-Heiling,
International cooperation and high-performance reduction in
Siberia. JOM 46(2), 23–25 (1994)
6. M. Dupuis, Les modèles thermiques. in 2e Symposium québécois
sur le procédé d’électrolyse de l’aluminium, CQRDA, 1997
7. M. Dupuis, Thermo-electric design of a 400 kA cell using mathe-
matical models: a tutorial. TMS Light Metals (2000), pp. 297–302
8. M. Dupuis, Thermo-electric design of a 740 kA cell, is there a size
limit. Aluminium 81(4), 324–327 (2005)
9. O. Fujishima, M. Takasawa, K. Wakaizumi, Advanced energy saving
in aluminum reduction cell. AIME Light Met. (1982), pp. 559–569
10. S. Tanji, O. Fujishima, K. Mori, Substantial energy saving in
existing potlines. AIME Light Met. (1983), pp. 577–586
11. AP60 and APXe: a breakthrough in productivity, energy con-
sumption and emissions. AP Technology™ Fact sheet, Mar 2015
12. F. Charmier, O. Martin, R. Gariepy, Development of the AP
technology through time. JOM 67(2), 336–341 (2015)
13. M. Dupuis, Thermo-electric design of a 500 kA cell. Aluminium
79(7/8), 629–631 (2003)
14. M. Dupuis, V. Bojarevics, Retrofit of a 500 kA cell design into a
600 kA cell design. Aluminium 87(1/2), 52–55 (2011)
15. D. Sverre Sæsbøe, Storvik high conductivity anode yoke with
copper core. in Proceedings of 33rd International ICSOBA
Conference, Travaux No. 44, Dubai, UAE, 29 November–1
December 2015, Paper AL23
16. R. von Kaenel and al., Copper bars for the Hall-Héroult process.
TMS Light Met. 2016, 903–908
17. M. Dupuis, “Development and application of an ANSYS based
thermo-electro-mechanical anode stub hole design tool”, TMS
Light Metals, 433–438 (2010)
18. M. Dupuis, H. Côté, Dyna/Marc 14.0 user’s guide. GeniSim
(2012)
19. P. Entner, CellVolt AlWeb application: http://peter-entner.com/ug/
windows/cellvolt/toc.aspx
20. J. Zhou, M. Dupuis, In-depth analysis of lining designs for several
420 kA electrolytic cells. TMS Light Met., 685–690 (2015)
 Minimizing Cathode Voltage Drop
by Optimizing Cathode Slot Design

Ralph Friedrich, Frank Hiltmann, Andreas Lützerath, Richard Meier,

Markus Pfeffer, Till Reek, and Oscar Vera Garcia

Abstract
Contact resistance between cathode block and cast iron plays an important role for the
ohmic resistance of the cathode system and hence for the cathode voltage drop (CVD).
Investigations of the standard dove-tail cathode slot design showed poor electrical contact
in the bottom of the slot and small contact area on the cathode wings. Different
thermo-mechanical properties of carbon cathode block, cast iron, and steel collector bar
resulted in displacements relative to each other after rodding, during cooling and handling.
To mitigate this effect without changing materials or procedures, different slot geometries
were modeled with respect to preheating and casting. By introducing anchoring grooves for
the cast iron at the bottom corners of the slot, bottom contact was achieved: Lab tests
proved that voltage drop between cathode slot bottom and cast iron decreased significantly.
Subsequent field trials showed a CVD reduction of 20 mV.

Keywords

Aluminum electrolysis Cathode Cathode slot Cathode voltage drop Contact
resistance Energy saving

R. Friedrich (&)
F. Hiltmann
M. Pfeffer
O.V. Garcia Introduction

SGL CFL CE GmbH, Soehnleinstrasse 8, 65201
Wiesbaden, Germany In the last years considerable efforts were made in primary
e-mail: Ralph.Friedrich@sglgroup.com
aluminum smelting technology development to reduce specific
F. Hiltmann energy consumption of the Hall-Héroult electrolysis process
e-mail: Frank.Hiltmann@sglgroup.com
[1–5]. With electrical energy as the main contributor to
M. Pfeffer smelting cost and economics, there is also a significant side
e-mail: Markus.Pfeffer@sglgroup.com
effect on greenhouse gas emissions when the energy is gener-
O.V. Garcia ated from fossil fuels [6, 7].
e-mail: Oscar.Vera-Garcia@sglgroup.com
Despite the cryolitic bath layer being the largest ohmic
A. Lützerath
T. Reek resistance in the cell, the cathode voltage drop (CVD) is
TRIMET Aluminium SE, Aluminiumallee 1,
45356 Essen, Germany another major contributor to cell voltage and therefore energy
e-mail: Andreas.Luetzerath@trimet.de efficiency of the smelting process. However, efforts for major
T. Reek decrease of CVD must take into consideration that joule
e-mail: Till.Reek@trimet.de heating of the cathode arrangement also contributes to the
R. Meier thermal balance of the cell, so counter-measures, such as
TRIMET Aluminium SE, Aluminiumstraße, thermal insulation or modified bath chemistry, may have to
21127 Hamburg, Germany be applied to compensate the lower heat generation until a
e-mail: Richard.Meier@trimet.de

© The Minerals, Metals & Materials Society 2017 705

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_86
706
sufficient number of cells has been relined to merit current
increases.
Measured between collector bar and liquid metal or
cathode surface, the CVD can be essentially regarded as a
series connection of resistances of collector bar, cast iron,
carbon cathode, and metal-to-carbon contact in between
(Fig. 1). If access to collector bars is constrained, measure-
ment is made against a specified position on the busbar
instead of a collector bar.
In case of measuring in the aluminum metal, resistances
of aluminum and contact to cathode block are included,
although these are almost negligible in normally operating
cells [8]. The contact resistance from cast iron to cathode
block strongly depends on contact pressure and temperature,
in particular because carbon is not readily wetted by liquid
cast iron [9, 10]. Due to thermo-mechanical and thermal
expansion effects, the electrical contact in the slot bottom is
much worse than at the sides of the slot [11]. Thermo-
electrical-mechanical (TEM) modeling calculations using
contact pressure and resulting contact resistance as variables
instead of arbitrarily fixed contact resistance values yielded a
lower current flow through the slot bottom compared to the
vertical sides of a dove-tail slot [12]. Since already the
measurement of the cathode contact pressure in situ during
electrolysis is extremely challenging [13], the contact resis-
tance is generally used as fitting factor for the modeling
calculations to match the experimental results. Similar con-
siderations were also made for cast iron-rodded anode blocks
[14–16].
The foundation for the cathode performance during
operation is laid already in the rodding process, where
electrical contact is established by pouring molten cast iron
in the gap between steel collector bar and carbon cathode
block. Temperature control for all components—collector
bar, cathode block, and cast iron—during preheating and
rodding is paramount to ensure a good performance,
Anode
Bath
Aluminum
Cathode block
CVD
Collector bar
Fig. 1 Hall-Héroult cell with CVD measurement technique (schematic
representation)
R. Friedrich et al.
i.e. establishing good electrical contact during electrolysis
while avoiding excessive mechanical stresses on the cathode
blocks during rodding and cell start-up [17–19]. This is
particularly important because the different materials
involved have different thermal expansion and shrinkage
characteristics, e.g. with the collector bar steel expanding up
to four times more than carbon, giving rise to movements
relative to each other during the entire rodding process. Last,
but not least, the cast iron composition must comply with
rodding equipment and process constraints, and forecast
dimensional changes in the whole arrangement during
pouring and cool-down [20].
Looking at the design of the cathode slot, rectangular or
—as a variant of it—dove-tail slots have emerged as the
most common shapes in the aluminum industry [21].
Figure 2 gives an overview about common slot designs used
in aluminum electrolysis today.
Although rodding practices became quite sophisticated
over the last decades, wing cracking can still occur with
inadequate rodding parameters, sometimes only at cell
start-up [19]. High cathode voltage drop and severe distur-
bance of the cathodic current flow result, leading to instable
operation, and in worst case to premature failure of the entire
cell [22].
As already pointed out by Haupin in the 1970s, the
increasing cathode voltage drop over time can be primarily
attributed to the deterioration of the electrical contact from
carbon cathode block to cast iron [8]. Several effects—some
of them still not fully understood—or a combination of them
can deteriorate the electrical contact: e.g. sodium-induced
creep of carbon cathode at high temperatures, creep of col-
lector bar steel, deposition of salts at the carbon-metal
interface, carbon diffusion into steel collector bar, or alloying
of cast iron with penetrating aluminum [8, 10, 21, 23].
Amorphous cathodes, based on calcined anthracite with
usually some synthetic graphite addition, are subject to
expansion by sodium intercalation into the carbon lattice,
and also to catalytic graphitization which lowers the resis-
tance of the cathode material [24, 25]. This effect is much less
pronounced for graphitic and especially graphitized cathode
blocks, commonly used in today’s high-performance smelt-
ing technologies.
A modified cathode slot design was developed to improve
the electrical contact in particular in the bottom of the slot.
slot bottom
slot
side
dove-tail rectangular trapezoid round double-slot
Fig. 2 Commonly used cathode slot shapes
Minimizing Cathode Voltage Drop by Optimizing Cathode Slot Design
Development, modeling and experimental results in both lab
and industrial environments are reported in this paper.
Current Status of Cathode Technology
The optimization project was carried out as part of a tech-
nical cooperation between SGL Group and TRIMET SE
with experimental work focused in their smelter in Ham-
burg, Germany. The smelter was started up in 1972 as
Hamburger Aluminium Werke (HAW), using Reynolds P19
technology. After acquisition by TRIMET in 2006, the idled
smelter was restarted [26] and is currently operating at
180 kA with an annual production of 133,000 t Al.
The cathode design is characterized by a single dove-tail
slot holding a split collector bar with cross-section of
180 × 140 mm in a block with outer dimensions of
530 × 410 × 3360 mm (W × H × L). 14 of such graphitic
—i.e. based on 100% synthetic graphite in dry aggregate—
carbon cathode blocks form the cathode bottom of the cell.
Conventional iron casting is used for collector bar rodding.
A gas pre-heating unit receives six cathode assemblies for
pre-heating the steel bars and cathode blocks. After pouring
cast iron and a cooling phase of several hours the cathode
assemblies are turned upside down for storage, until instal-
lation in the pot.
When turning the cathode assemblies, the steel bars slide
downwards and a gap formation of up to 10 mm between the
slot bottom and the top of the cast iron layer was observed
over the full length of the cathode block, as shown in Fig. 3.
Gaps between the slot bottom and cast iron do not fully
close during installation of the cathode blocks in the pot:
With a caliper gaps between 2 and 5 mm were measured and
not one single cathode block was found without a gap. Gaps
in the measured range will not close by thermal expansion of
7.3 mm
Fig. 3 Rodded cathode block after turning (cut slab)
707
the materials and hence it is very doubtful that under such
circumstances a reasonable electrical contact between slot
bottom and cast iron layer around the collector bar is
established in operation.
In order to determine the contact resistance to all sides of
the slot, lab tests on slabs of graphitic 5BGN-R cathode
blocks of SGL Group with a length of 300 mm were carried
out. The test slabs were iron-cast at exactly the same
pre-heating and rodding conditions as for standard blocks in
Hamburg. One slab was positioned in a lab furnace with
cathode and cast iron at the same level and the gaps between
cast iron and cathode slot determined at all sides. Wing gaps
between 0.1 and 0.2 mm were recorded at both sides and the
gap between slot bottom and top of collector bar (cast iron)
was measured with 1.5 mm while the collector bar was
supported at the same level as the cathode. In order to
simulate the operational conditions in an electrolysis cell, the
working surface and steel bar were electrically contacted and
placed in a lab furnace, as shown in Fig. 4. A direct current
of 1000 A was applied, while the slab was heated up in a lab
furnace under argon with 135 °C/h until it reached a final
temperature of 950 °C. After a two-hour soaking time at
950 °C the furnace was switched off.
During heat-up and soaking time the block temperature
and the voltage drops at several positions at the wings and
the slot bottom were recorded. In this first trial configuration
current flow could be measured only through the wings, but
not through the slot bottom area.
In a second trial the initial gap at the slot bottom area was
reduced to 0.5 mm by re-positioning of the steel bar. With
this new configuration a measurable current flow through
the slot bottom was observed above 200 °C and contact
resistance values could be calculated, which were at some
temperatures, however, still more than 100 times higher
Fig. 4 Experimental set-up for laboratory contact resistance
measurements
708
10000
1000
Contact Resistance [Ω·mm²]
100
10
0.1
0 200
Fig. 5 Contact resistance for cathode wings and slot bottom as a function of temperature, measured on laboratory slab
compared to the contact resistance at the wing areas (Fig. 5).
As a detailed thermo-electrical-mechanical finite-element
model was not available at that time, it was decided to take a
more empirical approach to further develop the slot design.
Based on these results a decreased contact resistance at
the slot bottom can be expected through further reduction of
the initial gap between slot bottom and cast iron which
subsequently should lead to a significant CVD reduction in
operation. This conclusion was taken as guiding principle for
the cathode slot design optimization.
Cathode Slot Design Optimization
In order to achieve electrical contact between slot bottom
and cast iron without any changes in cathode rodding, pot
assembly and start-up procedures, modification of the design
of the cathode slot itself turned out as most promising
development avenue. Therefore the slot geometry and dif-
ferent possible anchoring systems as well as positions of the
anchoring point for the collector bar/cast iron arrangement
were evaluated by modeling thermal expansions and elec-
trical contacts. This analysis showed that the anchoring
point should be as close as possible to the bottom of the slot
to minimize the gap formation between slot bottom and cast
iron during turning of the cathode assembly. The root causes
for slot formation are mechanically weak connections on the
one hand and different thermal expansion of carbon and
steel in the length between holding point and slot bottom on
the other hand. In the standard dove-tail design the
anchoring is provided by the pinch point, i.e. the point of
lowest slot width, which is usually at or near the half height
of the slot.
R. Friedrich et al.
LeŌ Wing
Right Wing
Slot BoƩom
~100x ~15x
400 600 800 1000
Temperature [°C]
The anchoring was carried out by machining an undercut
groove into the corners of the standard slot, which resembles
the shape of the Greek letter omega (Ω), as shown in Fig. 6
[27]. During rodding this cavity is filled with cast iron, and
forms a firm anchor when the liquid cast iron solidifies.
When turning the cooled-down block into the assembly
position the steel bar remains in position without any
downward shift or gap formation between slot bottom and
cast iron.
The cathode resistance for the new slot design was
measured in the lab by applying the same test configuration
and conditions as described for the standard slot design in
Chap. 2. The test results showed a reduction of this resis-
tance by approx. 30% at pot operating temperature compared
to the standard slot (Fig. 7). Considerations from tests and
modeling indicated a potential for CVD reduction of about
20 mV in an industrial cell.
This attractive savings potential encouraged a field trial in
an industrial electrolysis cell, for initial validation of the
novel cathode slot design.
Field Trial at Hamburg Smelter
Field Trial with Two Cathode Blocks in One Pot
Proof of concept was done with two cathode blocks out of
14 in a standard pot. All cathodes were made out of graphitic
material (grade 5BGN-R by SGL Group). Standard rodding
conditions were applied and both cathode blocks were suc-
cessfully iron-cast without wing cracks or other damages.
The preheating temperatures on one side of the cathode
blocks were rather low, due to not properly working gas
Minimizing Cathode Voltage Drop by Optimizing Cathode Slot Design
Fig. 6 Drawing for novel slot design (left) and rodded test slab (right)
Fig. 7 Cathode resistance for novel slot design and standard slot
design, measured on laboratory slabs
burners. This was accepted due to the general nature of this
first trial.
The downward shift of steel bar and cast iron after turning
the cathode assembly was determined on each side of the
cathodes at cold conditions. With a digital caliper the dis-
tance between slot bottom and steel bar surface (cp.
Figure 3) was measured and compared with the standard slot
design. The downward shift was calculated as the difference
of the distance between the measurement in rodding position
and operating position. Measurements compiled in Table 1
showed very low downward shifts—in the range of mea-
suring equipment accuracy—for the two test blocks with the
novel slot design only.
After cell start-up in November 2015 the CVD between
aluminum metal pad and end of steel collector bar as well as
current pick-up per collector bar (to determine the cathodic
resistance) were measured weekly. As the two OMEGA test
blocks were operated in one cell with twelve conventional
blocks, a lower CVD should appear with the measurements
described above as well as an above-average current pick-up
due to the lower cathodic resistance of the trial blocks.
709
A distinct and significant difference was not visible in the
voltage readings, but in the current pick-up rates per col-
lector bar. The bars with the new slot design were taking up
10% more current than the others. The difference was also
visible in the cathodic resistance which was consistently up
to about 4 µΩ lower over the 280 days operation period to
date, as shown in Fig. 8. Transferred to milli-volt saving,
4 µΩ correspond to 25 mV, which is in the same range as
observed in earlier lab tests. The resistance reduction was
more pronounced on the downstream side of the cathode
blocks. On the upstream side the resistance was similar to
the standard slot design. Further investigations showed that
the higher resistance corresponded to the cooler block part
during rodding mentioned earlier. This emphasizes the
importance of precisely controlled rodding conditions and
temperatures, which strongly influence the performance of
the cathode assembly in operation. This subject was however
not part of this study and will therefore not be analysed
further here.
Field Trial on a Complete Pot
After the positive results from the two-blocks cathode field
trial, a full pot was installed with the new OMEGA cathode
slot layout in otherwise standard cell design. All these gra-
phitic 5BGN-R blocks were rodded without particular
observations. Start-up of the trial cell was on February 6,
2016, using electrical pre-heating. Since cell start-up, mon-
itoring of CVD and cathodic resistance was done on a
weekly basis. The CVD was measured as a voltage differ-
ence between aluminum metal pad and a fixed busbar con-
nection at the tap-end corner riser. A peer group of eleven
pots was selected as reference with the same line current as
the trial pot. This group is also equipped with the same
cathode grade 5BGN-R and was started within the last
1.5 years. The measured CVDs are classified into age groups
of 30 days, averaged, and compared in Fig. 9.
710 R. Friedrich et al.

Table 1 Downward shift of Cathode block OMEGA design (mm) Standard design (mm)
collector bar after turning of
rodded cathode assembly #1 End A 0.0 0.9
#1 End B 0.1 4.1
#2 End A 0.2 0.8
#2 End B 0.0 1.0

Fig. 8 Cathodic resistances for

trial cell, per individual collector Boxplot of Cathodic Resistance [μOhm] per each steel bar
bar
55

Cathodic Resistance [μOhm]

Upstream Downstream

50

Trial blocks
45

40

35
Trial blocks
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28
Collector bar no#

Fig. 9 CVD for OMEGA trial

pot versus reference pots, Interval Plot of Cathode Voltage drop [mV]
grouped by pot age intervals
Bars are 2 Standard Errors from the Mean
340
Cathode Voltage drop [mV]

330

320

310

300

290

280
Pot A ce A ce A ce A ce A ce A ce A ce A ce
E G r en EG ren EG ren E G r en EG r en EG ren E G r en E G r en
M M M M M M M M
O efe O efe O efe O efe O efe O efe O efe O efe
R R R R R R R R
Pot age
30 60 90 12
0
15
0
18
0
21
0
24
0

Individual standard deviations were used to calculate the intervals.

The OMEGA slot design showed significantly lower design showing significantly higher standard deviation. This
CVD values until 120 days of age. The values found are up is a typical indicator for sludge formation in the cell, which
to 20 mV lower than the average of the reference group. At is independent from the trial design. The trial cell recovered
120 days, the averages are similar with the OMEGA slot however and shows lower CVDs again.
Minimizing Cathode Voltage Drop by Optimizing Cathode Slot Design
At 180 days pot-age and higher, both values start to
swing, albeit the OMEGA test cell remains at 15–20 mV
lower CVD level than the reference group. These swings
indicate larger overlaying trends in the potline. Due to the
age distribution in the reference group, these swings are
smoothed and do not match the pot age of the single
OMEGA test cell.
It is important to note, that even at periods of high CVD
of the test cell, it reports similar values than the reference
group at its best. To better validate the results, a larger test
section with OMEGA cathode slot design is to be installed in
the near future.
Conclusion
The standard dove-tail cathode slot design does not give
sufficient electrical contact through the slot bottom. By
anchoring the collector bar at the slot bottom with omega-
shaped grooves electrical contact between collector bar and
slot bottom can be achieved and potential for significant
CVD decrease realized.
First trial results in the Hamburg smelter showed a sig-
nificantly higher current pick-up on cathode blocks with the
OMEGA design compared to standard dove-tail cathode
blocks installed in the same cell, already indicating a better
overall contact to the cast iron surrounding the collector bar.
Installed in a complete cell, the OMEGA slot design
shows CVD values which are up to 20 mV lower than for a
reference group in the same line. All cells used SGL’s
5BGN-R graphitic cathode grade. During operation the
difference in CVD between test cell and reference group was
not stable, however, the test cell always reported values at
least as good as the best CVDs measured in the reference
group. This indicates that the new OMEGA slot design is a
simple and effective way of reducing CVD without neces-
sitating changes in relining or rodding procedures. To further
validate the results, a larger test group of cells using
OMEGA slot design cathode is going to be installed in
TRIMET’s smelters.
References
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high energy efficiency aluminum reduction pot (“HEEP”) tech-
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11. R. Beeler, Bar to block contact resistance in aluminum reduction
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13. M. Emami et al., Development of a new methodology to measure
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contact between steel and carbon cylinders using the finite element
method. Light Met., 523–528 (2000)
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rodded anodes. Light Met., 1067–1072 (2009)
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steel-carbon interfaces. JOM 68(1), 49–57 (2016)
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 Part XVII
Aluminum Reduction Technology:
Potroom Operations
 Crane Electrical Insulation Monitoring
in Potlines New CANDI™ 4.0 Development

Serge Despinasse and Eric Norel

Abstract
The still on-going productivity improvement realized in potlines outlines the importance of
the tending crane availability rate, which results from both their reliability and their
easiness to repair. In the field of the crane electrical insulation monitoring—essential for
ensuring operator safety and avoiding equipment damage, it is now expected that
preliminary incidents being quickly tracked and fixed, in order to minimize the
investigation time. This paper presents the new version 4.0 of the Fives ECL CANDI™
monitoring system. It deals with a new modular architecture, which allows its
implementation on green field projects as well as on retrofitting ones; it also focuses on
the evolution of the scanning which brings faster results. It finally presents the information
the operating or maintenance people will benefit thanks to a thoroughly redesigned
human-machine interface and new data transmission capabilities.

Keywords
Potroom operations Pot tending machines Electrical insulation Safety monitoring
Maintenance

Introduction
Operations in reduction pot-rooms producing aluminium
require a very regular task sequence in order to keep the
process as steady as possible. Many of these tasks are carried
out by special cranes, generally called Pot Tending Machi-
nes (PTM), which perform the anode changing, the metal
tapping and from time to time the raising of the anode beam.
With pressure on capital expenditures costs when erecting
new smelting facilities and on operating costs for running
them, the PTM availability rate is of the upmost importance.
As an example, a potline of 424 pots can be operated with
only 12 PTM, tapping operation included. This can be
achieved thanks to a good PTM performance concerning the
time cycle to execute the tasks on one hand and to a good
availability rate on the other hand. That later one typically
S. Despinasse (&)
E. Norel
Fives ECL, 100 Rue Chalant, 59790 Ronchin, France
e-mail: serge.despinasse@fivesgroup.com
exceeds 95%, resulting from both a low breakdown rate and
a fast time to repair.
One of the causes a PTM cannot be available on time is
related to its electrical insulation level; as it is detailed in
article [1], such insulation is critical both for people safety
and for the PTM integrity. It is well known that cranes
running in a potline can be in contact with two metallic
structures having an electrical potential difference of several
hundred volts. For example the main crane girders are per-
manently in contact with the building railways at earth
potential, meanwhile the anode extracting wrench can be in
contact with the anode stem of one of the anodes of a pot
located far away from the grounding-to-earth point of the
potline. The crane must be built with electrical insulating
barriers, on its embedded electrical power distribution circuit
and on its metallic structure. One single insulating barrier
between the extremal potentials would not be safe enough as
one single defect of that barrier would create certainly a
short-circuit of the potline, initiating by this way an electrical
fire on the crane, given the available potline power; it would

© The Minerals, Metals & Materials Society 2017 715

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_87
716
also create a very dangerous situation for the people working
close to the crane as they would be exposed to electrical
shock hazard. Consequently, cranes operating in potlines are
designed with atleast two electrical insulating barriers. Such
arrangement allows for a first insulation default event
without resulting in dramatic consequence, provided that all
the insulating barriers are monitored. Systems employed for
such monitoring will generate alarms based on the measured
impedance level of the insulating barriers. Depending on the
alarm management, the crane can be idled before the cause
of the alarm is fixed.
The CANDI™ monitoring system proposed up to now by
Fives set a first threshold, said “Alarm”, for which a main-
tenance intervention must be planned, and a second thresh-
old said “Fault” for which the operation must be stopped and
the crane must be placed in a safe location, in order to be
inspected by qualified maintenance operators. The time
required to locate and fix the isolation defect will obviously
impact the availability rate of the crane. The CANDI™
monitoring system as described in article [1] allows for a
location of the defect by ground class and facilitates the
investigation of the defect area during the maintenance
diagnostic.
Users of the monitoring system expressed some addi-
tional needs that lead Fives to develop a new generation
solution, called CANDI™ 4.0, which aims at a better crane
availability, an easier understanding of the system, a wider
applicability range taking into account existing crane refit-
ting needs while implementing the latest technology trends
by easing the access to data.
New Modular Architecture
One of the key driver which has been set for the new
CANDI™ 4.0 development team was to design a solution
available not only for the brand new cranes, but also for the
ones of the existing fleet, where the oldest cranes can exceed
thirty years and lead to obsolescence concerns.
The new system should cope with a wide variety of
configurations:
– There are cranes equipped with programmable logic
controllers (PLC), others with “traditional” relay logic;
– Some of them are built with three successive insulating
barriers (i.e. four isolated ground levels), others with two
barriers (i.e. three isolated ground levels);
– The number of trolleys can vary from one to three, each
of them being a middle ground structure with two insu-
lations to monitor;
– The PTM electrical power supply can be grounded either
with the TN mode (neutral to ground) or the IT one
(impedance grounded neutral).
S. Despinasse and E. Norel
The new system has been designed around a basic core
included in a single cabinet, combined with remote ground
boxes which house local switches.
Then options can be added such as electrical power dis-
tribution monitoring (IT version), connection with graphic
tablet.
The new monitoring system is based on a modular
architecture (Fig. 1) comprising:
– A core unit in a cabinet, which integrates a controller, a
local Human Machine Interface (HMI) screen, High
Voltage relays and an Insulation Monitoring Device
(IMD);
– A batch of local “Equipotential bounding” boxes related
to one single potential structure (for example a trolley),
allowing for the adaptation of the monitoring architecture
to the crane physical architecture. Thanks to their internal
arrangement, they allow for the differentiation of
sub-grounded parts through a set of switches;
– All the cabinets and the boxes are connected together
through a communication network, for example the PTM
one if existing.
The system can run in a stand-alone configuration or
connected to the crane PLC network. CANDI™ 4.0 is
compatible with 2 or 3 insulating barriers and with various
crane structural architectures. It can be used on PTM,
Cathode Transport Cranes (CTC) and Tapping and Miscel-
laneous Assembly cranes (TMA).
Wider Application Field
Thanks to its modular architecture, the system can evolve
easily to be adapted to any specific situation. It comprises a
basic configuration being able to monitor cranes built with
two insulating barriers and fed with a TN power supply
(power circuit neutral connected to earth ground). Options
can be added to monitor a third insulating barrier or an IT
power supply.
This allows for a quite easy installation on both cranes of
greenfield project and retrofitted cranes in existing plants.
Figure 2 illustrates a “complex” case of CANDI™ 4.0
implementation on an old equipment fitted with two tapping
trolleys, one endless revolving tool turret and one cabin turret
fixed under a travel trolley, the “earthed A” potential of the
long travel trolley being separated from the “tool turret”
potential by one insulating barrier. For that particular case,
two core cabinets and two equipotential bounding boxes are
used, each system runs independently.
Figure 3 illustrates a “simple” case of CANDI™ 4.0
implementation on a recent equipment fitted with a single
trolley, the “earthed A” potential of the long travel trolley
Crane Electrical Isulation Monitoring in Potlines … 717

Fig. 1 Architecture of CANDI 4.0 system

Fig. 2 System architecture for a complex case (old PTM generation)

718
Fig. 3 System architecture for a simpler case (new PTM generation)
being separated from the “tool turret” potential by one
insulating barrier. For that particular case, one core cabinet
and one equipotential bounding box are used.
Core cabinets and Equipotential Bounding Boxes are the
same in both cases.
Smarter Alarm Management
For cranes equipped with PLC automation, an intelligent
interconnection between the new monitoring system and the
crane PLC will allow a smarter management of the alarms.
With the previous system, an alarm or a fault is generated
if an impedance threshold is reached during the monitoring,
each isolation concerning a couple of grounds being mea-
sured one after the other on a fixed scanning sequence. For
PTM, the alarm which is reported in the cabin informs the
operator with the default type (ALARM or FAULT) and the
ground levels concerned, without precise location. For
example a said C–D default will inform the operator that the
insulation level between the carriage and one of the tools is
too low, without indicating if it is related to the
crust-breaker, the shovel, the anode extracting wrench, the
anode covering product tube or the tapping hook (refer to
Fig. 3). The identification of the concerned area has to be
done at a later stage by maintenance people.
With the new CANDI™ 4.0, the information issued by
the scanning sequence indicates automatically the location of
the isolation fault without operator maintenance interven-
tion. Only the faulty machine subassembly is OFF, the rest
of the machine remaining operational.
S. Despinasse and E. Norel
As the isolation level is measured analogically by the
IMD, each measure can be stored for various couples of
grounds, including separated “sub-ground” measurement,
which can be associated with a PTM tool for example.
Human-Machine Interface (HMI)
The core cabinet is fitted with a 6″ HMI, which allows to
communicate locally with the system, it is obviously dedi-
cated to maintenance people in charge of making the
diagnostics.
Those HMI screens can also be plotted on the HMI of the
PTM cabin (Fig. 4).
As an option, the same HMI screens can be duplicated on
a wireless graphic tablet, from the ground nearby the crane
for example (Fig. 5).
Monitoring and Trouble-Shooting
The HMI “home screen” gives general information on the
system, such as: present measuring status (ground couple
identification), last measured value, possible alarms or faults
(Fig. 6).
Specials screen pages with popups have been developed
for maintenance people, who will be able to access to:
– Clear messages associated with fault codes, which guide
the operator in carrying out its diagnostic by displaying
troubleshooting scenario; expected faceplate states, etc.;
Crane Electrical Isulation Monitoring in Potlines …
Fig. 4 HMI screen shots
Fig. 5 HMI screen on tablet
– The electrical diagram of the monitoring system;
– The main component documentation, like the IMD one.
In addition to those “troubleshooting” screens, data are
logged by the CANDI™ 4.0 controller and can be dis-
played on HMI graphics in order to detect some trends
concerning an isolation level (dust or oil deposit effect for
example) or the frequency of alarms per location/tool
(help for tracking intermittent faults for example) (Figs. 7
and 8).
719
As for the other HMI screen pages, such logged data can
also be reached on a remote tablet.
A special care has been taken for filtering all the alarm
and fault messages, especially when a first event generates a
cascade of secondary ones. Only important messages are
reported to the operator.
Such evolution is an important step compared with the
previous generation of monitoring systems, where the
available information, mainly lights and fault codes, had to
be interpreted by skilled and well trained people.
720 S. Despinasse and E. Norel

Fig. 6 Typical HMI page showing an overview of the system

Fig. 7 HMI page showing an insulation level trend

Crane Electrical Isulation Monitoring in Potlines …
Fig. 8 HMI page showing the alarm numbers per tool
Safety Performance
This new generation of insulation monitoring system has
consolidated the same safety performance as for the previous
CANDI™ one. It is compliant with a potline voltage up to
2000 V. High voltage relays, high voltage connecting boards
have been carefully selected for that purpose. The connect-
ing cables between the IMD and the high voltage connecting
boards are monitored by the device itself.
High voltage connecting boards are designed to limit the
current which would occur during a short circuit.
The proper functioning of all the components is tested in
magnetic field, for various intensity and direction, on a
specific bench available at Fives ECL facilities in Ronchin,
France.
The system logic is qualified by applying a testing pro-
tocol on a development plate-form which reproduces various
architecture configurations.
Conclusion
Insulation monitoring systems are essential devices for
maintaining cranes running in a potline at their highest level
of performance. CANDI™ family products have evolved
721
significantly since the first generation release 34 years ago.
The Gold version introduced a first help for investigating
possible defects and could cope with large high voltage
potlines; this new 4.0 version improves the system super-
vision and management by giving a clearer, simpler, com-
prehensive information directly on local HMI or connected
tablets. It will be also more precise for locating defects, as
main structural grounds are now split in sub-ones, typically
one per tool. And last but not least, its modular design allows
for implementation on a wide variety of cranes, including the
oldest ones.
It also allows maintenance people to keep pace with the
industry practices which promote predictive maintenance on
the basis of data collection and processing.
Reference
1. A.-G. Hequet, Effective insulation control monitoring system: the
CANDI™ solution for a safer production, Light Met. 905–907
(2012)
 Surviving an Extended Power Outage After
a Break Down in the Sub Station

T. Reek and R. Düssel

Abstract
TRIMET Aluminium SE operates the Essen aluminium smelter with 3 potlines in
Germany. On April 12th 2016 a smoke alarm in the substation triggered an emergency
shutdown of the whole plant. The smoke alarm was triggered by a short circuit on a 21 kV
bus bar. While potline II and III could be restarted within 2 h, the damaged bus bar had to
be removed, separating potline I from the redundant high voltage power supply and fixing it
on a single 220 kV transformer. When potline 1 was able to be restarted, the 220 kV
transformer was found to have an insulation fault. An emergency bus bar replacement was
welded in place and potline I could be re-energized after 5 h 50 min and 30 s. Due to the
immediate steps taken in the potrooms, any pot loss could be prevented and the potline was
back to normal operation in 12 h.

Keywords
Power outage Aluminium reduction Recovery

Introduction Continuity in electrical power supply is therefore of very

The aluminium reduction process is an electrochemical
process operating close to 960 °C. This temperature is
necessary to keep the electrolyte in a molten state. Typically
the process temperature is only a few degrees Celsius above
the liquidus temperature of the molten electrolyte. The sole
heating agent is electrical current pathing through the cell
and enforcing the electrolytic reduction of alumina. As soon
the heating is interrupted, the cells start to cool and imme-
diately the superheat of the electrolyte is reduced to 0 °C and
solidification starts. As pure cryolite starts to solidify first,
the concentration of additives in the electrolyte, such as AlF3
increases and in turn keeps the bulk of the electrolyte liquid.
As long as enough electrolyte is liquid in all of the cells, the
potline can be restarted. Typically this period is stated as 4 h
[1, 2].
high importance for operating a smelter. However, there are
regular instances of power outages affecting aluminum
smelters. However, detailed publications on power outages
and their effects on potlines are limited. Øye and Sørlie detail
some outages, but seldomly the exact duration or the cause is
given. Measures to preserve heat in the cells or steps taken to
re-energize the potline are typically not discussed.
Effects vary from little effect, to 10–20% of the produc-
tion being shut down, to failures of full potlines [3–5].
Effectively, this limits successes of recovery to the
experience (and nerves) of the staff on site. While there can
be no universal emergency plan, there are some simple rules
and guidelines to at least increase the chances for success for
re-energizing the potline.
This paper summarizes the experiences made in Essen
during a 6 h power outage in one of the potlines.

T. Reek (&)
R. Düssel

TRIMET Aluminium SE, Aluminiumallee 1, Essen, Germany
e-mail: till.reek@trimet.de

© The Minerals, Metals & Materials Society 2017 723

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_88
724
Course of Events
On April 12th 2016 at 05:10:35 the full plant dropped
off-line while a smoke alarm in the building of the
medium-high voltage was detected. The fire brigade was
called to investigate the cause and did not find a fire source.
After ventilation, maintenance was cleared to enter the
building (still devoid of power) and found partly scorched
and melted bus bars in the 21 kV switch room.
The damaged section was a redundancy cross link
enabling potline I to receive electricity from another than a
single 220 kV transformer. Thus, the bus bar was perceived
as uncritical for the immediate restart. The damaged section
is shown in Fig. 1.
The damaged section was removed and the plant
including the compressed air station, cast house and GTC
were smoothly restarted. Potline III and potline II could be
restarted at 7:23 and 7:25 am respectively with slightly more
than 2 h power outage.
Potline I could not be energized. Isolating and removing
the damaged 21 kV bus bar had isolated potline one on a
single 220 kV transformer. When this transformer was to be
switched on, it immediately failed.
With the usual redundancy removed and isolated on a
damaged transformer, a contingency plan was needed. The
potroom relining department, who also repairs and modifies
potroom bus bars when damaged, were called to prepare an
emergency weld to bridge the gap the removed bus bars had
created. While this was in preparation the plant was
scourged for material that could be used as 21 kV bus bar—
both in material quality as well as in diameter and length.
Replacement bus bars were welded in place on all three
phases and the potline could be reenergized at 11:01 am,
close to 6 h after the initial power outage.
Fig. 1 Scorched 21 kV busbar
T. Reek and R. Düssel
Post event analysis showed the course of events leading
to the damage as follows:
In one 21 kV panel for the auxiliary power a cable end
sealing of one phase failed in isolation towards earth. This
led to an arcing short circuit with a neighboring phase.
About 10 ms later a full 3-phase short circuit developed with
a short-circuit current of up to 25 kA. About 100 ms later
the vacuum power switch disconnected the affected trans-
former as expected. This dropped the auxiliary power for the
plant off-line and consequently dropping the potlines as well.
Before the shut down, the electric arc had jumped to the
21 kV power bus bar in the upper part of the section panel,
short circuiting the inlet transformer on all three phase with
up to 27 kA. This led to 220 kV power switch to trigger
after 1.3 s.
While the transformer should have been able to survive a
short circuit current for this duration, its insulation was
found to be damaged afterwards.
Measures to Preserve Heat in the Cells
TRIMET enrolls their potlines to the German grid relieve
system. Thus the grid operating companies can shutdown
enrolled electricity consumers instead of activating spinning
reserve power plants.
TRIMET Essen’s potlines had been switched off one day
earlier for 50 min. TRIMET is familiar with such procedures
and therefore the potlines had recovered their heat balance
when the large blackout occurred.
As per regulations and standard procedure TRIMET’s
Environmental Officer had to inform the authorities imme-
diately of the black out, as all environmentally relevant
facilities—such as the central GTC—were powered down as
well.
According to procedure, the GTC was started at reduced
capacity for the restart of the first potline. The ducting is
centralized and when suction is applied, a reduced suction
rate is realized on all cells across the plant.
When potline III was started 7:23 am, 7 out of 20 mod-
ules of the central GTC were in operation. The number was
immediately raised to 14 modules with the restart of potline
II. Anticipating a rapid start of potline I as well, the GTC
was brought to full capacity at 7:29 am.
Still assuming a quick restart of the last potline and to
minimize emissions, the GTC was kept at full capacity while
investigations were ongoing in the rectifier to determine the
cause for the inability to energize potline I.
As soon as the damaged rectifier was found to be the root
cause, it became clear that an immediate restarted was not
possible. As a result, the GTC team started to install damper
plates to disconnect potline I from the GTC. The steel
damper plates were large enough to cover the two 2.5 m
Surviving an Extended Power Outage after a Break Down …
diameter collection main ducts of potline I. These plates
were luckily already available onsite from the crisis faced in
2009, when two potlines had been idled and disconnected
from the GTC.
To speed up the process, at 9:50 am the decision was
taken with the environmental authorities consent, to power
down the GTC. At 9:53 am the GTC was shut down. With
the under pressure gone from the ducts, the damper plates
were able to be installed immediately and the GTC could be
restarted with 2/3 capacity to service the operational potlines
within minutes. The development of the GTC volume is
shown in Fig. 2.
Disconnecting potline I from the GTC significantly slo-
wed the decay of residual voltage on the potline as shown in
Fig. 3. The voltage dropped by 6 V/h before. This trend was
reduced to 2 V/h after placing the dampers. The inflection
point is clearly visible in the graph. Internal measurements
have shown that during normal operation TRIMET Essen is
losing about 30% of the heat to the dry scrubber. By drop-
ping the rate of decay by 60% when disabling the draft at the
top side of the cells, the mechanics for heat loss during
power outage appear to be significantly different.
Additional measures to preserve heat were also discussed.
Most notably was the idea to apply additional cover material
to the top of the crust to reduce the heat loss even further.
To judge the possible impact of cover spillage into the
cooled electrolyte, one single electrolyte height measure-
ment was performed on a cell. Only 8 cm of a very sludgy
electrolyte was found. The risk of cover material spillage
into the cell cavity was deemed to risk and not followed up
on.
Fig. 2 Line amperage (blue) and GTC capacity (red) during the power outage
725
It was decided to leave the cells as they were for the
remainder of the outage.
Decision to Restart and Preparation
Drawing on previous experiences and difficulties of suc-
cessfully restarting the potline after close to 4 h of power
outage after storm damage in 2002, discussions with the
CEO started at about 9:30 h for an orderly shutdown and
removing the anodes from the electrolyte.
Informed of the situation in the potrooms, the casthouse
had kept all furnaces empty and waited on standby for
potroom metal, in case a controlled shut down of potline I
was decided.
Previous experience of tapping metal more than 1 shift
after shutting down a cell resulted in the assessment that in
an ideal case, 400 t or 30% of the metal inventory could be
salvaged before the cells would be frozen.
The outlook was bleak and the team was close to being in
a position that all would be lost, when the supervisor for the
rectifiers checked the residual voltage of the potline and
found it to be 37 V. The rectifier supervisor had been on site
at the power outage in 2002 and recalled that the residual
voltage had decayed to 30 V after 4 h at that time. Based on
this knowledge the situation was re-assessed and it was
decided that the potline was still in a condition to be
restarted as soon as the bus bar welding had finished.
During the whole power outage, normal work routines
had not been resumed, not even in the potlines back in
operation as lead times for necessary work during a restart in
726 T. Reek and R. Düssel

potline I was to be kept to a minimum and all work routes 60

for anode transport and metal delivery would have led

through potline I. With the restart decision made and a time 50

frame of less than 1 h until electricity should be restored,

40

Linevoltage [V]
further preparations were made in the potrooms, this inclu-
ded the distribution of a large number of wooden poles at
30
every other pot in the potline for quenching anode effects
after current pickup.
20
In addition, in potline II, two cells were originally V (min)

scheduled to be started after gas preheating on that day, V (max)

10
however the decision was taken to postpone the start-up by
one day. 0

10:00:00
10:30:00
11:00:00
11:30:00
12:00:00
12:30:00
13:00:00
13:30:00
14:00:00
14:30:00
5:00:00
5:30:00
6:00:00
6:30:00
7:00:00
7:30:00
8:00:00
8:30:08
9:00:00
9:30:00
The electrolyte gathered in donor pots for this scheduled
pot startup was to be redirected for use to increase liquid
electrolyte levels when needed after the potline I restart.
However the amount of electrolyte was deemed to be Fig. 3 Residual voltage of potline I
insufficient as the need for massive electrolyte amounts was
anticipated. To provide electrolyte easily, 10 additional cells Restart
in potline II were forced into anode effect by switching off
the alumina feeding. Crushed electrolyte was prepared in The restart was carried out at 11:01:05, 5 h 50 min and 30 s
large buckets so that it could be added to the cell in anode after the initial power outage. At restart the residual line
effect to melt it quickly. voltage was measured at 35 V (Fig. 3). The whole potline
With re-energizing the potline after more than 5 h, the was evacuated as it was not known how the pots and
risk of clad failures due to overloading of single anodes was especially bottlenecks such as the bimetal clads would react.
expected. It was decided to have hot anodes available as In case of rapid clad failure, open electrical arcs were
replacements if needed. Anodes in the middle of their life expected as the open circuit protection had been deactivated.
were removed from cells in potline II and III. In total 20 It was important to start with an amperage that would not
anodes in potline II and III were removed, ready to be result in too high total line voltage to avoid overloading the
introduced into potline I cells if needed. rectifiers. 60 kA was targeted and achieved after a short
While these restart measures were being organized, the amperage spike up to 100 kA. The line voltage jumped from
Essen potrooms manager saught advice from all other 35 V residual load to 350 V almost immediately. Within a
TRIMET smelters (3 other smelters) on how to manage the
restart. The main items of advice were:
200

– Block feeding on all cells until potline has been opera- 180
tional for some time to prevent sludging
160
– Increase line current as fast as possible to at least 120 kA
(75%) to get heat into the cells and to exceed the lower 140

feeding limit of 80 kA (the rate is shown in Fig. 4)

Amperage [kA]

120
– Buzz down all beams for 1–2 s to optimize wetting of the
100
anodes by the remaining electrolyte as soon as line cur-
rent was back to improve the wetting of the anodes with 80
liquid electrolyte
60
– Deactivate automatic anode effect quenching to avoid
short circuits 40

– Have as many operators as possible in the line for anode 20

effect termination
0
– Have one engineer at a computer for changing parame-
11:00:00
11:01:00
11:02:00
11:03:00
11:04:00
11:05:00
11:06:00
11:07:00
11:08:00
11:09:00
11:10:00
11:11:00
11:12:00
11:13:00
11:14:00
11:15:00
11:16:00
11:17:00
11:18:00
11:19:00
11:20:00

ters (e.g. unblock feeding)

– Have a permanent phone line to the rectifier until the
potline seems safe to minimize reaction time. Fig. 4 Line current development immediately after re-energizing
Surviving an Extended Power Outage after a Break Down …
few minutes line voltage increased to 600 V. The normal
line voltage before the outage had been 512 V, however
600 V is still safely within the operational limits of the
rectifier.
With this information and the knowledge that the
amperage had stayed on for a few minutes without any
noticeable problems, 20 operators were deployed into the
potroom to manually buzz down the beam of every single
pot.
As anticipated this increased the wetting of the anodes
with the remaining liquid electrolyte and potline voltage
dropped to 450 V. This freed capacity in the rectifier to
further increase line current. As a plan, the line current was
increased at a rate which allowed the line voltage to be at or
below 600 V. The line current was increased continuously in
coordination between potrooms and rectifier.
Within 20 min after restart 140 kA was reached. The
rectifier was able to hold the line amperage stable. Line
voltage had dropped continuously peaking at 635 V, but
during the time it was still around 600 V at 140 kA.
Having stabilized the potline, the attention turned to
individual pots. At reaching 140 kA pot voltages varied
between 1 and 20 V. Even though 32 out of 120 cells
reported cell voltages below 2 V, these cells appeared stable.
Anodic current distribution showed wide swings, but visual
inspection on some cells showed no red stubs or other
indications of too high current load. Obviously a number of
anodes had been pushed into the metal to carry the current
safely. The cell would not recover by themselves, but ohmic
heating was deemed sufficient to avoid further freezing of
the cell.
With the line current being stable, the decision was taken
to re-activate the alumina feeding. The cells below 2 V
should not receive alumina to not sludge even more, but
voltages that low were registered by the process control
system as cut-out and alumina feeding was deactivated
automatically.
Due to the high traffic on the communication bus,
parameter changes had to be sent multiple times to indi-
vidual cell controls and all cell controls had to be checked
manually if they had received the new parameters.
A team was established to continuously measure anodic
current distribution on cells with both low and high voltage
and to check electrolyte levels. The anode setting team was
ordered to re-set anodes with high current load, if electrolyte
levels permitted.
Electrolyte levels varied widely. Some cells had regained
electrolyte levels of 15 cm or more, while the most critical
cells were found with only 5 cm of electrolyte. Another team
was deployed to start electrolyte transfers from the opera-
tional potlines and targeting those cells. Typically cells with
low pot voltages showed low bath levels as well.
727
With sufficient electrolyte additions the anode beam was
raised, targeting regular pot voltages. For some cells this was
achieved by moving the beam only a few millimeters, while
other beams were raised up to 10 mm with little response.
Electrolyte transfer capacity and electrolyte availability
was limited even though steps as described above had been
taken to generate additional electrolyte. Due to these limi-
tations the team was forced to raise beams of low voltage
pots without electrolyte addition. This was done while
carefully monitoring the electrolyte level in the cell. This
restored several cells to normal working condition. Even
though this process was considered risky, no problems
occurred. If a beam raise of 10 mm did not result in a gain of
pot voltage, the cell was scheduled for the next available
electrolyte addition.
It is notable, that during the early hours of the restart, clad
failures did not occur. Several cells in potline I had damaged
cathodes and had been targeted for cut out earlier. No action
had been taken during the power outage and cutting out any
additional cell after the restart would have necessitated
another shut down for at least 30 min or more as short cir-
cuiting a cell in Essen is rather cumbersome and involves
working on a forklift platform in the basement. Thus the
decision was taken to keep all cells in operation if possible.
To free up more electrolyte, two high iron cells in potline
III were shut down around 13:00 h. The electrolyte was
immediately transferred to potline I.
About 2 h after the restart there were only 11 pots below
2 V and another 9 pots below 3.5 V. It is important to note,
that out of these 20 pots, only 1 cell was in the booster
section, which had been equipped with Shell Heat
Exchangers® as described by Düssel et al. [6]. The heat
exchangers had not been restarted after the power was
recovered and had been running in maximum insulation
mode for the whole time. Even though this is not a statis-
tically significant test, it shows the heat retaining ability of
the SHE.
These 20 cells were subsequently handled in the same
manner as described above. After the restart overloading of
individual anodes and subsequent clad failures were not an
issue. It was only during the very last pots that had been
operating at 2 V for several hours that anodes failed when
the beam was moved.
The late shift also re-started metal delivery to the
casthouse.
Due to undercooling and lack of superheat, many cells
had alumina dissolution problems. Figure 5 shows the
development of anode effects following the restart of the
line. Immediately after re-energizing, nearly every pot that
was not short circuiting reported an anode effect. This
number stayed high until 21:00, 10 h later, when the rate
rapidly dropped back to more normal levels.
728 T. Reek and R. Düssel

80 A separate work crew was still checking the anodic current

distribution of every pot for the better part of the late shift.
70
Continuing with the mentioned actions the late shift was
60 able to stabilize the whole potline until 10 pm (11 h after the
restart).
50
AEs/h

40
Follow up
30

20
10
0
Fig. 5 Development of anode effect rate after restart
Considering the generous amount of alumina added to the
cells normally during automatic anode effect quenching, the
amount was lowered considerably for all cells in the potline.
The consequently lower success rate of the quenching rou-
tine was accepted in these circumstances.
Figure 6 shows the current situation in the pot line at about
16:00 h. Even though the potline was slowly stabilizing, the
number of pots registering noise was still high (orange); the
number of anode effects is given in red next to the pots.
During the black out all work was delayed in the reduction
department. A mayor concern was the backlog in anode
change. To accommodate this a skip day was introduced in
the anode change plan. This was possible firstly due to the
extended power loss, and secondly due to the majority of
cells in potline 1 being primary alumina cells that have a
short-than-usual anode rota to achieve higher metal purity.
A possible loss in high purity metal was accepted under
these circumstances.
Metal tapping was intensified in the following shifts and
the backlog was cleared within 2 days. Flexible operation
using tapping trucks and a casthouse capacity that is con-
siderably higher than the reduction production helped
significantly.
Another shut down for 1.5 h for further repair on the
21 kV bus bars had to be made the following day and was
coped with easily.

Fig. 6 Screenshot of the process menu at about 16:00 h

Surviving an Extended Power Outage after a Break Down … 729

975 The following key points can be highlighted as critical for

this success:
970 During the power outage:

– Install an emergency team and communicate all relevant

Temperature [°C]

965

information
960 – Retain heat in the cells
– Do not touch the cells
955 – Prepare for all options while there is time (emergency
shut down teams, logistics, on-call response people)
950 – Prepare electrolyte
– Prepare hot anodes
945 – Distribute the work and name responsible persons
01 Apr 03 Apr 05 Apr 07 Apr 09 Apr 11 Apr 13 Apr 15 Apr 17 Apr 19 Apr
– Let these people do their job
T(Bath) T(Liq)
– Prepare contingency plans.
Fig. 7 Development of electrolyte and liquidus temperature after the
power outage During the restart:

The temperature measurements after the outage recorded – Block alumina feeding for the restart
a significant drop to 941 °C as average electrolyte temper- – Block automatic AE quenching
ature in potline I the following day. Manual additions of – Buzz down all beams for 1 s when the energy is back.
soda and raised cell voltages recovered temperatures within
4 days (Fig. 7). Last but not least it should be mentioned that such a crisis
Summarizing total damages to the potline due to the cannot be managed if the whole team in the plant is not
power outage, 2 cells in potline III were cut out as they were working hand in hand to solve any issue that might arise.
iron pots and the electrolyte was deemed necessary. A big ‘thank you’ to everybody who was involved in the
In total only 14 clad failures were recorded on the day of restart and the subsequent recovery.
the restart. On that day and the following, 19 anodes spikes
were found and removed from the cells—10 of which were
in potline I. References

1. H. Oye, M. Sorlie, Power failure, restart and repair, Aluminium Int.

Today (2011)
Conclusion 2. A Tabereaux, Mechanism for the formation of cathode ‘cooling’
cracks’, TMS Short Course ‘Shutdown and Restart of Potlines’,
The Essen smelter survived a major power outage in one of Seattle (2010)
the 3 potlines. The potline was without power for close to 3. Hydro, Hydro Årdal power outage has limited effect on production,
hydro.com. Accessed 5 Aug 2016
6 h.
4. Dubal, Power outage slows Dubai smelter, thenational.ae. Accessed
The recovery was considered smooth and the potline was 5 Aug 2016
operating in a stable condition within 11 h after restart and 5. Noranda, Power outage idles two of Noranda’s three smelters,
electrolyte temperatures normalized within 4 days. aluminiuminsider.com. Accessed 5 Aug 2016
6. R. Düssel, N. Depree1, P. Patel, T. Reek, The ‘virtual battery’—
The section equipped with Shell Heat Exchangers®
operating an aluminium smelter with flexible energy input, TMS
showed less impact to the power outage than the rest of the (2016)
line.
 Retrofit of Damaged Corner Risers by Means
of Bolted Connections

André Felipe Schneider, Donald P. Ziegler, Maxime Pouliot,

Daniel Richard, Jason Robillard, Jérémie Blais, Olivier Charette,
and Pouya Zangeneh

Abstract
Unlike pot-to-pot cathode busbars, often protected by the potroom working floor (or
gratings), risers are usually exposed to accidental collisions with pot tending machine tools,
anode assemblies, crucibles and even heavy vehicles. The tap end corner risers of several
pots located immediately after the passageways of the Baie-Comeau Smelter’s Potline D
had been damaged throughout the years, which led to the mechanical failure of a
considerable amount of the welded plates connecting said risers to the passageway liaison
conductors. The retrofit of damaged pot-to-pot conductors is traditionally based on welding
techniques, often requiring bypass bridges or potline shutdowns. In the fall of 2015, an
integrated Alcoa-Hatch multidisciplinary team succeeded to safely replace one of these
risers, without production downtime or auxiliary conductors, by resorting to bolted
connections in lieu of standard welded joints. This unique piece of equipment has been
operating consistently within target for about 10 months.

Keywords
Busbar repairs Bolted connections Risers Finite element analysis

A.F. Schneider (&)
J. Robillard
J. Blais

Hatch, 5 Place Ville-Marie, Suite 1400, Montréal, QC H3B 2G2,
Canada
e-mail: aschneider@hatch.ca
D.P. Ziegler
Alcoa Primary Metals, Alcoa Technical Center, 100 Technical Dr,
New Kensington, PA 15068, USA
M. Pouliot
Alcoa Primary Metals, Aluminerie de Baie-Comeau, 100 Route
Maritime, Baie-Comeau, QC G4Z 2L6, Canada
D. Richard
Hatch, 322 Industrial Ave, Kitimat, BC V8C 2E9, Canada
O. Charette
Hatch, International Tower, Suites 1506–1507, Capital Centre,
PO Box 41096Abu Dhabi, UAE
P. Zangeneh
Hatch, Sheridan Science & Technology Park, 2800 Speakman
Drive, Mississauga, ON L5K 2R7, Canada

© The Minerals, Metals & Materials Society 2017 731

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_89
732
Introduction
The Alcoa Baie-Comeau smelter (ABC), built in 1957 by the
Canadian British Aluminum Company, is located on the
North Shore of the St-Laurent River in the province of
Québec, Canada. It was acquired by Alcoa in 2000 following
the merger with the Reynolds Metals Company. The smelter
was expanded on four different occasions, including an
upgrade of its (recently decommissioned) Vertical Studs
Søderberg potlines in the early 1980s (Fig. 1).
Currently yielding a total throughput of 295 ktpy, its two
operating prebaked potlines (Lines D and E) were respec-
tively commissioned in 1985 and 1991 employing AP18
pots, a successful side-by-side, side risers technology.
Unlike pot-to-pot cathode busbars, often protected by the
potroom working floor (or gratings), risers are usually
exposed to accidental collisions with pot tending machine
tools, anode assemblies, crucibles and even heavy vehicles,
as suggested by Fig. 2.
Fig. 1 Aerial view of the Alcoa Baie-Comeau smelter
Fig. 2 Large aisle corner riser most likely deformed due to a
high-energy collision
A.F. Schneider et al.
Fig. 3 Example of heavily distorted welded plate joint connecting a
passageway liaison busbar to a corner riser
Corner Risers Adjacent to Passageways
The tap end (TE) corner risers of cells located downstream
(DS) of the passageways are of special interest for, if not
protected by means of concrete walls or other appropriate
devices, they are particularly exposed to collisions with
service vehicles turning from the passageway into the large
aisle and vice versa. Furthermore, the fixed part of these
risers is connected to the passageway liaison busbars by
means of a set of welded plates acting as a pivot point. These
welded plate joints are considered as the weakest mechanical
link of this arrangement.
In situ observations performed in 2009 revealed that the
aforementioned welded plate joints from both Potlines D and
E had sustained considerable distortions, as evidenced by
Fig. 3.
A series of follow-up inspections initiated in Q4 2014
revealed that several weld fillets from the welded plates
connecting the corner risers of 5 different pots to their
respective liaison busbars were either cracking or sheared
throughout. Figure 4 shows a particular joint that had 7 out
of the 15 weld plates completely severed. Note that a coating
of a known emissivity was applied to the plates to allow their
monitoring using non-contact thermography.
This motivated an integrated ALCOA-HATCH NE
Alliance team to undertake a prototype repair of one of those
damaged corner risers to investigate the feasibility, health &
safety implications, impact on operations and cost of
accomplishing such a task.
Replacement Corner Riser Design
An Option Analysis study was performed to identify the
solution that would meet the strict criteria for the reliable
operation of the affected cells, the safe retrofitting of the
Retrofit of Damaged Corner Risers by Means of Bolted Connections 733

Fig. 4 Infrared thermography of a particular welded plate joint

(Q4 2014)

risers, the least impact on operations, and the minimum

possible cost. Fig. 5 Typical TR48 outside bolted joint (actual electrical protection
Firstly, three distinct welding-centered options were gratings not shown—reproduced from [1])
considered as potential repair methodologies only to be
dismissed due to either technical difficulties or cost:
the replacement corner riser assembly, whose key design
• Exothermic welding (CAD welding): the available room features are briefly described below.
between the top surface of passageway liaison busbars
and the ceiling prevented the mounting of the moulds as
required by the process; Prefabrication and Tie-in
• Electroslag welding (ESW): available clearance also
prevented the installation of the ESW machine. Fur- To completely avoid any on site welding, the replacement
thermore, the usage of this method would involve one corner riser was designed to be prefabricated and delivered
potline shutdown per repaired riser; to the smelter as a single part—Fig. 6—while its tie-into the
• Conventional arc-welding: the execution of the repair
works by means of conventional arc-welding would
require either 2 potline shutdowns per conductor or the Connection to the removable
(flexible) riser end
fabrication and installation of a dedicated bypass bridge.

This led the integrated project team to consider an

unorthodox approach, i.e., to replace the damaged conductor
by a prefabricated corner riser assembly that will be bolted
against the existing passageway liaison busbar. While not
straightforward, such a solution could be implemented
without production downtime or auxiliary conductors when
short-circuiting the concerned pot—ideally following the
relining schedule.
The bolted concept received support from ABC opera-
tions, partly due to the adequate long-term performance of
the “TR48” booster busbars [1]: installed strictly by means
of bolted connections in Q4 2008, voltage drop readings
performed in Q4 2014 showed that its “outside” joints pre-
sented an average electrical contact resistance of
0.024 lX m2 after 6 years of service and exposure to the
weather—see Fig. 5.
Contact lug
Once the required approvals from both ALCOA man-
agement and subject matter experts (SMEs) were obtained, Fig. 6 Replacement corner riser was prefabricated in order to avoid on
the project team proceeded to the Detailed Engineering of site welding works
734
existing busbars network, provided by means of a bolted
connection, was designed to meet the following criteria:
• Provide a maximum contact resistance of Rcontact 
Rcontact,target = 0.03 lX m2, while considering a maxi-
mum contact current density of Jcontact  0.3 A/mm2
thus, yielding a target contact voltage drop of
DVcontact  9 mV;
• Keep an appropriate contact pressure during both in- and
off-duty conditions. Note that best design practices [2]
recommend a nominal (tightening) contact pressure
between 6 and 8 MPa in a bolted joint;
• Keep the tie-rods within the elastic domain at all times;
• Accommodate the differential thermal expansion
between aluminum conductors and steel tie-rods under a
wide temperature range (−40 °C, winter shutdown, to
150 °C, summer operation) by means of spring washer
stacks, sized to be kept within the recommended
deflection range at all times [3].
Furthermore, the riser-to-liaison busbar bolted connection
was sized to prevent joint separation [4] (and, consequently,
oxidation of the contact surfaces) in case of lateral impacts to
be eventually suffered by new corner riser assembly.
Thermo-electrical Behavior
Even though the deployment of the replacement corner riser
introduces a modification to the busbars network, it should
not impact the anodic current distribution.
A series of thermo-electrical Finite Element (FE) analy-
ses1 were used to design the equivalent electrical resistance
of the new assembly such that it was within close tolerance
to that of the original. For instance, the horizontal segment
of the new prefabricated corner riser had its cross-section
enlarged to compensate for the contact resistance of the new
interface.
Figure 7 shows the predicted temperature distribution for
the proposed geometry when operating normally at target
amperage, summer conditions and Rcontact,target.
Mechanical Anchoring System
A flexible joint was included in the new riser assembly—
Fig. 6—to facilitate installation by enabling the proper
mating of both liaison busbar-to-riser contact surfaces and
the alignment of the threaded rod holes, as well as helping to
1 2
A detailed description of the employed modeling approach can be
found in [5].
A.F. Schneider et al.
Removable
(flexible)
riser end
Passageway
liaison Potline current
busbar
[°C]
Fig. 7 Predicted temperature distribution for the new corner riser at
target amperage, summer conditions and Rcontact,target
accommodate some of the displacements due to eventual
collisions with other pieces of equipment. However, in order
to protect the new riser assembly from excessive rigid body
movement, guides and stoppers were designed and installed
—see Fig. 8.
Supported at both extremities, the corner riser has its
upward movement2 prevented by means of a “dovetail-like”
structure formed by its own footing (“male”) and by the
combination of the contact lug and of an additional tight-
ening plate installed on the opposite side of the existing
liaison busbar (“female halves”). This dovetail-like assem-
bly, when combined with a “mechanical anchoring system”,
prevents the new riser from moving sideways (i.e., along the
length of the cell) and from rotating with respect to the
vertical axis. Finally, the longitudinal (i.e., parallel to cell
short axis) displacement of the conductor is limited by a cut
made into the existing passageway liaison busbar and a
stopper integrated on the new tightening plate.
The mechanical anchoring system, mounted on the head
busbar and lined with electrical insulating plates, is made of
stainless steel to allow for its assembly in a live potline. This
component was sized to withstand a lateral inelastic collision
of 9.81 kJ, which represents the kinetic energy of either a
heavy vehicle of about 19.6 metric tonnes at 1 m/s or that of
an anode assembly of about 2.2 metric tonnes at 3 m/s
moving towards the exposed corner riser bolted connection
(refer, once again, to Fig. 2). It is important to stress that said
anchoring system is to be considered as a sacrificial com-
ponent: its main function is to protect the welded plate joints
of the new corner riser assembly in the event of such a
collision. Should it happen, the part would be permanently
deformed and would have to be replaced during the next pot
relining cycle.
Resulting from potential collisions with a pot tending machine
(PTM) tool or anode assembly moving downwards.
Retrofit of Damaged Corner Risers by Means of Bolted Connections
Fig. 8 Mechanical guides and Functional description
stoppers limit the rigid body
movement of the new riser
assembly
Figure 9 shows the equivalent stress distribution pre-
dicted by means of a non-linear, displacement-controlled FE
mechanical analysis of the anchoring system, where the
prescribed displacements were gradually increased until the
total (elastic + plastic) strain energy of the system matched
the target energy input, i.e., Utot = 9.81 kJ.
Fig. 9 Equivalent stress distribution for the mechanical anchoring
system resulting from an inelastic lateral collision
735
(1) Dovetail-like structure = prevents upwards displacement
(2) Cut into liaison busbar + integrated stopper = prevents
displacement along cell short axis
(3) Dovetail-like structure + mechanical anchoring system
= prevents displacement along cell long axis and
rotation with respect to vertical axis
Cut into passageway liaison bus
Potline
current
Mechanical
anchoring
system
Contact lug (dovetail Integrated
female half) stopper
Corner riser footing Tightening plate
(dovetail male) (dovetail female half)
With all pertinent studies and engineering documents
completed, the Project Implementation phase finally began
in Q3 2015.
Prototype Corner Riser Implementation
One particularly challenging aspect of the Project Imple-
mentation phase was the management of its health and safety
(H&S) aspects, given that the Mobile Earthing Trolley
(MET) was not functional on Potline D throughout the
construction effort. In order to mitigate the corresponding
electrical risks, project-specific working procedures had to
be developed in order to safely accomplish the installation of
the new riser assembly.
Apart from the usage of electrically insulated boots,
workers were required to use dielectric (covered by leather)
gloves at all times. Electrical protection elements such as
dielectric plastic covers as well as a combination of dielectric
rubber carpets and dry plywood sheets were employed to
ensure that pot potential was not accidently brought in
contact with either the potroom building structure or the
basement, considered to both be at ground potential—
Fig. 10. Finally, it is important to stress that no safety
incident was recorded throughout the construction period.
736 A.F. Schneider et al.

Dielectric
plastic
covers

Layer of
dielectric
rubber
carpet
covered by a
dry plywood

Fig. 10 Electrical protection elements installed as an integral part of

the project-specific working procedures that enabled the safe installa-
tion of the new riser assembly

With the concerned cell taken to the pot relining shop and
all required electrical protection measures in place, the
construction team proceeded to the removal of the existing
corner: a visual inspection of this part confirmed the
advanced stage of degradation of its welded plates, as
depicted in Fig. 11.
In order to obtain a suitable contact surface on the
existing passageway liaison busbar, its outer vertical surface
was machined by means of a special purpose pneumatic
milling tool, Fig. 12, and holes were made with a pneumatic
3 welded
plates fell off
while
removing the
existing
corner riser
Fig. 12 Liaison busbar machined on site by means of a special
purpose pneumatic milling tool
drill—Fig. 13. The top portion of said busbar was then cut
by resorting to a chain saw.
The contact surfaces of both the liaison busbar and the
contact lug (refer yet again to Fig. 6) were prepared and the
replacement riser assembly was then installed by means of
an overhead crane—see Fig. 14. Both contact surfaces were
cleaned with acetone and the bolted joint was tightened—
Fig. 15—according to a specific procedure by using a cali-
brated stainless steel manual torque wrench. This operation
was completed 4 h after the contact surfaces preparation.
All temporary electrical protection measures were
removed and the site was returned to ABC operations, which
proceeded to the installation of the new cell. The new corner

Weld fillet
cracked
halfway
through

Fig. 11 The welded plates of the original TE corner riser presented an Fig. 13 Holes were drilled into the liaison busbar with a pneumatic
advanced stage of degradation tool
Retrofit of Damaged Corner Risers by Means of Bolted Connections 737

Additional electrical protection at Evolution of R contact Over Time - Prototype Corner Riser
Rcontac,target
the working floor level 3.00E-02

R contac , [μΩ⋅m^2]
2.90E-02

2.80E-02

2.70E-02

2.60E-02

2.50E-02
27-Sep-16
2.40E-02

2.30E-02 4-Nov-15
2-Sep-16

2.20E-02

2.10E-02 20-Nov-15

2.00E-02
3-Sep-15 23-Oct-15 12-Dec-15 31-Jan-16 21-Mar-16 10-May-16 29-Jun-16 18-Aug-16 7-Oct-16 26-Nov-16

Fig. 16 Evolution of the liaison busbar-to prototype riser bolted

connection quality over time
Mechanical anchoring system

Fig. 14 Replacement corner riser installed by means of an overhead

crane • Follow-up: A bolted joint that shows elevated contact
resistance (2Rcontact,target < Rcontact  4Rcontact,target) and
requires close monitoring. It indicates a joint that might
Fig. 15 Replacement corner be experiencing a process of continuous degradation;
riser-to-existing passageway • Intervention threshold: A bolted joint of unacceptable
liaison busbar bolted joint,
including stacks of spring quality (i.e., Rcontact > 4Rcontact,target) thus, requiring
washers maintenance. Such a bolted joint must be opened and
have its contact surfaces cleaned and prepared prior to
retightening.

The contact resistance of the new bolted joint was esti-

mated based on both current split between risers3 and the
voltage drop readings across the liaison busbar-to-riser
interface itself: Fig. 16 shows that the prototype corner riser
has been performing consistently within target for about
10 months.
Motivated by the successful experience with the proto-
type replacement corner riser, ABC operations decided to
proceed with replacement of the 4 remaining damaged TE
corner risers.
riser assembly was commissioned once the pot went into
preheating at full potline current.

Second Replacement Corner Riser Design,

Prototype Corner Riser Commissioning Implementation and Commissioning

The integrated project team identified four distinct bolted
connection quality levels to assess the continuous perfor-
mance of the prototype corner riser assembly:
• Good quality: A bolted joint that operates within the
specified design parameters, i.e., Rcontact 
Rcontact,target = 0.03 lX m2;
• Acceptable limit: A bolted joint that behaves adequately
although it presents a contact resistance up to twice as
large as the target figure (i.e., Rcontact  2Rcontact,target).
It is usually associated with mildly oxidized or poorly
prepared contact surfaces;
A second corner riser was installed at ABC Potline D on
September 2016 and its contact resistance during commis-
sioning was Rcontact = 1.42E-2 lX m2 or 62% of the aver-
age figure presented by the prototype over the last
10 months. Key differences between the two pieces of
equipment include:
3
Estimated by means of both temperature and voltage drop readings for
all risers and normalized by the actual potline current with an accuracy
of 3%.
738 A.F. Schneider et al.

(δ i - δ500 lbf⋅ ft ), [mm]

Tightening Test - Hydraulic Torque Wrench
the influence of strong magnetic fields was verified by
means of the calibrated stainless steel manual torque
1.60 Theoretical spring washers
stack deflection
wrench.
1.40 Measured deflection
1.20
1.00
0.80 Conclusions
0.60
0.40 An integrated ALCOA-HATCH NE Alliance team suc-
0.20 ceeded to safely replace a damaged corner riser from ABC
0.00
Potline D without production downtime or bypass conduc-
500 700 900 1100 1300 tors, by resorting to bolted connections in lieu of standard
Torque, [lbf⋅ft] welded joints. This unique piece of equipment has been
operating in a stable manner for about 10 months. In order to
Fig. 17 Tightening tests performed in shop showed that the hydraulic
torque wrench is able to provide the required deflection to the stack of minimize further damage to existing conductors, physical
spring washers barriers where installed on both ends of the passageways,
thus protecting these cells from collisions with service
vehicles turning from the passageway into the large aisle and
vice versa (Fig. 18).

Acknowledgements The authors would like to express their gratitude to

Fig. 18 Physical barriers protecting cells from collisions with service
vehicles were installed on both ends of the passageways
• A minor design modification in the contact lug to
improve the mating of new contact interface;
• Improvements to the in situ machining technique;
• A new installation sequence which enables the elapsed
time between new contact surfaces preparation and joint
tightening to be less than 2 h;
• The usage of a calibrated hydraulic torque wrench to
tighten the liaison busbar-to-corner riser bolted joint.
Tests showed that it can effectively provide the required
deflection to the stack of spring washers during joint
tightening, according to design specifications (refer to
Fig. 17). Furthermore, the performance of this tool under
the following people whose support and dedication made this achieve-
ment possible: Patricia Gagnon, Richard Lafontaine, Marie-Ève
Laframboise, Denis Tanguay, Gino Boucher and Francisco Salgado from
Alcoa Baie-Comeau; Patrick Barbieri, François Bouchard, Jean-Pierre
Voyer and Guillaume Normandeau from Hatch; Sylvain Deshaies,
Louis-Philippe Tanguay and Nelson Fraser from Pro-Métal Plus.
References
1. D. Champagne, D.P. Ziegler, A.F. Schneider, D. Richard, in Busbar
Circuit Design And Installation For Boosting Already Boosted Pots.
Proceedings of the Light Metals (TMS, Warrendale, PA, 2010),
pp. 479–84
2. Aluminum Electrical Conductor Handbook, 3rd edn. (The Alu-
minum Association, 1989), pp. 13–41
3. Handbook for Disc Springs (Adolf Schnorr GmbH & Co. KG,
2003), pp. 11–40
4. R.G. Budynas, J.K. Nisbett, in Shigley’s Mechanical Engineering
Design, 9th edn. (McGraw Hill, 2008), pp. 409–59
5. A.F. Schneider, D. Richard, O. Charette, in Impact of Amperage
Creep on Busbars and Electrical Insulation: Thermal-Electrical
Aspects. Proceedings of the Light Metals, (TMS, Warrendale, PA,
2011), pp. 525–30
 Theory and Practice of High Temperature Gas
Baking Technology for Aluminium Electrolysis
Cells

Chengbo Wu, Yingwu Li, and Xudong Wang

Abstract
This paper comes up with a new baking approach, high temperature gas baking technology,
based upon aluminium cells characteristics and raw material properties. Research
achievements have been widely used in actual practice after numerous laboratory and
industry tests. It turns out that, high temperature gas, as heating media, is able to ensure
uniform surface temperature distribution of cathode lining. What’s more, it reduces the
possibility of paste and carbon blocks oxidation damage during baking process. Its good
baking results create favorable condition to prolong cells’ s service life. This approach is
also proved to be energy-saving, safe and environment friendly.

Keywords
Gas baking Aluminum electrolysis cells Secondary startup New potline baking
Combustion air Numerical calculation Module

Preface At present, there are mainly three baking approaches in

Normally, there are three stages for aluminium production:
baking, startup, and production. As for prebaked anode
aluminium cells, its anode has experienced the baking pro-
cess, so the main baking purpose is to dry the furnace, sinter
ramming paste between cathode and lateral carbon blocks,
and heat anode and cathode for further step. Basic baking
requirements for anode cells in aluminium industry are as
follows, firstly, increasing cathode temperature slowly until
950–980 °C in order to avoid thermal stress; secondly,
heating cathode surface evenly and narrowing down tem-
perature difference for the same reason; finally, making sure
that binder in ramming paste shall be coking in a proper rate
to keep binding property.
C. Wu
Chongqing University, Chongqing, China
Y. Li
X. Wang (&)
Zhengzhou Jingwei Technology Industrial Co., Ltd., No. 11,
Changchun Road, Zhengzhou, China
e-mail: wxd@jwkjzz.com
Y. Li
e-mail: lyw@jwkjzz.com
China: liquid aluminium baking, coke baking and fuel
baking. Compared with other two approaches, fuel has the
following advantages. Its heating rate can be easily con-
trolled. Cathode surface temperature increases slowly and
regularly. Due to little temperature difference between
cathode and surface during baking process, thermal stress is
relatively low. Therefore, there are no cracks in cathode
surface. Because of the complete closeness, radiant heat and
asphalt fume hardly release. As a result, surrounding envi-
ronment is better improved. What’s more, this approach can
guarantee the best baking effect for lateral paste that other
methods cannot achieve. At the beginning of startup, elec-
trolyte will first fill in the cracks of cathode lining and lateral
paste, which is caused by the baking process. When it is
finished, there is no need to clean carbon residue. Practice
has proved that fuel baking approach can prolong cells’
service life. However, it also has the less admirable aspects.
Present fuel baking method widely used in global is directly
heating by flame, which will possibly damage cathode car-
bon blocks. This happens in actual operation. And paste
seam burning can be commonly seen. Besides, oxidation

© The Minerals, Metals & Materials Society 2017 739

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_90
740
problem will occur in cathode and anode surface if improper
actions are taken, which will affect cells’ normal operation.
In order to fully utilize fuel baking advantages and make
up the shortness of above-mentioned flame heating tech-
nology, this paper comes up with a new fuel baking tech-
nology, that is high temperature gas baking technology. It
uses the hot gases generated from fuel combustion to pre-
bake aluminium cells. Whether cathode, anode and ramming
paste will be badly oxidized or not during the baking process
becomes a major concern for this new technology.
Theoretical Research on Carbon Electrodes
Oxidation
First, electrolytic electrodes oxidation theory in high tem-
perature gas baking process.
Gases generated from fuel combustion are relevant with
fuel material and excess air ratio. During lab experiment, hot
gas produced by combusting natural gas is simulated as the
high temperature gas in actual baking process. In normal air
mixture, content of CO2 is 8.5%, H2O 17% or so, while CO
and H2 are lower than 1.0%. Based on which, relation
between reaction rate and temperature of C–CO2 and C–H2O
can be seen in Fig. 1.
Figure 1 shows that carbon gasifying rate is very slow at
low temperature, 0.00245 mol/m2 s at 900 °C while
0.0079 mol/m2 s at 950 °C, which shows carbon gasifying
rate is a little obvious above 950 °C. Under the same cir-
cumstance, reaction between carbon and vapor is much
stronger, 0.00135 mol/m2 s at 700 °C, while
2
0.00507 mol/m s above 750 °C. Some even thinks that
carbon oxidizes faster with vapor than with CO2. The
question is not reaction rate but diffusion rate. It is known to
all that relative molecular mass of CO2, H2O, CO, and H is
respectively 44, 18, 28 and 2 g/mol. According to molecular
physics, the smaller molecular has the higher average rate for
gas molecular as well as diffusion coefficient at the same
temperature. Vapor’s diffusion coefficient is higher than
CO2, while hydrogen’s coefficient is much higher than CO.
Fig. 1 Reaction rate of C–CO2 and C–H2O changing with temperature
C. Wu et al.
Therefore, carbon oxidation rate is much higher with vapor
than with CO2. Based on the dynamics analysis on C–O2 and
CO2-vapor reaction, it can be shown that C’s oxidation rate
has a certain relation with rate constant, oxidizing atmo-
sphere and temperature. In low temperature phase (below
700 °C), C-vapor reaction rate is very slow and negligible.
Within cells’ baking temperature range (below 900 °C),
CO2–C reaction rate is also negligible. As a result, in baking
process, electrodes oxidation is mainly caused by excess air
when the temperature is below 700 °C. When it is above
750 °C, excessive air and vapor may cause oxidation
reaction.
Second, study on oxidation characteristics of anode,
cathode and ramming paste
To study oxidation characteristics of anode, cathode and
ramming paste, we put hot gas while sample electrodes are
heated, then calculate oxidation rate by measuring electrode
weight loss. Sample weight in different temperature and
atmosphere is measured by electronic balance. This paper
discusses temperature and excess air influence on oxidation
rate of anode, cathode and ramming paste.
It can be seen from Fig. 2 (where n is air excess coeffi-
cient), when n = 0.97, cathode oxidation rate in fuel gas is
6–7% of that in air. Even though there is much air left, the
oxidation rate is 10% of that in air when n = 1.17. 2.3 shows
that cathode oxidation rate increases with excess air coeffi-
cient, but its increasing speed changes with n (Fig. 3).
From Fig. 4, when n < 0.952, upper limit of cathode
oxidation rate in flue gas is 5–7% of that in air. When
n = 1.017, cathode oxidation rate is 9% of that in air. From
Fig. 5, anode oxidation rate increases with excess air
coefficient.
Fig. 2 Relation of cathode oxidation rate and temperature
Theory and Practice of High Temperature Gas Baking Technology …
Fig. 3 Cathode oxidation rate-excess air coefficient curve
Fig. 4 Anode oxidation rate and temperature coefficient
From Fig. 6, when n = 0.94, paste weight loss rate is
4–8% of that in air. When n = 1.06, its weight loss rate is
10% of that in air. It can be seen from Fig. 7 that oxidation
rate is exponential as excess air coefficient increases.
According to experiment results, sample oxidation rate is
rather slow in low temperature and low excess air coefficient.
Similarly, oxidation rate is higher in high temperature and
high excess air coefficient. So, to prevent oxidation of
cathode, anode and ramming paste during actual baking
process, n, excess air coefficient shall be under strict control
and proper heating process should be made.
741
Fig. 5 Anode oxidation rate and excess air
Fig. 6 Ramming paste weight loss rate and temperature
Heating Process for High Temperature Gas
Baking Approach
As for carbon paste heating process, the ideal process is
soften phase (below 200 °C): the main purpose is to remove
absorbed water and combined water, heating rate should be
rising fast and can reach to 10 °C/h. Otherwise, long soften
time will lead to carbon deformation. From 200–700 °C,
especially 200–500 °C, there will be a large amount of
carbon paste volatile to release. Heating rate in this period
should be kept low enough, no more than 5 °C/h. Otherwise,
742
Fig. 7 Paste oxidation rate and excess air coefficient
rapid discharge of carbon volatile will cause cracks, loosing
structure, strength loss and large porosity. Binder’s coking
process almost has finished above 700 °C, this process could
appropriately speed up. From economic aspect, baking time
should not be too long. The longer baking time is the higher
cost will be. However, short baking time may also effect
cells’ service life and increase maintenance expense. In
conclusion, baking time is a significant parameter for heating
process. Besides baking time, heating rate, bottom temper-
ature distribution and other factors are also important ref-
erences to heating process.
Based on cells’ bottom heat transfer mathematical model
and gas baking transfer property, this paper describes the
impact of heating rate on temperature distribution in bottom
section and influence of thermal physical property of carbon
material on bottom temperature. And it also states the tem-
perature distribution in different heating process, heat sup-
plying and fuel consumption for providing theoretical basis
for the heating process.
To study its influences on bottom temperature distribu-
tion, heat supplying and fuel consumption, calculation about
Fig. 8 Cathode surface
temperature in different heating
process
C. Wu et al.
heat transfer property in different heating process is made
through above mentioned transfer model. Heating processes
are listed as follows.
No. 1 process: t  16 h, tf = 150 + 50 t °C; t > 16 h,
Tf = 960 °C
No. 2 process: t  20 h, Tf = 150 + 40 t °C; t >20 h,
Tf = 960 °C
No. 3 process: t  27 h, Tf = 150 + 30 t °C; t > 27 h,
Tf = 960 °C
No. 4 process: t  40 h, Tf = 150 + 20 t °C; t > 40 h,
Tf = 960 °C
No. 5 process: t  54 h, Tf = 150 + 15 t °C; t > 54 h,
Tf = 960 °C
No. 7 process: t  5 h, Tf = 150 + 20 t °C; 5 < t < 10 h,
Tf = 250 °C;10 < t < 15 h, Tf = 250 + 30 t °C; 5 < t <
20 h, Tf =400 °C; 20 < t < 40 h, Tf = 400 + 20 t °C;
40 < t < 50 h, Tf = 800 °C; 50 < t < 65 h, Tf = 800 + 15
t °C; 65 < t < 72 h, Tf = 960 °C
Heating time is subject to surface temperature while
cathode upper surface temperature is above 900 °C and
lower surface temperature is above 750 °C. From Figs. 8 to
9, there is a big difference between different heating pro-
cesses. No. 1 has the shortest heating time that is 41 h while
No. 6 has the longest time, 70 h. The maximum temperature
difference in process 1 can reach to 530 °C. No. 5 has the
shortest temperature difference, 273 °C. The secondary
shortest is No. 6, 306 °C at most. In addition, heating rate
and temperature is rather stable in No. 5. No. 6 has stable
heating rate but its temperature fluctuates strongly and its
heating curve is more complex than No. 5 (Fig. 10).
Figure 11 shows that other processes have similar heat
supply changing tendency, but rather different value, except
No. 6, which heat supply curve is more complex. Reason for
this situation is that No. 6 has more heat preservation periods
while others have only one period. From Fig. 12, we can see
heating time in No. 1–No. 6 ranges from 41 to 70 h. All
processes can meet the temperature requirements before
Theory and Practice of High Temperature Gas Baking Technology …
Fig. 9 Cathode surface
temperature in different heating
process
Fig. 10 Cathode surface
temperature in different heating
process
startup. Therefore, the heating rate has a rather wide range,
which is also one of many advantages of this high temper-
ature baking approach.
For high temperature gas baking process, the ideal heat-
ing process is short time, short cathode surface temperature
difference, simple heating supply, low fuel consumption and
short high temperature period. Cathode surface temperature
and high temperature period are two more important aspects
among those indicators. Prolonging high temperature period
may add risks for anode and cathode oxidization, which will
impact cell’s service life. In addition, large temperature
difference may enlarge thermal stress in carbon blocks, thus
causing cracks, and impacting cell’s service life. Taking
consideration of above situation, process No. 5 and No. 6 are
better options. Despite of simple heating supply, low tem-
perature difference and low consumption in No. 5, there is
no heat preservation measure in evaporation and paste
coking step, so it will lead to cracks caused by rapid volatile
releasing, then loosing structure and low strength. In con-
clusion, No. 6 is the optimal choice.
743
High Temperature Gas Baking Equipment
Compared with conventional fuel baking technology, main
difference of high temperature gas baking approach lies in
fully combustion in preheating room. It uses fully combusted
gas to heat the furnace and keep oxygen content below 1% in
order to avoid electrodes oxidation problem. Therefore, the
key component for gas baking technology is the combustion
part. Its main functions are: a. fully combusting fuel in fur-
nace, and ejecting hot gases into aluminium cells to heat
anode and cathode; b. proper arrangement of burners shall
ensure uniform temperature distribution, with a fair propor-
tion of hot gas; c. presetting heating curve to well monitor the
process; d. controlling oxygen content to prevent anode and
cathode oxidation damage; e. heating system be easily dis-
mantled when it is finished. Upon above conditions, com-
bustion part is consisted with control station, combustion
racks, burners, oxygen analyzer and so on (see Fig. 13).
With rational heating curve and air-fuel ratio, fuel gas and
air pressure and flow is kept in a certain degree in the fuel
744
Fig. 11 Heat supply in different process
Fig. 12 Heating time and fuel consumption in different process
station. Then mixed gases pass through combustion racks
into burners. After fully combustion within these burners,
hot gases are ejected to aluminium cells for startup. Heating
Fig. 13 Gas baking equipment
skeleton diagram (diesel)
C. Wu et al.
curve is made subjected to different cell types. The baking
process enables cathode upper surface above 950 °C with
less than 40 °C temperature difference while lower surface
above 750 °C, less than 40 °C temperature range. Com-
bustion step is stable and load regulation ability is strong
during the whole process. When excess air coefficient is
below 1.05, oxygen around burner exit can be kept within
1%. The whole heating system is capable to meet all baking
requirements before the startup.
Industrial Application
Based on high temperature gas baking requirements, this
paper analyzes hot gas’s influences on cathode, anode and
paste oxidation mechanics, and bottom temperature distri-
bution in different heating processes and baking require-
ments for materials and their basic property. Depending on
that, high temperature gas baking system and the whole set
of equipment have been developed for cells startup. At
present, it has already been used in many different potlines
and successfully applied in various situation. It proves that
this technology has achieved outstanding accomplishments
in economy, environment protection and labor saving.
In 2015, one aluminium plant with a capacity of
700,000 t/year, introduced this technology in 500 kA pot-
lines. With natural gas as the fuel, they transported natural
gas from gas station to the plant by a tank through tempera
pipeline. It took 96 h to reach to 960 °C. In the end, 20 tons
of hot electrolyte was put into cells and successfully started
as current went through. Impulse voltage was 4.0–4.5 V.
It can be seen from Fig. 14, upper surface temperature
can reach to 960 °C after 96 h, while lower surface tem-
perature can reach to 790 °C at the end of heating process.
From Fig. 14a, upper surface temperature is evenly
Theory and Practice of High Temperature Gas Baking Technology …
Fig. 14 Temperature curve of cathode surfaces
Fig. 15 500 KA potline startup
distributed below 350 °C. However, temperature increases
afterwards. Temperature difference increases to the upper
limit at 700 °C, but it diminishes when temperature is above
800 °C. The maximum temperature difference is 50 °C, at
the end of heating process, and 30 °C on average. From
Fig. 14b, temperature in spots of lower surface has similar
tendency curve. Heating rate between 150 and 200 °C is
slow, due to water vaporizing in ramming pate. In the whole
baking process, cathode bottom temperature varies a little,
40 °C at most. At the end of heating phase, there is basically
no oxidation by visual observation. Cracks may appear in
lateral paste. But electrolyte will then fill in the cracks which
helps prolong cells’ service life (Fig. 15).
745
9000–9500 Nm3 natural gas is needed for one 500 kA
aluminium cell for the whole baking process. It costs
RMB30,000–35,000. Compared with coke baking method, it
saves nearly RMB30,000/per cell annually.
Conclusion
This high temperature gas baking technology is one pio-
neered in China, which not only has advantages of fuel
baking method, but also makes up the gap of cathode and
paste oxidation resolutions. It proves that it is an ideal
baking process. It has also promoted the application of fuel
746
baking technology and filled the gap of research and
development in this field in China.
We studied the oxidation properties of cathode, anode
and paste in gas baking process with the experimental
methods firstly to whether they will be badly oxidized in
the process. We have developed the proper heating pro-
cess and excess air coefficient-n to reduce the oxygen
content in high temperature gas and to further reduce
oxidation.
Heating rate is adjustable to a large range. Compared with
other baking methods, this technology can ensure a uniform
heating and baking effect as well as a fully lateral combus-
tion. This method can achieve an unsurpassable result.
Industrial application proves that high temperature gas
baking technology can guarantee an even and slow heating
rate of cathode lining, and then a uniform surface tempera-
ture. In this way, it avoids paste and cathode damage while
fuel burning, so their oxidation can be well controlled. The
whole baking effect of all parts can be seen clearly after this
procedure. In addition, while aluminum cells’ starting-up,
C. Wu et al.
electrolyte will first fill in cathode lining and lateral paste
cracks. This is favorable to prolong cells’ service life.
References
1. Q. Zhuxian, Aluminium Electrolysis Introduction and Application
(China University of Mining and Technology, 1998)
2. L. Zhang et al., High Temperature Flue Gas Heating Regulations
for Prebaking Aluminium Cells (Journal of Chongqing University
(Natural Science), 2001)
3. W. Zhiqi et al., Cathode Stress Numerical Simulation in Gas
Preheating Process (Light Metals,1st edition), 2008
4. M. Desilets, D. Marceau, D. Mario, Start—curve The—mao—
electro—mechaical Transient Simulation Applied to Electrical
Preheating of fl Hall—Heroult CeU. Light Met. 9, 247–254 (2003)
5. S.V. Patanker, Numerical Heat Transfer and Fluid Flow (Beijing
Science Publication, 1984)
6. Y. Jiianhong, L. Qingyu, Present Damage Reasons and Solutions
for Prebaked Aluminium Cells (Mining and Metallurgical Engi-
neering, 2000)
7. H. Bentzen, J. Hvistendahl, M. Jensen, Gas Preheating end Start of
Soderberg CdJs. Light Met. 8,741–747 (1991)
 Part XVIII
Aluminum Reduction Technology:
Technology Development
 Implementation of D18+ Cell Technology
at EGA’s Jebel Ali Smelter

Daniel Whitfield, Sergey Akhmetov, Jose Blasques,

and Harishchandra Devadiga

Abstract
In March 2012, EGA started seven test cells to validate its new D18+ cell technology.
Designed with the latest technological advances to upgrade the original D18 potlines, the
test cells quickly met their design targets with specific energy of 12.75 DC kWh/kg Al and
AE frequency less than 0.02/cell/day. After successful validation, a project was commenced
in August 2015 to upgrade the original D18 potlines to the newly developed D18+ cell
technology. Unlike previous capacity expansion at EGA, the D18+ project required
construction within the existing potrooms, which continued to operate while the upgrade
was underway. Despite the challenges involved, full conversion of Potline 1 was
successfully achieved ahead of schedule and without injury. Through increased amperage
to 235 kA and higher efficiency EGA’s production capacity will be increased by 23 kt per
annum. Further conversion of 272 cells to D18+ in Potline 3 will commence in September
2016.

Keywords
D18+ technology Potline modernization Live conversion of a potline

Introduction to be installed in the existing D18 potline and includes new

In December 1979 hot metal was produced at EGA Jebel Ali
smelter from the first of three potlines of 120 Kaiser P69
cells each. After the addition of a fourth potline of 144 cells
in 1990, the revised P69 cell technology was referred to as
D18 [1]. The D18 cell technology has since been continually
improved including conversion to pseudo-point feeding,
additional busbar and 36% increase in anode length [2, 3]
and has continued to be a major contributor to EGA’s pro-
duction capability.
To make the next step in terms of efficiency and pro-
ductivity, a completely new cell design was developed by
EGA [4, 5]. Designated D18+, it utilises the latest advances
in reduction cell design such as magnetic compensation,
point feeders and direct alumina distribution. It is designed
D. Whitfield (&)
S. Akhmetov
J. Blasques
H. Devadiga
Emirates Global Aluminium (EGA), Dubai, United Arab Emirates
e-mail: dwhitfield@ega.ae
busbars, new superstructures and an elongated pot shell to
increase the number of anodes to 20 (Fig. 1).
D18+ Implementation
EGA has previously completed brownfield expansions at its
Jebel Ali smelter with the eventual addition of 1213 cells to
the original 360 D18 cells. The D18+ project was the first
project where expansion took place in an operating potline.
To manage both the D18+ upgrade and continuing operation
of the existing D18 cells, Potline 1 was converted in sections
of 30 to 32 cells at a time, commencing in Section #2 and
then continuing to Section 3, 1, 4, 6, 7, 5 and finally section
#8 (Fig. 2).
To bypass the line current while a section was undergoing
D18+ upgrade, a temporary busbar consisting of intercon-
nected sections of 12 m length were placed on rails at the
duct end of the potroom (Figs. 3, 4, and 5).

© The Minerals, Metals & Materials Society 2017 749

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_91
750 D. Whitfield et al.

Fig. 1 D18+ test cells in potline 1

Fig. 4 Bypass busbar in situ

Section #1 Section #2
wedges would be installed so that the bypass busbar would
carry current in parallel to the existing D18 busbar. Once the
voltage drops and connections of the bypass busbar were
Section #4 Section #3
South End

North End

verified, the shunts on the D18 cell busbar would be opened

and the bypass busbar would take the full potline current.
The voltage drops on the bypass busbar were then
Section #5 Section #6
Rectiformers

re-measured every 24 h during the construction period to

ensure no deterioration.
After the D18 shells and superstructures were then
Section #8 Section #7
removed (Fig. 6), the old D18 busbar was cut up and taken
away to allow the necessary civil works to start.
Fig. 2 Potline 1 schematic One of the challenges of the project was the construction
of the new D18+ cells occurring simultaneously with con-
tinuing normal production activities in the same potroom.
Some of these challenges included:

• Restrictions in the centre passage from construction

vehicles, trucks transporting busbars, shells and super-
structures as well as normal potroom movements such as
anode raising beam, hot metal transportation and anode
transportation (Fig. 7).
• Constricted access due to construction works related to
the cross-over busbar.
• Greater number of people and activities in potrooms,
requiring greater care to avoid possible collision and
injury.
• Periodic potline amperage reductions to allow for busbar
Fig. 3 Drawing of bypass busbar connection and other work.

Upon installation (but not energisation) of the bypass
busbar, the cells in the section would then be cut-out.
Cut-out of each section of D18 cells typically occurred at the
rate of 6–7 cells per 8 h shift, resulting in the full section of
30–32 cells being fully cut-out in less than 48 h.
Once the cut-out of a section was complete, the potline
amperage would be temporarily reduced to 50 kA and
Despite these obstacles, the project and operations teams
worked co-operatively within the potrooms to successfully
implement the D18+ project without incident or injury.
With the planned phase-out of D18 technology, and to
minimise costs, younger cut-out D18 shells were segregated
to be restarted later to replace routine cut outs elsewhere in
Potlines 1 and 3 (Fig. 8). The age of the restart cell location
Implementation of D18+ Cell Technology at EGA’s Jebel Ali Smelter
Fig. 5 Drawing of bypass busbar installed in potroom section
Fig. 6 Original busbar after removal of D18 cells
Fig. 7 Constricted access due to cross-over works
was based on the anticipated cut out date for future D18+
conversion (i.e. younger shells prioritised for Potline 3 with
older shells being restarted in other Potline 1 D18 sections).
It was also necessary to balance the number of D18 shells set
aside for restart and those for necessary shell modification to
supply the D18+ project.
It was important to minimise the time out of circuit for the
section, both to keep the project on schedule and to minimise
the hot metal production loss. For the first section the total
751
Fig. 8 D18 cell under restart
time between the cut-out of the first D18 cell to bath-up of
the last D18+ cell was 68 days. Learning from experience,
the project and operation teams significantly reduced the
time required to convert a section to D18+, achieving an
average total time of 47 days for the subsequent seven
sections converted (Fig. 9).
With the reduced section turnaround time, the Potline 1
D18+ project was able to be fully completed 86 days ahead
of schedule on the 24th of July 2016 (Fig. 10).
The main bottleneck was the supply of new superstruc-
tures, as quicker fabrication was not possible without
incurring additional costs. This issue will be resolved for the
planned conversion of Potline 3 to D18+ and should reduce
the turnaround time further.
The new D18+ technology incorporates the latest EGA
cell control system. Based on a PLC controlling up to 10
cells, the system is operated by a new touchscreen
human-machine interface (HMI) (Fig. 11). The introduction
of the more sophisticated control logic and interface meant
additional training for operations personnel. This was ini-
tially done in a classroom with a simulator that fully
resembled the new control logic interface. This was then
followed by familiarisation in potrooms with the first new
D18+ cells (Fig. 12).
752 D. Whitfield et al.

Fig. 9 Total time for D18+ 90 2.25

Time For SecƟon D18+ Turnaround (days/cell)

conversion per section

Total Time For SecƟon D18+ Turnaround (days)

80 2.00
Time For D18+ Conversion
70 1.75
Time / Cell
60 1.50

50 1.25

40 1.00

30 0.75

20 0.50

10 0.25

0 0.00

2 3 1 4 6 7 5 8
Potline SecƟon #

Fig. 10 Potline 1 D18+ project Sec #2

schedule Sec #1 Plan
Sec #3
Plan

Sec #4
Sec #6
Sec #5
Sec #7
Sec #8
Sec #2
Sec #3 Actual
Sec #2
Actual

Sec #4
Sec #6
Sec #7
Sec #5
Sec #8

0 50 100 150 200 250 300 350 400 450

Project Progress (days)

Fig. 11 D18+ HMI Cell Information screen Fig. 12 Technician using D18+ HMI
Implementation of D18+ Cell Technology at EGA’s Jebel Ali Smelter 753

On the 8th of October 2015 the first Section, #2, con-

verted to D18+ was formally handed over from the Projects
team to Potline Operations. Cell 31 was the first cell cut in
(Fig. 13), and after 52 h of pre-heat it was successfully
bathed up on the 11th of October (Fig. 14).
Section #2 cells were then gradually cut-in at the rate of
four per day with the final cell in the section bathed up one
week later on the 18th of October. The same procedure was
followed for subsequent sections with four cells cut in per
day and all cells cut in after 8 days.
The first D18+ section started had lower than expected
final cathode temperature during preheat with an average of
826 °C. This was gradually improved by altering the resistor
template, increasing duration and higher amperage (Figs. 15
and 16). Fig. 14 Bath-up of first D18+ cell in section #2
Constant refinement in the setup of the cell control system
during early operation resulted in the anode effect frequency
1000 225
(AEF) and anode effect duration (AED) quickly stabilising

Average Final Cathode Temperature (°C)

during the first week of operation (Fig. 17). 950 220
Considerable effort was also made by the operations team

Amperage (kA)
to minimise anode effect after bath-up and during subsequent 900 215
metal pouring. This resulted in reduction of AEF during the
first 48 h from 0.70/cell/day to 0.03/cell/day (Fig. 18). 850 210

One of the challenges during the upgrade process was

that the D18 cells were near the upper limit for amperage, 800 205

while the D18+ cells were conversely near their lower limit.
750 200
At the start of the project in September 2015, the amperage
2 3 1 4 6 7 5 8
in Potline 1 was 207 kA. This was increased to 210 kA by
SecƟon #
February 2016 (Fig. 19).
At 210 kA the anode butts of the D18 cells were close to Fig. 15 D18+ final pre-heat cathode temperature and amperage
their minimum size. To mitigate possible stub wash the
anodes where closely monitored and raised if necessary.
66 34
Problem anodes were also replaced more frequently with the

Average Pre-heat Energy (MW.hrs)

64 33
many mid-rota anode butts available due to the D18 cell
62 32
Pre-Heat DuraƟon (hrs)

cut-outs. While this resulted in additional work for the

operations team, it was able to be effectively managed given 60 31

58 30

56 29

54 28

52 27

50 26

2 3 1 4 6 7 5 8
SecƟon #

Fig. 16 D18+ pre-heat duration and energy

that it was only temporary until the D18 cells were replaced
with D18+.
The D18+ cells were also susceptible to low superheat
and associated problems despite the low metal height target,
very high anode cover, low gas draft and other steps taken to
Fig. 13 Section #2 under preheat conserve heat within the cell. Hence the base resistance set
754 D. Whitfield et al.

Fig. 20 D18+ net cell voltage

Fig. 17 D18+ early operation AEF and AED

0.8
AEF for first 48 hours aŌer

0.7
bath-up (#/cell/day)

0.6

0.5

0.4

0.3

0.2

0.1

0.0
2 3 1 4 6 7 5 8
SecƟon #

Fig. 18 AEF for first 48 h after bath up Fig. 21 D18+ noise

point of D18+ cells was set to an equivalent 70 mV higher

until the project was completed and the amperage could be
increased.
Upon cut-out of the final D18 cells, the Potline 1
amperage was gradually raised to 220 kA (Fig. 19). Further
amperage increase is limited by the current fume treatment
plant (FTP) capability and rectifier capacity. Once upgrade
work on the FTPs is completed and a spare rectifier is
installed, amperage will be increased further to 235 kA by
the end of 2016.
Performance
Figures 20 and 21 illustrate the average section voltage up to
300 days of operation. The time to reach target voltage was
gradually reduced from 40 days to 26 days. Average noise
was less than 20 mV three weeks after start-up and is now
averaging 10 mV after 100 days.
Figures 22 and 23 show the average section current
efficiency and net specific energy. The first three sections

Fig. 19 Potline 1 amperage

increase and number of D18+
cells
Implementation of D18+ Cell Technology at EGA’s Jebel Ali Smelter 755

Fig. 22 D18+ current efficiency Fig. 25 D18+ AlF3 concentration

Fig. 26 D18+ metal height

Fig. 23 D18+ net specific energy

Fig. 27 D18+ bath height

Fig. 24 D18+ bath temperature

started (1, 2 and 3) show higher initial current efficiency (as

tapped) due to higher metal heights. For subsequent sections
the first metal tap was done earlier, reducing the need for
larger corrective taps to reduce the metal height to target. At
approximately 60 days age in Section #3 there were issues
with the cell alumina conveying system, which negatively
affected the AEF, bath temperature and current efficiency.
This was subsequently remedied and the section quickly
returned to stability. With the increase to 220 kA, further
work is being done by the operations and process control Fig. 28 D18+ anode effect frequency
756
Table 1 D18+ performance at Variable
220 kA
Net voltage
Current efficiency
Net specific energy
Noise
Net carbon consumption
Anode effect frequency
Anode effect duration (>8 V)
PFC emissions
teams to stabilise the D18+ cells at the new amperage set
point.
Figures 24 and 25 show the average D18+ bath temper-
ature and electrolyte AlF3 concentration. For the initial
sections, the bath temperature was above target and AlF3
concentration was below target for the first 30–40 days. This
was successfully mitigated by gradually reducing the target
net cell voltage during the same period (Fig. 20).
In February 2016 the AlF3 supply changed from low
(0.68 g/cm2) to high density (1.48 g/cm2) AlF3, which
resulted in some additional variation in sections 2 and 3
during the transition period but was quickly overcome
(Fig. 25).
Figures 26 and 27 demonstrate average D18+ metal and
bath height. As per cell start-up procedure, the metal height
target of 15 cm and bath height of 16 cm were gradually
reached after 30 days of operation and with minor variation
thereafter.
Figures 28 shows the average D18+ AEF. Despite the
spike in AEF in Section #6 due to the alumina conveying
issues, the D18+ AEF quickly reduced during the start-up
period and continues to remain at low levels.
Fig. 29 Cross-over works underway in potline 3 for D18+ project
D. Whitfield et al.
Unit D18+
V 4.133
% 94.72
DC kWh/kg Al 13.00
mV 11
kg C/tAl 0.420
#/cell/day 0.042
s 63
CO2eq. kg/t Al 51
Table 1 shows the initial 35 day performance of Potline 1
D18+ after stabilisation at 220 kA. Net specific energy is
13.0 DC kWh/kg Al and current efficiency is stable and
improving at 94.7%. The cells remain stable with an average
noise of 11 mV and PFC emissions are at a low level of 51
CO2eq. kg/t Al.
Future
Pre-work has begun to convert Potline 3 to D18+ technol-
ogy. The first D18 cells will be cut-out in September 2016
and it is anticipated that all 272 cells will be converted by
October 2017 (Fig. 29).
Conclusion
Conversion of all 241 Potline 1 cells to D18+ was achieved
ahead of schedule without incident or injury on the 24th of
July 2016 with the bath-up of the final cell. During the same
period amperage was increased from 207–220 kA. Upon
completion of the FTP upgrades and installation of a swing
rectifier at the end of 2016, the amperage will be increased
further to 235 kA.
Conversion of the 272 D18 cells in Potline 3 has begun
with the aim of completion this by October 2017. The D18
+ project will increase EGA hot metal production by
47 kt per annum and will reduce the energy consumption
of the original Jebel Ali potlines by a targeted 2 kWh/kg
Al while also significantly reducing their environmental
footprint.
Acknowledgements The effort and dedication of Potline Operations,
Jassem Mohammed and Faisal Majid and their teams has been crucial
for the successful conversion of Potline 1 to D18+. Also, the invaluable
work and support of Mohammad SW Ali, Adam Sherrif, Maitha Faraj
and the D18 Process Control team have been indispensable for the
smooth conversion to the new D18+ cell technology.We are also
Implementation of D18+ Cell Technology at EGA’s Jebel Ali Smelter
thankful to Amer Al-Redhwan and the EGA Capital Projects team, as
well as Alexander Arkhipov, Syed Fiaz, Konstantin Nikandrov and
EGA Technology team for the significant work that has been carried
out for the D18+ design and implementation.
References
1. D Whitfield, A. Said, M. Al-Jallaf, and A. H. A. Mohammed,
‘Development of D18 cell technology at DUBAL’, Light Metals.
477–481 (2009)
757
2. D. Whitfield, T. Majeed, S. Akhmetov, M. Al-Jallaf, K. Al-Aswad,
I. Baggash, A. Al-Zarouni, ‘Update on the development of D18 cell
technology at DUBAL’, Light Metals. 727–732 (2012)
3. D. Whitfield, S. Akhmetov, M. Al Jallaf, J. Blasques, K. Al Aswad,
and I. Baggash, ‘From the least to the most energy efficient DUBAL
Potline—The P69/D18 developments’, 11th Australasian aluminium
smelting technology conference, December 2014, Dubai, UAE, 6–11
4. S. Akhmetov, D. Whitfield, M. Al-Jallaf, A. Al-Zarouni, A.
Al-Redhwan, W. A. Sidou, ‘D18+: Potline modernisation at
DUBAL’, Light Metals. 561–566 (2013)
5. D. Whitfield, S. Akhmetov, M. Al-Jallaf, J. Blasques, K. Al-Aswad,
I. Baggash, ‘From D18 To D18+: progression of DUBAL’s original
potlines’, Light Metals. 499–504 (2015)
 Integrating a New Smelter Supervision HMI
in Existing Control Systems at ALBRAS

Vanderlei Oliveira Fernandes, Geir Sandnes, Leonel Vicente Mota Ivo,

and Rogério Cosendey Labanca

Abstract
ALBRAS needed to align its operation with the follow-up methodology used by Hydro
Aluminium, its majority owner. To achieve this goal, ALBRAS decided to standardize its
potline production information by installing Hydro’s APICS system. A tight integration
with the underlying pot control systems was needed to replace their supervision HMI by
APICS’s one. To design an interface to integrate both systems and install it in the running
control systems without disturbing the smelters’ operations was a challenge. In this paper
the interface solution provided to integrate APICS with two different versions of the
SCORE supervision and control system, installed in all four smelters at ALBRAS, will be
presented. Challenges will be discussed, the defined interface solution will be detailed and
the results along with some lessons learned will be presented.

Keywords
Smelter supervision Systems integration Potline interface

Introduction
ALBRAS is a primary aluminum producer located in
Barcarena/PA in the north part of Brazil and started its
operation in 1985. It is owned by Norsk Hydro ASA, with
51% of the capital and NAAC—Nippon Amazon Aluminium
Co. Ltd with 49% of the capital. It has four potlines, each
potline with 240 pots each, making a total of 960 pots. They
operate with pre-baked anodes on a side-by-side arrangement
using AP13 technology from Pechiney. Potline 1 was origi-
nally designed to operate with 135 kA line current while the
V.O. Fernandes
ALBRAS, Barcarena, Brazil
e-mail: vanderlei.fernandes@albras.net
G. Sandnes
HYDRO, Oslo, Norway
e-mail: geir.sandnes@hydro.com
L.V.M. Ivo (&)
R.C. Labanca
Accenture, Nova Lima, Brazil
e-mail: leonel.ivo@accenture.com
R.C. Labanca
e-mail: rogerio.c.labanca@accenture.com
others to operate with 150 kA. After some changes they
operate now with 172 kA at potline 1 and 181 kA on the
other three potlines. The total production capacity is
460,000 tons/year.
All the pots at ALBRAS are controlled by SCORE
Smelter Supervision and Control System, delivered by
Accenture.
The first version of SCORE was designed in 1989 and
installed at Alcan potlines in Brazil. The first version
installed at ALBRAS was SCORE 7. SCORE 7 is a cen-
tralized control system designed in 1992 and installed in
other smelters in Brazil and one smelter in Poland. In 2008 a
new version was designed with distributed control called
SCORE 9. Potline 1 and 2 have the newest version 9,
upgraded in 2010 and 2015. Potlines 3 and 4 are controlled
by the version 7. All servers for both SCORE 7 and 9 are
placed in computer rooms in the reduction area.
APICS solution portfolio has three modules that cover all
areas of a smelter: electrolysis, casthouse and carbon.
Before the implementation of the Aluminium Production,
Information and Control System (APICS) there were several
additional systems to support the operation: Laboratory

© The Minerals, Metals & Materials Society 2017 759

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_92
760
Information System (SISLAB), Reduction Supervision
System (SISRED), Production and Planning Control (PCP),
Shift Report Edition System (SERTU) and many Excel
spreadsheets that provide information to the operational and
process teams. All these systems communicate with a SQL
Server Database. Information between SCORE and SERTU
was exchanged by FTP protocol.
APICS Electrolysis partly overlaps with some of the
functionality in the current SCORE 7/9 systems (typically
resistance graphics, alarms /deviations, control parameter
settings, event logs). However, APICS includes also func-
tionality that is able to cover the additional systems
(SERTU, SISRED, PCP and Excel reports) that were in use.
The solution defined was to reuse the centralized control
system in SCORE 7 and the communication layer towards
remote units and pot controllers in both SCORE 7 and 9.
All end-users use APICS as the supervisory system for all
four potlines. The user interfaces for SCORE 7/9 are only
needed in emergency situations if APICS is not available.
To implement this architecture a reliable and efficient
interface between SCORE and APICS was needed.
The two versions of the SCORE supervision and control
system, SCORE 9 and SCORE 7, installed in the four pot-
lines have significant architecture and technological
differences.
SCORE 9
Potlines 1 and 2 have SCORE 9 version installed. SCORE 9
is a modern fully distributed supervision and control system
developed and installed by Accenture. It is an open and
scalable system. Control strategies are developed using
Fig. 1 ACN9e pot controller installed at ALBRAS
V.O. Fernandes et al.
standard IEC 61131-3 programming and ALBRAS has all
the necessary resources to change existing control algo-
rithms and to develop new ones.
Its pot controller—ACN9e—has a graphical HMI inte-
grated to the control algorithm and controls two pots. Figure 1
Shows an ACN9e pot controller installed at ALBRAS.
SCORE 7
Potlines 3 and 4 have SCORE 7 version installed. SCORE 7
is a more than 15 years old semi-distributed supervision and
control system developed and installed by Accenture. It is a
centralized supervisory and control system where pot control
strategies run in a centralized computer while IOs are
semi-distributed, with centralized analog interface and
decentralized digital input/output (one RTU per pot).
To create the interface for all four smelters with APICS it
was necessary to develop the solution for both systems,
SCORE 7 and SCORE 9. As they are different systems, with
different architecture and running in different software plat-
form, the interface solution needed to be designed and built
independently for both.
Challenges Faced
Control Systems Perspective
Both versions of SCORE supervision and control system are
a complete integrated solution. The proposed interface with
APICS should provide another HMI interface connecting to
SCORE supervision system and at the same time preserve
SCORE original HMI to act as a backup for additional
redundancy. The architecture for both SCORE systems were
not designed to have an external agent acting like another
supervisory system, which would be the case for APICS. As
a result, the interface could not be a simple read/write tag
values interface. APICS needed to act as a SCORE HMI
performing most of the same commands and functions
available in the SCORE HMI, which increased the interface
complexity. All of these commands and functions in SCORE
system needed to be adapted and tested to work having
APICS acting as a remote HMI, and at the same time
maintain them working with the original SCORE HMI.
SCORE 7 and 9 have an open control concept, which
means that ALBRAS developers can develop new control
strategies and change the HMI interface accordingly, creat-
ing new reports and graphics. To maintain this open concept,
the interface between APICS and SCORE should be
designed in a way that gives ALBRAS the ability to include
or change commands and variables without changing
the interface code, preserving the ability of ALBRAS
Integrating a New Smelter Supervision HMI in Existing …
Fig. 2 ALBRAS original landscape
developers to change the HMI by themselves. This
requirement added one more level of complexity to the
interface.
Another challenge faced was the obsolescence of the
SCORE 7 hardware. Old computers with low computing
power and using legacy boards which limited computer
upgrade possibilities imposed a challenge to implement a
fast and flexible interface with APICS.
In the first tests with the actual environment, the OPC
server performance was very poor due to this hardware
obsolescence. It was a challenge to improve its performance
to have a better response time. First was tried to find a better
hardware compatible with the old system but this turned to
be difficult to find in the available time. Despite the fact that
Fig. 3 ALBRAS current
landscape after installing APICS
761
SCORE 7 control servers could not be virtualized due to use
of special hardware, it was identified that the SCORE 7 HMI
server could. As the HMI server could provide the interface
between SCORE 7 and the OPC server, it was moved to a
virtualized environment, greatly improving the performance
and reliability of the interface.
Finally, this new interface must be started with the pot-
lines in normal operation. The running control systems must
be changed to include the new interface and for that, the
SCORE system upgrade had to be installed without dis-
rupting the potline control and current SCORE HMI oper-
ation. APICS HMI interface on the other hand could be
tested in parallel as the operators could still use SCORE
original HMI.
Interface Solution
Systems Landscape Overview
The original production information systems landscape at
ALBRAS before APICS installation is shown at Fig. 2.
In the original landscape there were many different
applications running on level 3, eventually collecting data
from SCORE control systems, each one performing a dif-
ferent production information task.
APICS replaced most of these level 3 legacy systems and
also replaced the smelters´ control system HMI. SCORE
native HMI are still available as a backup option and can
operate in parallel with APICS.
The new landscape after APICS installation is shown at
Fig. 3.
762
APICS Integration Requirements
All the control strategy and communication with the pot
controllers must continue to be done by SCORE 7 and
SCORE 9 systems.
In the integration with SCORE systems, APICS would
need to cover the following:
• Supervisory level (Operator would stop to use the
supervisory level in SCORE 7/9)
• All user interaction needs must be covered by APICS
Data to exchange:
• APICS would need the following data from SCORE
– Cell measurements
– Pot line measurements
– Cell and line events
– Cell and line statuses and alarms
• APICS would need to retrieve only actual values from
SCORE. No historical data would be needed since
APICS creates its own historical data based with the
actual values read from SCORE.
• APICS would need to send orders/update parameters in
SCORE
– Fluoride additions
– Manual measurements like bath level etc.
– Pot and line parameters like reference resistance etc.
– Commands to change pot status like alumina feeding
status, anode control status etc.
Interface Solution
The control systems interface with APICS was done through
SCORE 7 and SCORE 9 supervisory systems.
The interface method selected to create the interface was
OPC. OPC provides a common interface for communication
between various process control devices and control objects
(control and supervision software), strongly increasing
interoperability between systems. OPC communication is
done between an OPC client and an OPC server. The OPC
standard has two versions. The first one is the OPC Classic
based on Microsoft Windows technology using the
COM/DCOM (Distributed Component Object Model) for
the exchange of data between software components. The
newest one is OPC Unified Architecture (OPC UA), a
service-oriented architecture that integrates all the function-
ality of the existing OPC Classic specifications but working
in a platform independent environment.
V.O. Fernandes et al.
Both versions of SCORE systems already had its own
classic version OPC DA server designed to read and write
tags. These OPC servers were reengineered to include the
new functionalities need to create the interface with APICS.
There were two versions of OPC servers for SCORE control
systems, one for SCORE 9 version and another one for
SCORE 7 version.
The APICS solution has standardized on OPC interfaces
towards underlying systems and includes an OPC Client for
this purpose. As OPC UA was the preferred solution for
APICS and the SCORE systems included a classic version
OPC server, an OPC UA wrapper (also referenced as
OPC UA Gateway) was used to connect to both versions of
SCORE OPC servers.
The OPC connection interface is show on Fig. 4.
To create the interface with APICS the following new
features were included in the SCORE 7 and SCORE 9
OPC DA servers:
• Interface protocol using OPC tags to provide a way for
APICS to send commands, like change pot feeding mode,
change pot status etc. With this interface SCORE 7 and 9
systems execute the same commands already available in
their HMI but receiving the inputs and sending the
responses from/to APICS instead of SCORE´s own HMI.
This greatly improved reliability and fast track the inter-
face development since all the commands used by APICS
were already running in production environment. All
parameters changed and commands sent by APICS to the
SCORE system are logged by SCORE system for track-
ing purpose.
• Interface protocol using OPC tags to send SCORE events
to APICS. SCORE events are maintained in a dedicated
FIFO buffer and a protocol with OPC tags permit APICS
to retrieve those events. Any event generated in SCORE
systems are included in the FIFO. Events in the FIFO are
exposed in a group of OPC tags in the same order they
arrive. Once one event is retrieved by APICS it is deleted
from the FIFO buffer and could not be retrieved again.
The events are sent in text format exactly in the same
format they were created in SCORE system. An example
of SCORE 7 event report and the corresponding event
format sent from SCORE to APICS for the last event in
the report is show in Figs. 5 and 6.
SCORE 7 OPC Server
SCORE 7 runs on QNX, a UNIX like real time OS and the
OPC DA server must run in Windows OS. As a result,
Integrating a New Smelter Supervision HMI in Existing … 763

Fig. 4 OPC connection between

APICS and SCORE

Fig. 5 SCORE 7 pot events report example

INDEX 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
STRING 1 4 0 5 2 8 1 2 4 4 5 0 4 2 6 M u d a A l i m M a n u a l

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72
0 0. 0 0 S e m i A u t o C h A l i S A u

Fig. 6 Example of pot event format sent by SCORE to APICS

Fig. 7 SCORE 7—APICS interface environment

SCORE 7 OPC server runs in a separate windows server
2012 environment and connects to the SCORE 7 system
using a dedicate protocol running in TCP/IP. This protocol
was developed using XML messages to make it flexible
enough to support changes made by ALBRAS´ developers
in the SCORE 7 control strategies without the need to
rewrite the protocol code. Figure 7 shows SCORE7—
APICS interface environment, where each system runs in a
different hardware and operating system. They are connected
through a network.
Due to limitations of the architecture and the hardware
of the SCORE 7 system the fastest scan cycle that the
SCORE 7 OPC server could read variables from SCORE 7
system is 4 s.
764 V.O. Fernandes et al.

Fig. 8 SCORE 9—APICS

interface environment

Fig. 9 APICS functionalities

SCORE 9 OPC Server A detailed description of the results and lessons learned
considering the perspective of both sides of the interface is
SCORE 9 runs in Windows server environment and as a presented below.
result, its OPC DA server could run in the same SCORE 9
server environment. Figure 8 shows SCORE9—APICS
interface environment, where each system runs in a different
APICS and Operation Perspective
hardware and operating system. They are connected through
a network.
Results
The fastest scan cycle that the SCORE 9 OPC server
All the legacy software used to manage information in the
could read variables from SCORE 9 system is 1 s.
reduction area were phased out and now all the functional-
In both SCORE 7 and SCORE 9 OPC Servers, ALBRAS
ities are in the same place as shown on Fig. 9.
developers could configure which SCORE variables should
All the functionalities and reports are standardized with
be exposed in the OPC interface and also how they could be
other plants of Hydro, as shown in Fig. 10.
accessed by the OPC Server (read only or read/write).
Figure 11 shows one example of APICS panel that sup-
One OPC UA Gateway is used to connect to one corre-
port users to take process and operating decisions.
sponding SCORE OPC DA server for each line. For SCORE 9
Now all Hydro’s plants have also standardized reports for
interface, the corresponding OPC UA Gateway runs on the
shift, day, week and month.
same SCORE 9 server environment, which eliminates the
network overhead to connect the UA Gateway with the
Lessons Learned
SCORE OPC server.
Having a good test environment available early in the
development phase is important. A tight project schedule
combined with limited test environment was challenging.
Results and Lessons Learned Relying on sequencing/orders of OPC items reduces
overall performance and imposes complexity on the UA
The project was a success, delivered on time and on budget.
client. These sequencing constraints exists on both SCORE
The interface and the systems worked well together as
command execution and event transfer to APICS.
expected.
Integrating a New Smelter Supervision HMI in Existing …
Fig. 10 APICS standardized
functionalities and reports
Fig. 11 APICS cell condition report
Command execution from APICS restricts performance
where only one active command is possible at one line at a
time where each command execution requires a number of
sequenced read and writes to the UA server.
Future Improvements Could be:
• Execute a command using a single OPC item with
command result in another item—preferably using an
765
array structure. Multiple command items or other proto-
col change would further improve performance.
• Event transfer could be simplified and made more effi-
cient by using a single string array OPC item containing
all new events. An even more efficient transfer method
could be to utilize the OPC historical data access but
would probably imply major changes in both server and
client.
766
Unified Automation UA Gateway was used to wrap the
OPC DA servers from SCORE.
Its installation is simple, but information in error mes-
sages requires some experience with both OPC and Win-
dows to be able to interpret.
Configuration was not straight forward and some con-
nection problems between the UA gateway and the OPC
Servers were experienced in the beginning.
There was some communication breaks after the go live
of the interface in all four lines and it was of great impor-
tance to have good cooperation between Hydro, Accenture
and Unified Automation to identify the root cause and solve
the problems. A few new versions of the Gateway have been
released since the start of the project and production envi-
ronment has been upgraded accordingly.
One future improvement is to eliminate the UA wrapper
by upgrading SCORE OPC DA Servers to an UA version.
Control Systems Perspective
Results
Thirteen commands were implemented in the interface for
SCORE 7 and seventeen commands were implemented for
SCORE 9. Some commands implemented for SCORE 7
interface with APICS are marked with red boxes in SCORE
7 HMI shown in Fig. 12. An example for SCORE 9 is also
shown in Fig. 13. Figure 14 shows these commands
implemented in APICS.
All the available pot and line parameters for both SCORE
7 and SCORE 9 systems were exposed in the interface. Any
Fig. 12 SCORE 7 commands implemented in APICS interface
V.O. Fernandes et al.
changes on those parameters are logged by SCORE systems
for tracking purposes.
There are on average 73,500 process variables been read
for each SCORE interface (each potline).
For SCORE 7 these variables are read in groups:
– The first group has the variables that need a faster scan
cycle. They are read every 4 s.
– The second group has the ones which could be read at
1 min scan cycle (control cycle). Those variables are read
in small blocks every 4 s so that every 1 min all of them
are read.
For SCORE 9, all variables are read every 1 s.
Besides variables and commands, process events gener-
ated in SCORE systems are also sent on the interface.
On average 44,000 events per day for each line are sent to
APICS through the OPC interface.
Table 1 summarizes some statistics for each potline.
Lessons Learned
Each pot in a smelter could have hundreds of parameters and
control values to be exposed in the interface with APICS. As
a result, for each interface there are thousands of tags. To
have a good performance in the data transfer between the
OPC client (APICS) and the OPC server (SCORE) it is very
important that the OPC server and the OPC client have the
capability to use vectors. Instead of having to read one tag
for each pot for a particular type of variable, using vectors
the client could read one vector of that variable for all the
pots at once, greatly increasing performance.
Integrating a New Smelter Supervision HMI in Existing … 767

Fig. 13 SCORE 9 commands implemented in APICS interface

Fig. 14 Score commands implemented in APICS

768 V.O. Fernandes et al.

Table 1 Variables and events Potlines Number of process variables read Average events per day
per potline
Potline 1 77,645 44,917
Potline 2 77,405 57,055
Potline 3 69,535 31,067
Potline 4 69,535 44,222
Total 294,120 177,261

Regarding SCORE 7 interface, which has a network
connection to interface the OPC Server and the SCORE 7, it
was of main importance to define different scan cycles for
the variables. As most of the variables change in intervals of
what is called control cycle (1 min), they could be read in
small blocks scaled over the one minute to reduce network
and CPU overhead on the old SCORE 7 computers.
SCORE 9 is a modern control system running in
today’s powerful servers in an up-to-date architecture.
Its OPC DA server runs in the same machine of SCORE 9
server eliminating network overhead from the OPC server
to get data from SCORE. In addition, the OPC UA
Gateway runs on the same machine of SCORE 9 server
eliminating network overhead from UA gateway to con-
nect to the SCORE OPC server. As a result of this
architecture, the time spent to move tag values between
SCORE 9 and APICS is much less than the time spent
between SCORE 7 and APICS. To further increase the
performance of the interface, a future improvement would
be the development of a new OPC UA server to replace
the classic DA Server and as a result eliminate the need
for the UA gateway.
 DX+ Ultra—EGA High Productivity, Low
Energy Cell Technology

Ali Alzarouni, Abdalla Alzarooni, Nadia Ahli, Sergey Akhmetov,

and Alexander Arkhipov

Abstract
After successful development and industrial implementation of DX and DX+ Cell
Technologies, EGA Technology Development launched several initiatives to lower
CAPEX and cell energy consumption. The result is DX+ Ultra Technology, which is
installed in five demonstration cells in the Eagle Section of Potline 5 Eagle at DUBAL
(EGA Jebel Ali Operations), which were started up in March to May 2014 at 450 kA. The
main new features of DX+ Ultra Technology are: reduced cell-to-cell distance as well as
proprietary novel-design split anode risers, collector bar copper inserts and cathode flexes.
More than one year of excellent performance at 455 kA with 95 % current efficiency and
net specific energy consumption of 12.8 kWh/kg Al has confirmed that the technology is
ready for industrial implementation. DX+ Ultra Technology has been selected for Alba’s
Potline 6 expansion. Further optimization of the cells is underway to deliver best-in-class
technology to the client. This includes larger busbar cross-sections for even lower energy
consumption.

Keywords
DX+ ultra cells High productivity—low energy reduction cells Alba potline 6

Introduction
DX+ Ultra Technology cells are designed to operate at lower
specific energy consumption than DX+ Technology. Several
design changes were introduced such as EGA proprietary
collector bar copper inserts, busbar design changes with
6.0 m cell-to-cell centerline distance, split anode risers and
longer anodes. The base design amperage was 440 kA and
the predicted net specific energy consumption at 440 kA was
12.5 kWh/kg Al [1].
Eagle section, the heart of EGA’s high amperage reduc-
tion technology development, was converted from DX+ [2]
to DX+ Ultra (Fig. 1) in early-2014 and four cells were
bathed-up in March 2014. The fifth cell, in the middle of the
A. Alzarouni
A. Alzarooni
N. Ahli (&)
S. Akhmetov

A. Arkhipov
Emirates Global Aluminium (EGA), PO Box 3627 Dubai, UAE
e-mail: nahli@ega.ae
group, was bathed-up in May 2014 to allow time for the
installation of a heat recovery system (HRS) [3].
After the start-up of the cells at 450 kA, the measured
external voltage drop was slightly higher than predicted and
the specific net energy consumption objective of the DX+
Ultra Technology Eagle cells was revised to 12.8 kWh/kg Al
at 440 kA. The objective was unchanged when the amperage
was increased and maintained at 455 kA. Consistent oper-
ation and performance at this amperage was achieved from
May 2015 onwards.
On the other hand, busbar design optimization for the
industrial version of DX+ Ultra Technology will achieve the
original objective of 12.5 kWh/kg Al at 440 kA.
In the following sections the cell design features and
improvements during the initial period of cell operation, the
impact of heat balance and actions taken, the improvements
in the cell control logic, the experimental evaluation and cell
performance are described.

© The Minerals, Metals & Materials Society 2017 769

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_93
770 A. Alzarouni et al.

Noise in DX+ Ultra Pot 276

80
70
60

Noise (mV)
50
40
30
20
10
0
02-Mar-14 29-Aug-14 25-Feb-15 24-Aug-15 20-Feb-16 18-Aug-16
Date

Fig. 2 7-day running average noise in Pot 276 until 31 August 2016.
Underneath busbars were modified on 16 December 2014 (indicated
with black arrow)
Fig. 1 A DX+ Ultra technology cell in the eagle section

This heat is dissipated from the cell into the environment [4].
Cell Design Features and Improvements
In equilibrium, freeze must cover the inner walls of the cell at
target bath temperature and composition. Too high internal
The key features of DX+ Ultra Technology as compared to
heat in the cell increases the temperature above target and
DX+ Technology are [1]:
melts the freeze. This also causes excess AlF3 variations in
the bath. Conversely, proper AlF3 feeding keeps excess AlF3
• Reduced pot-to-pot centerline distance from 6.3 to 6.0 m,
on target and helps maintain the target bath temperature.
• Improved busbar design featuring split riser concept,
Cell heat balance can be affected by uncontrollable heat
• Lower resistance cathode assembly design with copper
generation due to current efficiency loss and anode spikes.
inserts,
However, to maintain the thermal equilibrium, some of the
• Longer anodes.
cell parameters, such as cell voltage, anode cover thickness,
external insulation on the potshell and ventilation of the
These features were selected to reduce CAPEX and lower
potshell can be adjusted.
the specific energy consumption so as to achieve both the
For DX+ Ultra Technology Eagle cells, in certain periods
highest production per surface of building and the lowest
of operation, a specific type of anode spike formation was
specific energy consumption compared to all available
observed near the sidewalls. Measurements of the sidewall
technologies.
freeze showed heavier freeze at the anode level, causing
The five DX+ Ultra Technology cells were started in the
narrower sidewall channels, hence limiting bath circulation.
period between March and May 2014. During the initial
This was one factor that led to a higher possibility of carbon
period of operation, the measured stability level was slightly
dust accumulation in these channels. The other factor was
poorer than DX+ Technology. After conducting several
higher generation of carbon dust driven by lower current
measurements and modelling studies, it was found that
efficiency and higher bath temperatures. To minimise the
minor busbar modification would improve the stability to the
possibility of forming this type of spike, the upper part of the
required level. These modifications were limited to moving
sidewall freeze thickness had to be reduced. This was
the underneath busbars towards the cell ends and adjusting
achieved initially by external insulation of the pot using
some of the cross-sections of the anode (positive) riser
aluminium shields placed on the upper part of the potshell.
flexibles. Figure 2 shows that the busbar modification
To obtain the same result, it was later decided to reduce the
improved the cell stability remarkably. The cell noise
height of the potshell cooling fins (facing the upper part of
became very low, even lower than in DX+ Technology.
the freeze), which allowed removal of the aluminium
Accordingly, very good cell performance is obtained.
shields. This reduced heat loss from the side channels made
Therefore, these simple modifications will be applied for the
the freeze thinner and the side channels wider. Finally, when
optimized industrial version of DX+ Ultra Technology.
good thermal equilibrium was established in the cells from
June 2015 onwards, the spikes near the sidewall disappeared
Cell Thermal Balance and consistent freeze coverage was achieved.
In the middle DX+ Ultra Technology Eagle cell, heat loss
Cell thermal equilibrium is determined by internal heat, from the sidewall is regulated by an HRS [3]. The behaviour
defined as net heat in the cell, i.e. the difference between of the heat balance and sidewall freeze is different to the
generated heat and the heat absorbed by making aluminum. other cells. The HRS provides greater thermal and chemical
DX+ Ultra—EGA High Productivity, Low Energy Cell Technology
stability of the pot, hence keeping bath temperature and
excess AlF3 closer to the targets.
Freeze profile measurements were taken at different
locations during anode change from time to time. Figure 3
shows a typical example of freeze profile measured during
anode change. The freeze is protecting the sidewall lining
well and leaves a 3–8 cm side channel width for liquid bath
at this location.
PLC Based Cell Control System
Several improvements have been implemented in the DX+
Ultra Technology Eagle cells. These cells are also used as a
platform to test develop and test the new control logic as
well as the new HMI screen displays before transferring
them to EMAL Potline 3 [5] and DUBAL Potline 1 [6].
The improvements in the cell control logic include opti-
mization of cell voltage control, alumina feeding control and
anode effect; and near anode effect minimization.
The improvements in the HMI screen displays include
more user-friendly displays, additional screens such as pre-
heat, start-up and metal addition and the corresponding new
control logic.
Experimental Evaluation
DX+ Ultra Technology Eagle cells have been monitored
closely through many measurements. Measurements of cell
thermal and electrical balance, magnetic field and cell stability
have been taken at various stages of amperage increase. These
data were very useful for mathematical model validation and
sensitivity analysis for higher amperage cell operation. In May
2016, another thorough experimental evaluation was carried
out on all five DX+ Ultra Technology cells.
Fig. 3 Freeze profile (red) and carbon block erosion (pink), measured during anode change
771
The following sets of measurements were taken for DX+
Ultra Technology Eagle cells:
• Cell voltage components:
– Anode voltage drop,
– Cathode voltage drop, and
– External voltage drop.
• Busbar current distribution and temperature, including
anode risers:
– Cathode collector bar current distribution.
• Cell thermal balance:
– Freeze profile (cathode erosion),
– Bath superheat,
– Excess AlF3, and
– Anode cover height.
• Shell temperature and distortion,
• Cell magnetic field distribution and
• Cell stability.
The evaluation of cell voltage components is described in
the next section in more detail.
Cell Voltage Components
Cell voltage components are measured for cell technology
evaluation and mathematical model validation [7]. For
energy balance and ACD calculations, anode voltage drop,
cathode voltage drop and external voltage drop are required.
Other voltage drops are used for the control of current dis-
tribution in anodes, collector bars and busbars. Cathode
flexible joint and full cathode flexible voltage drops are used
for quality control of the joint contacts and of current dis-
tribution in the flexes. The anode clamp drop is used to
assess the quality of anode rod to anode beam contact. These
measurements were made at different amperages.
772 A. Alzarouni et al.

Anode, cathode and external voltage drops were also

predicted using mathematical models. Anode assemblies
have the same design as in the former DX+ Technology
Eagle cells, except for the length of the carbon block, which
is 1850 mm, compared to the DX+ Technology Eagle anode
length of 1820 mm. The anode voltage drop is practically
unaffected by this difference. Copper inserts in the collector
bars in DX+ Ultra Technology cells give a cathode voltage
drop of approximately 80 mV lower than in DX+ Tech-
nology cathodes with no copper inserts.
The industrial version of the DX+ Ultra Technology
busbar design is predicted to give an external voltage drop of
253 mV at 455 kA, a reduction of 61 mV with respect to Fig. 6 Current efficiency
DX+ Ultra Technology in the Eagle prototype cells at the
same amperage. The external voltage drop of 253 mV is
close to the original objectives for DX+ Ultra Technology
cell design for the Eagle prototypes.

Cell Performance

DX+ Ultra Technology key performance indicators presented

in Figs. 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 and Table 1,
show 30-day running average of stable operation at 455 kA

Fig. 7 Net specific energy consumption

Fig. 4 Potline amperage

Fig. 8 Bath temperature

during 15 months from 1 June 2015 to 31 August 2016. The

average pot age was 887 days at the end of this period.
Profiled anodes at the top helped achieve the low gross
carbon consumption of 518 kg C/t Al. PFC emissions were
only 1 kg CO2 equiv./t Al, calculated from anode effect
frequency and duration, using the IAI Tier 2 method and
IPCC Second Assessment Report as described in detail in [8].
These excellent performance indicators were the result of
continuous process optimisation and best operational prac-
Fig. 5 Net cell voltage tices, supported by extensive measurements.
DX+ Ultra—EGA High Productivity, Low Energy Cell Technology 773

Fig. 9 Excess AlF3 percentage in the bath Fig. 12 Anode effect frequency

Fig. 10 Fe percentage in the metal Fig. 13 Anode effect duration

Fig. 11 Si percentage in the metal Fig. 14 Net carbon consumption (monthly average)
774 A. Alzarouni et al.

Conclusions

Good and steady pot operation since June 2015 has proven
that DX+ Ultra Cell Technology is a high productivity and
low energy technology. In its industrial version with opti-
mised busbars, it will be capable, of achieving a specific
energy consumption of 12.5 kWh/kg Al. This is based on
the performance of the DX+ Ultra Eagle Technology cells,
which are operating at 95 % current efficiency and
12.8 kWh/kg Al at 455 kA.

Acknowledgements The achievements of DX+ Ultra Technology

Fig. 15 Gross carbon consumption (monthly average) were due to a large amount of work, analysis and optimisation. The
implementation would not have been possible without the support of
many people. We would like to extend our gratitude and appreciation to
all who made valuable contributions to the success of this technology.
Special thanks go to Prof Barry Welch and Dr Vinko Potocnik for their
Table 1 Key performance indicators of DX+ Ultra technology eagle
continuous input and advice during the design and performance
cells
enhancement programme throughout this project.
KPI Units 1 June 2015–31
August 2016
Amperage kA 454.8 References
Current efficiency % 95.0
Metal production kg/pot-day 3479 1. M. Bastaki et al., DUBAL cell voltage drop initiatives towards low
energy high amperage cells. Light Met., 451–455 (2014)
Cell voltage V 4.08
2. A. Al Zarouni et al., Development history and performance of
DC specific energy kWh/kg Al 12.8 DUBAL DX+ demonstration cells. Light Met., 489–494 (2015)
consumption 3. A. Aljasmi et al., Heat recovery from aluminium cells based on heat
Gross carbon kg C/t Al 518 pipe technology, in 11th Australasian Aluminium Smelting Tech-
consumption nology Conference, Dubai, 6–11 Dec 2014
4. A. Al Zarouni et al., Energy and mass balance in DX+ cells during
Net carbon consumption kg C/t Al 402 amperage increase, in 31st International Conference of ICSOBA,
Bath temperature °C 964 19th Conference, Aluminium Siberia, Krasnoyarsk, Russia, 4–6
Sept 2013, pp. 494–498
Excess AlF3 % 10.3
5. M. Reverdy et al., Advancements of DUBAL high amperage
Fe % 0.033 reduction cell technologies. Light Met., 553–556 (2013)
Si % 0.028 6. S. Akhmetov et al., Implementation of D18 + technology in potline
1 at EGA Jebel Ali, in 34th International ICSOBA Conference &
AE frequency AE/pot-day 0.011 Exhibition, Quebec, Canada, 3–6 Oct 2016, Paper AL01, Travaux
AE duration s 5.6 45, pp. 473–483
7. A. Al Zarouni et al., Mathematical model validation of aluminium
PFC emissions CO2 kg/t Al 1
electrolysis cells at DUBAL. Light Met. 597–602 (2013)
equivalent
8. A. Al Zarouni et al., DX+, an optimized version of DX technology.
Light Met. 697–702 (2012)
 Potroom HF Emission Reduction by Anode
Inert Tray Technology Performance of ALRO
Industrial 1st of Class

Vincent Verin, El Hani Bouhabila, Jérémy Neveu, Serge Despinasse,

Gheorghe Dobra, and Marian Cilianu

Abstract
Today, in the electrolysis area of modern aluminium smelters, treatment of pot gas
emissions has been drastically improved by the latest generation of dry scrubbing
technologies, with efficiency rates close to 99.8%. As a consequence, stack emissions now
only represent a very small amount of the total fluorides emitted over the entire smelter.
Most of the HF is released to the atmosphere directly from the potroom, where in many
smelters no specific treatment is provided to limit emissions related to pot maintenance
activities (pot hoods opening, spent anodes removal, etc.). FIVES SOLIOS now proposes a
solution to eliminate emissions coming from hot spent anodes stored in potroom thanks to
an Anode Inert Tray (AIT) designed to confine anode butts. This paper presents the results
of the industrial first of class AIT, developed conjointly between FIVES SOLIOS and
FIVES ECL and which has been operated by ALRO for several months.

Keywords
Potroom emissions HF Hot spent anode Anode inert tray

Introduction However, potroom emissions offer plenty of room for

Nowadays, modern GTCs release around 0.03–0.06 kg of
HF per ton of aluminum (kgHF/tAL) at stack outlet.
Over past years, FIVES SOLIOS has been working on
developing innovative systems to reach an unequaled level
of performance regarding pot gas treatment by filtration, by
implementing for example a new range of dry scrubbing
modules (Ozeos®) or by developing a cascade feeding
system [1]. The level of emission performance is nearly at its
maximum and any further progress would be very costly for
minimal gain.
V. Verin (&)
E.H. Bouhabila
J. Neveu
FIVES SOLIOS, 66 Route de Sartrouville, 78231 Le Pecq, France
e-mail: vincent.verin@fivesgroup.com
S. Despinasse
FIVES ECL, 100 Rue Chalant, 59790 Ronchin, France
G. Dobra
M. Cilianu
Vimetco ALRO, 116 Pitesti Street, 230048 Slatina,
OLT, Romania
improvement, especially when regulation becomes more and
more stringent over global emissions in a smelter. For
smelters without boosted suction features, emissions can be
up to ten times higher at the roof of potroom buildings
(commonly 0.4–0.5 kgHF/tAL) in case of poor operating
practices and/or poor sealing of electrolysis pot hoods.
For years FIVES SOLIOS has been providing boosted
suction technologies (YPRIOS and S-YPRIOS) to reduce
emissions when pot hoods are opened during anode
replacements. However, these technologies do not tackle at
emissions caused by spent anodes, which often cool down
right next to pots, thus emitting HF for several hours into the
potroom atmosphere.
Such anodes are among the main sources of emissions,
contributing up to 40% of total potroom emissions [2].
Consequently, FIVES SOLIOS has focused on develop-
ing solutions to provide treatment for spent anode butts HF
release.

© The Minerals, Metals & Materials Society 2017 775

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_94
776
Spent Anode Butts Treatment in Potroom
As presented in TMS 2015 [3], HF emission is produced by
the reaction of the hot spent butt and the attached layer of hot
bath crust when exposed to the humidity contained in the
ambient air. Therefore, a simple method to stop these
emissions consists in isolating the anode butt from ambient
air.
The theory is simple but practical implementation is more
complex. Up to date, several systems have been deployed by
various competitors but do not solve entirely all challenges
related to this matter (cost, storage capacity, alumina con-
sumption, maintenance, etc.) [3].
FIVES SOLIOS AIT Concept Description (2014)
Taking past achievements into consideration, FIVES
SOLIOS has been developing a system since 2014 that
isolates spent anode butts as fast as possible, with handling
operations reduced to the bare minimum, while maintaining
low CAPEX, low OPEX and easy operation.
The solution which has been selected consists in sinking
the hot butt into a tray containing alumina, as shown on
Fig. 1. As soon as the butt is placed on the tray, fluidization
is activated, causing the sinking of the anode butt. Once the
butt is buried into alumina, it is totally isolated from ambient
air and fluidization can be stopped. This process only takes
few seconds, thus limiting vastly emissions during butt
handling.
In such configuration, trays do not require any lid, seal or
moving part as alumina ensures tightness around the butt.
Connection to a compressed air network is the only element
required for the system to operate properly.
Fig. 1 AIT first prototype receiving spent anode in ALRO
V. Verin et al.
FIVES SOLIOS First Prototype Presentation
at ALRO (2014)
Following the first trial performed at the ALRO plant in 2014
(Fig. 1), the prototype has been validated by ALRO opera-
tional teams. For FIVES SOLIOS, the next step was to improve
and propose an industrial solution to its partner and validate the
theoretical concept of confinement. Hence, the industrial first
of class has been commissioned beginning 2016.
FIVES SOLIOS AIT Industrial First of Class
at ALRO (2016)—Tests and Results
Since the first tests on the prototype presented at TMS 2015
[3], FIVES SOLIOS has reviewed in depth the design of the
AIT, focusing on operational and practical use (see Fig. 2).
The system has been designed to be ultimately used for
industrial application. It is now designed to entirely replace
the pallets used to handle spent anodes and to fit at best in
ALRO aluminum smelter. The new system was commis-
sioned beginning 2016 in ALRO. FIVES SOLIOS took into
account the recommendations of the ALRO teams based on
feedback made over the prototype (Fig. 3).
HF emissions have been monitored on the new AIT
Industrial First of Class on ALRO potline.
A group of 4 spent anodes were placed on the
non-fluidized alumina bed.
Then, fluidization was activated for a short duration (30 s)
following completion of deposit of the fourth anode. Fluidiza-
tion caused the sinking of hot spent anodes in the fluidized bed
of alumina within 20 s. HF emissions were measured with a
Unisearch LASIR analyzer, simultaneously with temperature
measurements with thermocouples (see Figs. 4 and 7).
Potroom HF Emission Reduction by Anode Inert Tray Technology …
Fig. 2 AIT industrial first of class design 2016 for ALRO
Butts temperature was measured with a contact high
temperature probe.
On Fig. 5, the external temperature of the butt is about
620 °C when installed in the AIT. When the butt is covered
with alumina, it takes nearly 12 h to reach 400 °C, the
temperature below which the HF formation reaction does not
occur [4]. Currently, in ALRO, anode butts are maintained
for 24 h in AIT, then transported to rodding shop for final
cooldown (between 24 and 48 h depending on operating
cycle). Overall, butts cooldown is made slightly longer by
AIT as butt confinement in alumina retain heat more than in
ambient air.
Fig. 3 AIT industrial first of class receiving spent anode in ALRO industrial first of class HF measurements
777
Temperature of alumina in the tray was also measured for
three days following reception of a set of anode butts
(Fig. 6), with a probe located between the fluidization fabric
and the butt. This data helped checking that the fluidization
fabric was not exposed to excess temperatures and it enabled
adjusting design height between alumina and fabric.
Results and operational checks have shown that the AIT
meets FIVES SOLIOS’ expectations.
Fluidization is operating well and efficiently. Butts have
penetrated easily into fluidized alumina. Butts positioning
and removal was performed easily with ALRO’s Pot
Tending Machine (PTM). The fluidization flow was mea-
sured via pressure drop measurements obtained with a dif-
ferential pressure sensor located between the space under the
fluidization fabric and the atmosphere.
Flow adjustment valves were adjusted to operate properly
and avoided any geyser of alumina in contact with the hot
anodes butts once proper flow was reached.
Regarding emissions, following start of fluidization—
therefore once spent anodes became buried under alumina—
HF emissions appeared to stop almost immediately (see
Fig. 7). Efficiency of the AIT for reduction of anode emis-
sions in potroom was therefore acknowledged.
In this configuration, FIVES SOLIOS’ teams calculated
the emission of butts lying on the alumina until the burial.
With this configuration (4 anodes butts), 0.360 kgHF or
0.061 kgHF/tAL were emitted in ALRO plant (0.090 kgHF/
anode).
Compared to normal conditions for one anode butt
without AIT treatment, emission measurements made in
ALRO in 2014 showed that one untreated anode butt in
ALRO would release 0.358 kgHF, or 0.245 kgHF/tAL [3].
778
Fig. 4 HF measurement on AIT
industrial first of class receiving
spent anode in ALRO
Fig. 5 Spent anode temperature
on AIT industrial in ALRO
The AIT solution therefore provides a 75% drop over
anode butts emissions.
Following cooldown, for each anode removal, an alumina
portion remains above the anode and is therefore removed
out of the tray. The measured loss of alumina is about 30 kg
per set of four anodes. However, such alumina is not entirely
lost as it is directed to rodding shop treatment.
V. Verin et al.
Today, ALRO operation team keeps using the AIT.
A complete drainage was made over the alumina which had
been used in the AIT for three months after its commis-
sioning. Extensive monitoring (quantity of product and
sampling) was made over the alumina.
After 3 months, 25% of the total content had been
withdrawn from the AIT during handling and extraction.
Potroom HF Emission Reduction by Anode Inert Tray Technology … 779

Fig. 6 Alumina temperature on

AIT industrial first of class
receiving spent anode in ALRO

Fig. 7 HF measurement on AIT

industrial first of class receiving
spent anode in ALRO

Fig. 8 Deposits after 3 months

on AIT industrial first of class

A control of the condition of the AIT itself was also No damage was observed over fluidization fabrics
made, especially regarding the bath and anode crust deposit after 5 months of operation (Fig. 9). The use of AIT will
inside the AIT. All these impurities were easily removed via be extended in ALRO plant to reduce potroom
the basket grid installed on the bottom of the AIT (Fig. 8). emissions.
780
Fig. 9 Inspection of fluidization fabrics after 5 month
AIT Industrialization for Greenfield and
Brownfield Plant
For industrialization purposes for greenfield and brownfield
plants, FIVES SOLIOS is currently working in partnership
with FIVES ECL to improve handling of AIT (Fig. 10) with
PTM (Pot Tending Machine) cranes.
The aim is to have an equipment readily usable by PTM
with minimal interference with other pot handling
operations.
Fig. 10 Design of AIT to replace actual tray in Potroom
V. Verin et al.
Anodes handling in potroom is highly ordered. Many
parameters must be integrated when designing a new ele-
ment, such as the dimensions of building doors, the maxi-
mum anode handling height, the height of pallets with
anodes, the pallet lift with vehicles, etc.
Time schedule and order of tasks are also very specific in
a potroom. This last point is critical as PTM operators have a
specific timeframe to perform their work during a shift.
Therefore, implementing an AIT in a plant implies additional
handling, which should last a minimal time to limit inter-
ference with other PTM operations.
Another challenge consists in providing a design which
suits existing anode trays.
Indeed, the AIT shall be transportable by current vehicles.
In ALRO, at prototype stage, AIT remains in the potroom
due to dimensional constraints in the rodding
shop. The PTM is therefore needed to remove anode butts
from the AIT after cooldown for transportation in traditional
anode trays. For industrialization, AIT will be transported
directly from potroom to rodding shop instead of anode
trays, thus engendering no extra operations for PTM oper-
ators after butts cooldown.
FIVES ECL’s expertise in anode handling in potroom is
critical and helps FIVES SOLIOS having an exhaustive
overview of all operational constraints related to the imple-
mentation of a confinement solution in potroom.
Conclusion
Between 2014 and 2017, AIT has evolved from prototype
stage to being a fully operational equipment in the ALRO
plant.
All tests undergone in collaboration between
FIVES SOLIOS and ALRO have provided satisfactory
results and tend to show that AIT is well suited to industrial
environment, both in terms of pure performance (HF emis-
sions become marginal once spent anodes are buried in
alumina) and operational integration (low maintenance,
limited CAPEX, low interference with other potroom
operations).
The product now enters its final development stage,
where FIVES SOLIOS’ R&D teams will be willing to fine
tune the equipment for integration in greenfield and
brownfield plants, while also working at further reducing its
impact for potroom operators.
In a context where reduction of fluorinated emissions
must remain a prime concern for aluminium producers,
FIVES SOLIOS is confident that AIT will soon become a
must-have in the aluminium industry when it comes to
reducing potroom emissions.
Potroom HF Emission Reduction by Anode Inert Tray Technology …
References
1. P. Martineau, J.-N. Maltais, V. Vérin, M. Frainais, Start-up of the ozeos
gas treatment center (GTC) for RTA AP60, in TMS 2015 (Feb 2015)
2. G. Girault, B. Petitjean, G Riverin, Solution to reduce fluoride
emissions from Anode Butts, in TMS 2015
781
3. B. Hureiki, A. Periers, A. de Gromard, C. Lim, G. Dobra, M.
Cilianu, Treatment of gas emissions in potrooms, in TMS 2015
(Feb 2015)
4. J.-P. Gagné, R. Boulianne, J.-F. Magnan et al., New design of cover
for anode tray. Light Met. (2006)
 Enabling Efficient Heat Recovery
from Aluminium Pot Gas

Daniel Perez Clos, Trond Andresen, Petter Nekså,

Sverre Gullikstad Johnsen, and Ragnhild Elizabeth Aune

Abstract
In the present work, previous studies carried out by the Norwegian aluminium industry and
research centres with the aim of recovering heat from aluminium production off-gas, are
reviewed. The main challenge in improving heat recovery is the fouling phenomena, which
is due to the presence of particulate matter and corrosive gases in the off-gas. Fouling can
occur due to particle deposition, condensation of corrosive acids and scaling reactions,
which in turn can build up hard layers, particularly, on heat exchanger surfaces. The review
focuses primarily on fundamental studies (theoretical and experimental), which address
off-gas composition characterization, particle size distribution and particle deposition
phenomena in laboratory and industrial environments. Moreover, it presents commercial
concepts already implemented in industry applications. Upcoming activities in regards to
the scaling phenomena, which include the design of a cold-finger for laboratory and
industrial measurements, as well as mathematical modelling using CFD, are also discussed.

Keywords
Aluminium industry Heat recovery Fouling Scaling CFD

Introduction loss to the environment. Recovery of such heat for useful

The impact of human activities on the environment is ever
more noticeable as new economic powers are emerging and
becoming rapidly industrialized. Governmental regulations
are becoming more stringent in order to avoid harmful
emissions and to enforce a better use of available resources
and energy. A large share of emissions and energy loss can
be tailored to different types of industry, which have some
things in common. On one hand, they are responsible for a
huge amount of low temperature (80–150 °C) waste heat
D.P. Clos (&)
T. Andresen
P. Nekså
SINTEF Energy Research, Trondheim, Norway
e-mail: daniel.p.clos@ntnu.no
S.G. Johnsen
SINTEF Materials and Chemistry, Trondheim, Norway
D.P. Clos
R.E. Aune
Department of Materials Science and Engineering, Norwegian
University of Science and Technology (NTNU), Trondheim,
Norway
purposes (e.g. power production, district heating, etc.) is a
challenge since highly efficient heat exchangers are required
in order to keep high enough temperature levels for practical
utilization. Additionally, heat recovery is usually hindered
by fouling phenomena caused by the unclean nature of
industrial effluents carrying the waste heat.
Fouling is a general term that refers to the unwanted
deposition of solid layers on surfaces, which reduce heat
transfer and may cause clogging problems amongst other
issues. Such layers can develop from different mechanisms
that are unique for every process but that share some char-
acteristics. Some examples would be deposition of particu-
late matter, scale formation from chemical reactions,
biofouling, corrosion and combinations thereof [1, 2]. Direct
precipitation from supersaturated species can cause the
growth of crystal layers strongly adhered to the heat
exchangers walls. Such layers can cause subsequent reac-
tions with other chemicals and increase the adhesion of
particulate matter. Further aging reactions can also generate

© The Minerals, Metals & Materials Society 2017 783

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_95
784
complex multi-phase structures. Fouling is very costly for
industry due to units oversizing, degradation, maintenance
and cleaning-induced downtime.
In order to tackle these issues and others, the Norwegian
Research Council has launched an ambitious research centre
(SFI metal production [3]) managed by the Norwegian
University of Science and Technology (NTNU) in con-
junction with relevant partners from the metal industry
(ferroalloys, aluminium and titanium), academic institutions
and supply industry. The centre was started on April 2015
and will go on for eight years with a total budget of
247 million NOK with the objective of developing new
production processes that are more environmentally
responsible and more energy and cost efficient.
The present paper, which has been produced within the
SFI metal production, has the objective of analysing previ-
ous work performed within the consortium and identifying
challenges ahead in the field of heat recovery from
aluminium production off-gas.
Fundamentals
This section presents studies that focus on the description
and understanding of different fouling mechanisms (i.e.
particles motion, adhesion, re-suspension, bulk behaviour,
chemical reactions, etc.) both using theoretical and experi-
mental approaches.
Theoretical Models
The first step required in the development of mathematical
models that can reproduce complex multi-phase systems is
the understanding of the relevant underlying physical prin-
ciples. This is performed by defining the governing equations,
which should account for the interactions between
particle-fluid, particle-particle, particle-wall as well as exter-
nal forces. Two main modelling frameworks exist for the
description of the physical governing equations accounting
for fluid and particles motion; namely Eulerian and Lan-
grangian descriptions.
The Eulerian framework treats both phases as a contin-
uum in a macroscopic scale. Space is discretized in fixed
nodes where fluxes of mass, momentum and energy are
computed to obtain the distribution of mass, velocity and
energy among others in the problem domain. The Eulerian
framework allows for separate description of fluid and par-
ticles flow, which can be computed in parallel. The fixed
mesh shows advantages when simulating high materials
deformation (i.e. explosions, high velocity impacts) com-
pared to the Lagrangian approach. However, this description
gives access to limited information on particles and fails to
D.P. Clos et al.
describe transient dynamics of multilayer formation from a
microscopic point of view. Moreover, it is difficult to treat
irregular geometries and it requires complicated mesh gen-
eration procedures [4, 5].
Lagrangian methods on the other hand involve trajectory
calculations typically for a large number of particles moving
in a fluid turbulence field, which can be generated with
different methods. Different subclasses exist within this
frame ranging from models that can resolve interactions
between all particles at a microscopic level to models where
statistical averaging is used to define mean-fields affecting
the different particles in a mesoscopic scale. Whereas the
former models can give insight to detailed mechanisms for
particle deposition and resuspension, they cannot be scaled
to real inhomogeneous 3D systems. Mesoscopic models
using “one point probability density functional” could
however have the potential of describing complex systems
with a larger level of detail than Eulerian models [6] and yet
be applied to complex real size systems. Rapid increase in
CPU power is making this field ever more attractive. The
main issue when modelling particle deposition is the
description of the complex events occurring in the near-wall
region. Different methods are used to try and describe the
boundary layer problem ranging from simple fully absorbing
walls to models were adhesion and re-suspension mecha-
nisms are introduced.
In an article published in 1990 by Johansen [7] an
Eulerian-Eulerian one-dimensional model was presented to
study particle deposition on fully absorbing vertical wall.
The main objective was to study the influence of the tur-
bulent migration and the transversal lift on the deposition
rate. Results were validated against experimental data from
the literature. The model represented deposition data very
well and could account for the large scatter of experimental
values found in the literature (3 orders of magnitude differ-
ence for particle deposition from different studies) which
could be assigned to different particle relaxation times
(proportional to particle size). Reynolds number, electro-
static charging of particles and Brownian motion were also
found to play a significant role as well.
The model was extended to account for the effect
of temperature gradients on particle deposition [8].
Re-entrainment of particles hitting the wall was also intro-
duced by considering that deposition could not occur if the
shear force (proportional to fluid velocity) acting on the
projected area of the particles exceeded the thermophoretic
adhesive force. Results showed that the introduction of
re-entrainment produced results in excellent agreement with
experimental data as can be seen in Fig. 1.
Years later the near-wall effects where specifically
addressed by Johnsen and Johansen in [9] where a detailed
boundary layer model was presented which could be applied
as boundary condition for coarse grid computational fluid
Enabling Efficient Heat Recovery from Aluminium Pot Gas
Fig. 1 Thermal-inertial deposition of particles [8]
dynamic (CFD) models. The one-dimensional boundary
layer was solved numerically in a fine grid capable of
resolving the near-wall XDLVO force lengths scales.
The model reproduced the typical deposition rate versus
particle relaxation time plot but was not further validated
with experimental data. The effect of various physical phe-
nomena like turbulence, granular pressure and XDLVO
forces as function of distance from the wall were studied for
different particle sizes. Results showed that dominant
mechanisms varied depending on region and particle size.
Close to the wall XDLVO forces were dominant suggesting
that achieving surface repulsive forces (i.e. using coating)
could prevent fouling.
In another paper published on the same year [10] the
same authors modified the model to account for particle wall
adhesion/re-entrainment by using an adhesion probability
derived from a turbulent shear stress probability function.
Results showed that in general deposition rate will increase
for increasing fluid velocities until shear induced
re-entrainment rate becomes of the same order as deposition
rate. Moreover, large particles were found to be more easily
re-entrained than smaller particles due to weaker adhesive
forces. Finally, results were compared with two experi-
mental studies with satisfactory results but it was concluded
that further development to handle thermo-chemical beha-
viour was required.
The previous models described above lack the possibility
to account for chemical reactions that are often involved in
the fouling process phenomena. The presence of gas species
785
that might become saturated upon cooling in heat exchang-
ers can cause their precipitation in heat exchanger walls
thereby causing corrosion problems and enhanced stickiness
and reactivity of the walls. This issues were addressed by
Johnsen et al. [11] by development of a generic modelling
framework to investigate the diffusive mass transport
through the turbulent, reactive boundary layer of multi-
component fluid mixtures precipitating in a heat exchanger
wall. In the same manner as the article previously described,
this framework can be used as boundary layer for coarse grid
CFD models. A fully developed flow was assumed parallel
to the wall and 1-dimensional equations for species and heat
transport perpendicular to the wall were formulated. Fluid
mixture properties required in the modelling framework
were based on the pure species properties. Future work will
involve implementation of the current modelling frame-
works via user-defined functions, in commercially available
CFD software.
Experimental Studies—Particle Characterization
and Deposition
The level of complexity of theoretical models is increasing
rapidly but there is still a big gap when trying to describe and
predict phenomenon occurring in industrial environments.
For the particular case of aluminium off-gas difficulties arise
due to both the complex interaction between particulate and
gaseous compounds present in the off-gas together with the
composition variability that occurs during cells operation.
This variability is smoothed as pipes from different sections
are joined into larger ducts eventually leading to the gas
treatment facilities. However, it is desirable to perform heat
recovery as close as possible to the heat source in order to
reduce the amount of heat loss to the environment.
This section will present experimental results obtained in
the last years in collaborative projects between the Norwe-
gian aluminium industry and research centres. The aim of
those studies, besides the understanding of the deposition
and clogging phenomena, is also to obtain a better knowl-
edge of the process material and energy balances in order to
improve materials recycling, product purity and emissions
control among others.
Laboratory Tests
Different laboratory studies have analysed the deposition and
resuspension phenomena of a particle-laden gas into differ-
ent substrates mimicking real life tubes and heat exchanger
walls.
A probe to monitor gas-side fouling in cross-flow heat
exchangers was developed and tested in NTNU laboratory
experiments in 2002 [12]. The probe was designed to
monitor both heat flux and mass accumulated on the front
786
and rear side (with respect of the incoming gas) of a cylinder
in cross-flow. Results showed that heat transfer was larger in
the front side for clean air (without particles) due to the
increased thermal convection given the higher gas velocities
in this side. It was also found that the deposition layer and
measured fouling resistance was larger in the front side of
the tube.
In 2012 a wind tunnel rig was designed and built in
NTNU to investigate in more detail deposition and resus-
pension mechanisms using both commercial (mainly of sil-
icon oxide and aluminium oxide) and industrial particles
(aluminium oxide) [13]. Velocity field inside the test section
was measured by means of Pitot static probes and Laser
Doppler Anemometry (LDA). Moreover, mass deposition
was studied by gravimetric means using probes and by
optical means using a camera to visualize deposited layer
thickness. Similar kind of experiments were performed in the
same rig by NTNU master students [14–16] which were also
combined with theoretical simulations. The circular probe
developed by Temu et al. [12] was used for the fouling
experiments. Results for the velocity field measured in the
test section with the cylindrical probe by LDA compared to
simulations using 2-D COMSOL software can be seen in
Fig. 2. Both results show the typical wake velocity profiles
in the front (left) and rear (right) side of the tubes with
respect of the incoming gas. Experiments were run for
45 min under isothermal conditions and particle deposition
was only observed in the front side (incoming gas). No
additional growth was observed after the first 15 min. The
effects of thermophoresis.
In Situ Tests in Industrial Plants
The experiments presented in the previous section are
valuable to get a better understanding of the fundamental
mechanisms that govern particle deposition and resuspen-
sion but they only represent idealized systems that deviate
substantially from real cases. Experiments in real plants are
Fig. 2 Flow velocities of the test section with a circular cylinder probe measured by LDA (a) and simulated using 2-D COMSOL software [13]
D.P. Clos et al.
therefore necessary to characterize the composition of the
different species present in the off-gas and to identify which
ones are involved in the fouling process.
In a study by Næss et al. in 2006 [17] a test section was
built where two different probes could be used to monitor
fouling effect on heat transfer over time. Both probes were
cylindrical, one of them having an annular fin. Off-gas from
aluminium smelting process was iso-kinetically extracted
from the centre of a duct leading to the bag filters, and
circulated through the test section before being redirected to
the duct. The transport pipe was wrapped with electric wires
that could increase the temperature of the off-gas before
entering the test section from 120 to 180 °C. Particle size
distributions were measured using a cascade impactor in
both the main off-gas duct and test section giving similar
results, with 70% (by mass) of the particles being in the
submicron range. The average particle concentration was
found to be 195 mg/Nm3 for the test section and
300 mg/Nm3 for the main duct. The discrepancy was partly
justified for the loss of larger particles in the extraction of the
gas in the test section. Acid dew point was reported to be
approximately 42 °C. Therefore, experiments were run
keeping wall temperatures between 60 and 70 °C to avoid
corrosion issues and increased deposition due to the
enhanced particle sticking in wet conditions.
Experiments were run for over 1500 h where heat transfer
was decreased asymptotically until stable conditions were
reached. For both geometries a massive deposition of parti-
cles was observed in the rear side of the tubes where the
shear forces are minimum due to the tube shading effect. This
effect is opposed to the ones observed in laboratory experi-
ments were deposits in the rear side were minimal [12, 13].
The reason for this discrepancy is not clear and should be
further investigated. Differences in the test section geome-
tries and increased complexity of particle size distribution
and chemistry for the industrial case might be important
contributions explaining such different behaviours. Both
Enabling Efficient Heat Recovery from Aluminium Pot Gas
geometries displayed very close heat transfer behaviour even
though the fouling resistance was larger for the fin case. That
was due to higher fin efficiencies when fouling increased,
which compensated the higher resistance. Experiments at
different superficial mass fluxes revealed that fouling was
minimized at larger gas velocities and that stable conditions
were reached more rapidly as can be seen in Fig. 3.
The effect of thermophoresis was also investigated by
using different gas temperatures. Results determined an
increase of 18% in the fouling factor due to 17% increase in
the mean temperature difference between the off-gas and the
pressurized air circulating inside the probe. Results from this
study suggested that heat exchangers that could reach stable
and acceptable fouling conditions need mass fluxes that are
above 10 kg/m2s. This means that local gas velocities in
narrow gap regions would be in the range 20 m/s, which
could cause erosion problems due to particle impaction and
high gas pressure drops. This might increase fan power
consumption to undesired levels.
In an NTNU master thesis from 2008 [18] an isokinetic
sampling system was built and used to measure particle
concentration from the pot gas of the Hydro aluminium plant
in Sunndal. The particle concentration in the flue gas from
56 electrolytic cells was found to be 363 mg/Nm3 with a
standard deviation of 12%, which is in good agreement with
the study by Næss et al. presented above.
In 2010 in situ measurements were performed to char-
acterize the flue gas in the aluminium plant of Nordural
during a master thesis from the university of Reykjavík [19].
Measurements were performed at the stack leading to the gas
treatment centre where gas from 180 pots was gathered.
A system for isokinetic sampling was built to collect
Fig. 3 Fouling factor versus
time for the annular-fin test tube
at various superficial mass fluxes
[17]
787
particulate samples, which were analysed by several means.
A pitot tube was used before each run to determine duct
gas velocities, which were found to be in the range of
14–17.5 m/s.
Chemical composition analysis by an Energy Dispersive
Spectrometer (EDS) coupled in a Scanning Electron Micro-
scope (SEM) showed that the dust mainly contained carbon,
oxygen, fluorine and aluminium. Notable amounts of sodium
and some trace amounts of sulphur, potassium, calcium, iron
and nickel were also detected X-Ray Powder Refraction
(XRD) was used to identify the different crystalline phases of
the particles. Results showed that the solid matter mainly
consists of alumina followed by cryolite (Na3AlF6), chiolite
(Na5Al3F14) and kogarkoite (Na3(SO4)F) with trace amounts
of fluorite (CaF2) and sodium aluminium fluoride (NaAlF4).
In addition, a Macro Elemental Analyzer (MEA) was
used to measure the concentration of organic carbon in the
samples, which was found to be 15.7% of the total particles
mass. It was pointed out that this value might have been
larger than usual since some cells were experiencing anode
problems. Particle size and dispersion were measured by
SEM and with a Laser Diffraction Meter (LDM). An average
particle size by volume of 18.5 µm was found. Moreover
particles with equivalent diameters between 4.5 and 61 µm
represented 80% of the total mass which is a rather large
discrepancy from the results reported by Næss et al. [17]
who reported 70% of the mass corresponding to particles in
the submicron range.
Finally, particulate deposition on a probe showed similar
results for both upstream and downstream deposits com-
pared to the samples extracted with the isokinetic sampling
system.
788
The particle sampling methods employed in the above
study give a good insight on the overall particulates com-
position but fail to provide with information regarding the
amount, composition and size distribution of the individual
particles. With this purpose in mind, an electrical low
pressure impactor was used in a Ph.D. thesis to perform
experiments in the aluminium plants of Alcoa Mosjøen and
Hydro Sunndal [20]. This innovative technique allows for
online monitoring of the particle size distribution by
charging the particles before entering the impactor section,
which separates them by size. The use of suitable substrates
in the impactor allows particle collection for further char-
acterization. Different publications from that thesis are
presented hereby.
In 2011 the Electrical Low Pressure Impactor was used to
sample particles from aluminium raw gas extracted from two
different sites [21]; on one hand from the main duct of a
production line before the dry scrubber and on the other
hand from the stack between the dry and wet scrubbers. This
equipment allowed for real-time sampling of 12 particle
classes divided in the size ranges between 7 nm and 10 µm.
Results showed that larger number of particles were mea-
sured with the impactor equipment in the sub-micron range
than were previously reported in a study using SEM for that
purpose [22]. SEM images of the size-classified particulates
revealed a change in agglomerate morphology for the
different particle size classes.
In another publication next year the same author investi-
gated the effect of different operational conditions on pres-
ence of impurities of ultra-fine particles (<10 µm) using a
similar methodology as described above [23]. Energy dis-
persive spectroscopy (EDS) and mass spectroscopy (HR
ICP-MS) analysis revealed a significant increase in contam-
inant level for particles with diameters larger than 0.75 µm.
The findings indicated that particles with diameters lower
than 1.2 µm consist mainly of quenched bath fumes NaAlF4,
Na5Al3F14 partly converted to NaAlF6 and AlO3. The effect
of distributed point suction (DPS) was also investigated but
although the suctions rates were drastically changed, the
variation between recorded mass-concentrations of different
measurements were surprisingly small.
Experimental Studies—Scale Formation
Scaling is the formation of hard and strongly adhered layers
on surfaces due to reaction of chemicals. Usually many
components and operational factors may influence the cre-
ation of such layers. The fact that the effect of scaling may
go unnoticed for long periods of time makes it difficult to
predict its formation and growth. Scaling in aluminium
production industry appears in the form of an amorphous
“hard grey scale” (HGS) which forms in high attrition areas
D.P. Clos et al.
Fig. 4 Samples of hard grey scale
such as dry scrubbers and some transport pipes. Its accu-
mulation reduces gas removal efficiency, hinders alumina
transport causing clogging in some extreme cases and
reduces filters life among other issues.
In 2008 Dando and Lindsay [24] presented a study aimed
to define the chemistry and formation mechanism of HGS.
Samples of HGS were collected from numerous Alcoa
smelters worldwide and some pictures were presented which
can be seen in Fig. 4. Chemical composition of HGS was
studied by means of X-Ray diffraction whereas synthesis
mechanisms were investigated by successfully synthesizing
HGS from smelting materials in a laboratory. A key mech-
anism for HGS formation seems to be the creation of alu-
mina high-energy surface induced by inter-particle
collisions, which upon rapid and exothermic reaction with
water creates local elevated temperatures that induce further
reactions with alumina fines and bath superfines.
Results based on elemental composition showed that
alumina, sodium and fluoride accounted for over 90% of the
total mass of hard grey scale, which suggested that scrubber
scale is formed principally from alumina and bath fines
together with minor contributions from adsorbed fluoride
and bath fumes (NaAlF4).
Another study from 2013 [25] which investigated trace
element concentration from pot exhaust and from depositions
in fume treatment facilities agreed in the following result
reported by the work on hard grey scale presented by Dando
and Lindsay [24]. Both studies pointed out that the compo-
sition of particulate solids collected at the inlet of an injector
scrubber shows similar chemical composition than the hard
grey scale which deposits in scrubbers, despite the higher
degree of crystallinity and higher carbon and sulphur content.
In this study, a cyclone was used to sample particles that
were analyzed by mass spectroscopy (HD ICP-MS). It was
observed that impurities concentration increased in the
coarse fraction of the samples (>1 µm). It was also con-
cluded that soluble glass forming elements in the raw gas
such as Na, K, Si and loosely bound surface water of the
alumina are key ingredients for the formation of an
Enabling Efficient Heat Recovery from Aluminium Pot Gas
amorphous binder matrix as scale forming elements settle
and moisture condensates at designated areas in the fume
treatment facilities.
A follow-up study presented by the same authors in 2014
[26] further compared chemical composition and crystalline
structure of pot exhaust particles and scale samples collected
from the gas treatment centre of the same aluminium smel-
ter. Samples were analysed by means of different X-ray and
mass spectroscopy techniques (XRF, XPS, XRD, ICP-MS)
as well as IR spectroscopy. A new mechanism for recrys-
tallization of sodium fluoro-aluminates due to HF adsorption
reactions in combination with moisture was suggested.
Available Commercial Solutions
This section presents commercial concepts that have been
already built with the aim of actively cooling down the
aluminium pot gas by the use of fouling-resistance enhanced
heat exchangers.
Alstom Funnel Heat Exchanger Design
A patent was developed by Alstom in 2011 [27] with the
objective of reducing fan power requirement to drive flue gas
through the cleaning system. It is based in a branched system
of ducts drawing pot gas from individual electrolytic cells
that merges in a common duct. The system was designed to
accelerate the gas flow right before the merging so gas
velocity from individual branches is larger than the gas
velocity from the main duct.
The idea is that individual regulatory flaps placed at the end
of each individual branch may replace dampers that are used to
regulate pressure drop across duct transporting gas from all
cells. Thus, a distributed and more efficient control of flow
conditions in each individual electrolytic cell may be achieved.
Moreover, individual heat exchangers are placed at every
individual branch right before the merging with the main
duct. Funnel shaped inlet channels will cause gas accelera-
tion which besides aiding pressure drop regulation as men-
tioned before, will enhance heat recovery due to larger heat
transfer caused by higher turbulent regime and lower particle
deposition rate.
Advanced Fume Treatment with Waste Heat
Recovery: Alstom
Alstom also developed a fume treatment method [28] with
heat recovery by circulating cooling water during the
789
scrubbing with alumina. The company claimed higher effi-
ciency in pollutant capture with lower emissions of HF and
tars including PAHs. The system does not increase humidity,
which significantly reduces corrosion, tar deposits and filter
bag hydrolysis.
A Method and Equipment for Heat Recovery:
Patent Hydro-NTNU
A prototype for heat recovery from flue gas was presented in
a patent in 2013 [29]. Flue gas from aluminium industry was
used in experiments conducted to find optimum gas veloc-
ities to minimize particle deposition and pressure. Heat
exchanger design consisted of circular or elliptical tubes and
rectangular fins.
Gas and tube wall temperatures in the experiments were
set around 130 and 70 °C respectively. Results showed that
stabilization of heat transfer due to fouling was achieved
between 50 and 500 h of operation. Gas velocities at
acceptable output conditions were found to be 12 m/s or
higher.
Results with such prototypes were also presented in a
conference in 2013 [30]. A large (129 m2) and small
(12 m2) were installed and tested in a Hydro test facility in
Årdal. Heat duty, gas side pressure drop and particle
concentration in the gas were monitored during 9500 h
tests. Results showed little fouling at the upstream side of
the heat exchanger and only moderate on the downstream
side where dust had formed a small wing-shaped profile
behind the tube. A thin layer of scale and small amounts of
debris were also found in the upstream side of the heat
exchanger.
Fives Solios Heat Exchanger Prototypes Installed
in Årdal (Hydro)
Two Heat exchanger prototypes following the lab-scale
concepts described above were installed in the Norsk Hydro
aluminium plant in Øvre Årdal with operational results
presented in 2014 [31]. Decrease of heat transfer coefficient
over time due to fouling was around 10%, lower than the
theoretical predictions. Pressure drop increased by 33% in an
asymptotic manner and the authors recommend occasional
cleaning of the heat exchanger with compressed air. The heat
exchanger has a segmented configuration that allows
switching of the different parts by clean ones while cleaning
procedures are applied. Future work was planned to test the
heat exchangers in more severe conditions, i.e. on wet and
hot exhaust pot gas in Gulf countries smelters.
790
Cold Finger Design and Planned Ph.D.
Activities
The present review has shown that quite some effort has
been spent in characterizing the complex mixture of gas and
particulate matter generated by the electrochemical alu-
minium production cells. There are still many uncertainties
regarding mechanisms for scale formation and growth. The
influence of different operational conditions on scaling is not
well understood and that makes this phenomenon difficult to
predict. Future process modifications such as the distributed
pot suction (DPS) will offer increased potential for heat
recovery from aluminium pot gas at higher temperatures but
at the same will present challenges when dealing with higher
dust and hazardous gas concentrations.
In order to advance in the understanding of the scaling
phenomenon under the current and future conditions a
cold-finger will be built with the following objectives in mind:
• Reproduce heat exchanger conditions in terms of tube
size and geometry, gas velocity and temperature
• Equipped with sensors in order to monitor heat transfer,
gas velocity and dew point among others
• Collect scale deposits for further analysis
• Obtain relevant experimental data for CFD models
validation.
As mentioned in Sect. 3.1 an Eulerian-Eulerian approach
will be initially used for the modelling of the test section.
Upgrading of the current boundary models from 1 to 2
dimensions will be necessary to assess deposition rates for
flow directed towards the wall as opposed to the parallel
flow described so far. This model will then be coupled with a
CFD coarse grid model of the test section by using function
calls. In this manner, different particle sizes will be com-
puted in parallel calls producing an overall deposition rate
that will be compared with the experimental results.
Particle size distributions from previous studies will be
used as inputs for the model although new measurements in
the same experimental site would be desirable and hence will
be pursued during the planning phase of the project.
Lagrangian methods for particle transport and deposition
might be considered in a later stage of the Ph.D. in order to
locally predict the formation of scale deposits with a
mechanistic model. Characterization of scale samples at
different timeframes will be carried out to get a better
understanding of the composition of the primary scale layers
and their evolution over time. Laboratory experiments using
“lab-smelters” which can reproduce industrial off-gas con-
ditions under controlled and known particle/gas composi-
tions will be used to investigate under which conditions
scale forms and to correlate those results with those obtained
from industrial sample analysis.
D.P. Clos et al.
Velocity profiles in the test section are also an important
input required for the models. Measurement of duct veloci-
ties by means of a Pitot tube will be performed in the same
hatch for gas extraction prior to the measurements. This is
important in order to choose a suitable nozzle diameter for
isokinetic extraction of the off-gas [20]. A fan or an ejector
will be placed downstream of the test section in order to
regulate the volumetric flow and thus assess the effect of
different gas velocities in the deposition profile and
composition.
The cold-finger will be designed in a tube in tube con-
figuration with two tubes staggered in two discs at both ends
of the tubes, which can be clamped at the walls of the test
section. Tubes clearance between themselves and the walls
will be fixed around 1 cm making the flow conditions rel-
evant for flow across a tube row. There are currently two
possible working fluids under consideration. On one hand
the use of pressurized air offers a safe and cheap choice
which has been used in previous industrial tests [17, 19]. On
the other hand the possibility of using pressurized CO2 will
also be assessed as this fluid could be potentially used in a
supercritical power cycle system for power production in the
future. The use of water is strictly forbidden in the potroom
but could be considered as well if the experiments were to be
performed in the large joining ducts in front of the dry
scrubber in the outer courtyard zone.
Measurement campaigns will be designed in order to
study short-term and long-term exposure effects on surface
fouling. The effect of distribution pot suction (DPS) will also
be investigated by performing experiments in the DPS test
cells available in the Hydro aluminium plant in Årdal.
Conclusions
Mitigation of fouling is desired in many industrial processes
as it supposes a great cost in terms of units degradation and
maintenance-induced downtimes. Research efforts on the
topic from the Norwegian aluminium companies, providers
and research centres have been reviewed with the purpose of
designing future work ahead.
In aluminium industry, fouling is caused by particle
deposition in low velocity regions and by scale formation in
high attrition areas. Both phenomena have been observed in
previous experimental studies trying to emulate heat
exchanger conditions. The mechanisms behind scale for-
mation are still not well understood, however fouling miti-
gation is key in designing novel efficient heat exchangers.
Some commercial heat exchangers exist with the aim of
cooling down the gas before the filters. However, those
concepts are not efficient enough from the perspective of
further heat utilization (especially for power production). In
conclusion, future efficient heat exchanger designs will
Enabling Efficient Heat Recovery from Aluminium Pot Gas
require better understanding of fouling and scaling formation
in order to find geometrical and operational conditions that
can minimize its detrimental effects. In this regard, the plans
for a future Ph.D. candidate within the SFI metal production
project have been described which include the design of a
cold-finger rig for industrial measurements and theoretical
modelling of the fouling effect using computational fluid
dynamics based models.
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 The Successful Implementation of AP40
Technology at Kitimat

Patrice Desrosiers, Martin Robitaille, Pierre Luc Voyer, Silvino Caetano,

René Gariepy, Olivier Martin, and Pascal Robert

Abstract
Positioned in British Columbia on the west coast of Canada, Kitimat smelter is in operation
for more than 60 years. A new era has started with the modernization of the smelter using
the AP40 smelting technology. AP40 technology has already been successfully used in the
Alma (Canada) smelter enabling operation above 400 kA. The new Kitimat potline, with its
384 pots, started production mid-2015 and reached full capacity in March 2016. The robust
start-up has been successfully concluded with a performance test achieving 96.1% Current
Efficiency and 12,800 kWh/t of Specific Energy Consumption. Thanks to new AP40
potline, the Kitimat production increases by about 48% to 420,000 tons annually while the
smelter’s overall emissions have been halved. Kitimat smelter is now one of the most
efficient, greenest and lowest-cost in the world.

Keywords
AP40 Plant start-up Technology package

Introduction Designed initially to operate at 280 kA, these cells rapidly

Initiated in a dedicated boosted section at the St Jean de
Maurienne smelter, the development of the AP30 technology
has not ceased to push the limits of pot productivity and
energy consumption since the beginning of the eighties. The
first AP30 potline was built in St Jean de Maurienne with
one hundred and twenty pots and was considered at that time
to be the most advanced technology in operation (Fig. 1).
P. Desrosiers (&)
M. Robitaille
R. Gariepy
ARDC, Rio Tinto Aluminium, 1955 Mellon Boulevard,
C.P. 1250 Jonquière (Québec), G7S 4K8, Canada
e-mail: patrice.desrosiers@riotinto.com
P.L. Voyer
Kitimat, Rio Tinto Aluminium, 1, Smeltersite Road,
PO Box 1800 Kitimat (British Columbia), V8C 2H2, Canada
S. Caetano
P. Robert
Aluminium Pechiney, Rio Tinto Aluminium, 725 Rue Aristide
Berges, BP 738341 Voreppe Cedex, France
O. Martin
LRF, Rio Tinto Aluminium, BP 114-73303
Saint-Jean-de-Maurienne Cedex, France
demonstrated their robustness and capacity for increased
productivity, with amperage reaching more than 300 kA by
the beginning of 1990 [1].
In order to enhance and accelerate this very promising
development, and aiming at cell designs still more efficient
for limited capital cost, a complete R&D program was
launched in 1990 based on trials in boosted sections in
several plants. A first trial section was installed in the brand
new Dunkerque smelter in 1991, followed by another one in
St Jean de Maurienne in 1996 and a third one in Alma in
2004 [2–4]. These test sections were then able to contribute
in an integrated way to the development of the AP30 tech-
nology in line with internal or external customer requests.
Combined to support a very aggressive vision of the AP30
technology, this R&D work was the starting point of a
development that has pushed the operating point from the
initial 300 kA to more than 440 kA today [5]. In parallel, the
number of AP30 type pots installed in the world has
increased steadily, reaching 6378 cells in 2016, which cor-
responds to about 12% of the world’s annual aluminium
production (see Fig. 2).

© The Minerals, Metals & Materials Society 2017 793

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_96
794 P. Desrosiers et al.

Fig. 1 AP30 in operation in G Line at Saint-Jean-de-Maurienne

Fig. 2 AP30 technology around the world

Table 1 Operating points of the latest AP3X–AP40 development

Version Location and period Goals
AP36 Saint Jean de Maurienne -Dunkirk 360 kA
2005–2007 13,100–13,500 kWh/t
AP37 Alma 370 kA
2006–2008 13,150–13,500 kWh/t
AP40 Saint Jean de Maurienne 405 kA
2009–2011 13,000–13,400 kWh/t
AP44 Dunkirk-Alma 440 kA
2014–2016 13,000–13,400 kWh/t
AP40 Technology development site
The Successful Implementation of AP40 Technology at Kitimat
By developing successive improved version (see
Table 1), Smelters from Rio Tinto or licences are able to
increase dramatically their production with reduced level of
Capex [6, 7].
For example Alma smelter started at 320 kA in 2000, has
reached 405 kA in 2015 by using AP40 cell technology.
Alma trial section now to operate at 440 kA by using the
new AP44 cell technology under development [8].
Kitimat Site
Located in Northern British-Columbia, in Canada, the Kitimat
River Valley is oriented approximately north-south from the
mouth at Kitimat Arm of Douglas Channel to about 30 km
inland. At this location, the valley alignment swings north-
east. The District of Kitimat is nestled at the end of the
Douglas Channel, a wide and sheltered fjord along the
Alaska-Vancouver ‘Inside Passage’. The Alcan Kitimat
Works Aluminum Smelter is Kitimat’s founding industry.
Between 1950 and 1954, the town of Kitimat, the smelter,
Kenny Dam in the Nechako River Canyon, and the Kemano
Power House were initially developed. The population of
8500 people was involved primarily with the Rio-Tinto
Aluminium Smelter, the Eurocan Pulp and Paper Mill (now
closed) and the sports fishing industry. The word Kitimat is
derived from the Haisla word Kitamaat, which means
“People of the Snow”. Kitimat is a small town which
occupies a strategic tidewater location on the great circle
shipping route, thus providing a link to Pacific shipping
lanes for over 60 years. Kitimat is serviced by deep-sea ship,
rail, as well as by road transportation.
The Kitimat smelter was started in 1954. The first 2
potlines (lines 1–2) were built with Electrokemisk VSS
technology. Later, in 1956 and in 1968, Potlines 3–5 and
7–8 were started with Pechiney Sumitomo VSS technology.
The plant had a total of 6 potlines (914 pots) for a nameplate
capacity of 277 ktm/year. A picture of the old smelter is
shown at Fig. 3.
Kitimat produce and use his own hydro-electricity by the
Kemano powerhouse and watershed. The plant is also
equipped with a deep sea wharf for raw material import
(alumina, coke and petroleum pitch) and for product export.
The wharf is equipped with 9 12,000 mt silo for alumina
storage. The facility also has a coke calciner for anode paste
production.
The modernization project evolved to build a new AP-40
potline on the footprint of the old smelter. So, in 2010, the
lines 7–8 were shut down in order to be dismantled. The
project required also to modernize the anode paste plant
(from Soderberg briquette to AP-40 pre-bake anode), and the
wharf by adding a calcined coke unloader and a new cal-
cined coke silo. Also, 4 of the 9 alumina silos were
795
Fig. 3 Kitimat smelter before modernization
refurbished to minimize the dead storage and the main alu-
mina conveyor was refurbished as well to transport the
alumina from the wharf to the new intermediate silo.
Other major facilities constructions were included in the
scope of the project:
• Anode baking Furnace
• Anode rodding shop
• Anode pallet storage building
• Small ingot casting center
• Intermediate 20,000 mt alumina silo
• Fluoride silo
• Alumina transportation system from the intermediate silo
to the potrooms
• Gas treatment centers (2)
• Substation
The new smelter is design in a unique potline of 384
AP-40 pots controlled by the ALPSYS® System. The potline
is divided in 4 building of 96 pots each.
The line is equipped with an optimized MHD compen-
sation loop. The substation is equipped with 5 105 kA
Rectifier and 2 units for the Compensation loop. The
reduction department is equipped with 10 pot tending
assemblies (PTA) and 2 tapping and miscellaneous assem-
blies (TMA). To reduce the cost of the project, the ALP-
SYS® Dual Potmicro were installed in the small aisle of the
potroom, and the operators can have access to it by WIFI
with a new handy portable Human-Machine Interface
(Fig. 4). This device allows the operator, after a scan of a pot
specific code number to operate and interrogate the dual pot
micro from the wide aisle and to get access to some feature
of the Level II system, like the pot graph viewing.
796 P. Desrosiers et al.

Fig. 5 Kitimat modernized smelter (KMP)

4096 3096 2096 1096

Fig. 4 Portable human-machine interface

Kitimat was in a special configuration were they have to

control the Kemano reservoir level and at the same time
optimizing the energy consumption of the plant in order to
meet the energy export contract with BC Hydro. To achieve
this, the planning of the Soderberg lines shutdown had to be
synchronized with the ramp-up of KMP. The decision to
shut down a line was dictated by the reservoir status and the
manpower needs to ramp-up the new plant.
This kind of challenge was affecting the paste plant as well
where we had to change from VSS paste briquette production 4049 3049 2049 1049
to green AP-40 anode blocks. The management of the raw Crossover Crossover
material was critical in order to get enough material to
operate the VSS lines to the end and the requirement of the
construction and the commissioning-start-up phase. A pic-
ture of the modernized smelter is presented at Fig. 5.

Start-up

Prior to the start-up, a short circuiting test was performed on

the potroom in order to measure and validate the design of
the busbar system and its components, including the MHD
compensation loop. This short-circuiting test was also an
occasion to test the operation of the substation in different 4001 3001 2001 1001
modes. At this stage, the short-circuiting wedges were
installed in the first section of pots and the different by-pass
Switch
bridges were installed as shown in Fig. 6. This was the
configuration used for the first stage of the start-up.
The first pot was started on June 22nd 2015. The start-up
rate was 1 pot per day for the first 8 pots and 2 pots/day Fig. 6 Potline configuration for the short-circuiting test and Phase I of
after. At some point because of a pause taken the start-up the start-up
The Successful Implementation of AP40 Technology at Kitimat 797

Fig. 7 Kitimat start-up rate

rate was raised to 3 pots/day. Figure 7 shows the start-up

rhythm of Kitimat.
4096 3096 2096 1096
The strategy adopted was to energize the pots in the same
building on a given day and alternate on the second building
the next day. With a pot preheating around 48 h, the ener-
gizing operation was done in the same building than the
start-up operation. This way, we were minimizing the
number of PTA needed for the start-up operation, because in
the second room no extra-PTA was needed. In the second
room only preheating monitoring activities, metal addition,
pot de-dusting and the final cover were planned. Those
activities were done with the PTA assigned on normal
operation in the section.
During the start-up, some pauses were taken for different
reasons and for different times. Some were planned and 4049 3049 2049 1049
others were related to the capacity of the plant to sustain the Crossover Crossover
start-up rhythm.
A planned pause was done for a week after 8 pots started
to evaluate the start-up procedure. Other planed pauses were
taken at other stage of the startup like the removal of the
temporary bridges and switch: August 2015 to energize the
north side of buildings 1000 and 2000 (Fig. 8); October
2015 to energize the south side of buildings 3000–4000
(Fig. 9) and December 2015 to energize the north side of
those building (Fig. 10). The other planned pause was taken
after 48 pots (24 on each side) to evaluate the different
material flow in the plant.
Other pauses had to be taken because of work delay in the
potroom and to give some time to the operation to get some 4001 3001 2001 1001
speed in regard of the workload that was increasing rapidly
(at 72 and 96 pots). But the biggest pause was taken after pot Switch
216 because the productivity of the anode rodding shop was
not sufficient enough to sustain the start-up rate (including
the requirement of the pot preparation). At this point, a
“Go-No Go” gate was done by the plant management on a Fig. 8 Potline configuration after disconnection of the first crossover
798 P. Desrosiers et al.

4096 3096 2096 1096 4096 3096 2096 1096

4049 3049 2049 1049 4049 3049 2049 1049

Crossover Crossover Crossover Crossover

4001 3001 2001 1001 4001 3001 2001 1001

Switch Switch

Fig. 9 Potline configuration after opening of the switch Fig. 10 Potline configuration after disconnection of the last crossover

weekly basis and the resume of the start-up was performed at
a slower pace for the next 3 weeks.
Including all the pauses the Kitimat start-up rate was
close to an average of 10 pots/weeks. The cathode current
distribution performed on all the pots showed only one cut
cathode bar which may be a sign of metal infiltration.
Overall, the potline start-up was considered a real success.
Performance Test and Results
After the start-up was completed, a performance test was
realized on a section of 24 pots in order to validate the tech-
nology package. The chosen section was pots 2073–2096,
mainly because of the pot age and the cathode block type
distribution. The test was carried out from April 20 to May 21
2016.
For this test, a process expert from the AP Technology™
team was assigned on each shift to get a 24 h/7 day cover-
age. His role was to follow the operation in order to access
the conformance of the work in regards of the best practices,
to follow the different measures and to make sure to gather
all the data, including the metal conciliation.
Dedicated metal cruces, bath cruces and bath sows were
identified to make sure all the metal was conciliated. The
major process results of the performance test are shown in
the Table 2.
Since the end of the start-up, the plant performance
continues to improve. The biggest contributor of this
improvement is the reduction of work delays. After only
3 months in full operation work delays were minimized and
the process parameters were fine-tuned. With this stabiliza-
tion phase, Kitimat operates in September 2016 at 409 kA
without major impacts. This confirmed the modeling results
The Successful Implementation of AP40 Technology at Kitimat 799

Table 2 Performance test KPI Results Expected

overall results for pots 2073–2096
Target amperage (kA) 405 405
Current efficiency (%) 96.1 93
Energy consumption (kWh/tm) 12,806 13,150
Daily metal production (kg/pot/day) 3118 3033

Table 3 Plant result for May– KPI Results (average 4 months)

August 2016
Amperage (kA) 404.6
Current efficiency (%) 94.6
Energy consumption (kWh/tm) 13,095
Daily metal production (kg/pot/day) 3079
Net carbon consumption (kg C/tm Al) 410.8
Anode effect frequency (EA/pot/day) 0.19
Iron content (%) 0.0723

showing the potential of the pot design. Table 3 presents the
major results from May to August (included) for the plant.
The principal challenges of the plant since the start-up are
the number of power outages. This problem affected the
plant results during that period, mainly the amperage (target
at 405 kA and more) and the anode effect frequency (aver-
age at 0.10 EA/pot/day without the power outages).
Also, despite of 3 months of start-up at the beginning of
2016 and a stabilization phase, the total fluoride emissions
reported for the period of January to June was 0.43 kg/tm Al,
which is a very good result.
Conclusion
Thanks to the AP Technology™ development, Kitimat
smelter was modernized from vertical studs Soderberg
technology to the state of the art AP-40. The production of
the smelter increased from 270 to 420 kmt/year.
The challenge to stop the Soderberg pot lines and to start the
new AP40 Potline was a great success. The performance test
realized at the plan showed the real potential of the pots with a
cell design robust enough for future production creeping.
References
1. B. Langon, P. Varin, Aluminium pechiney 280 kA pots, in Light
Metals (1986), pp. 343–347
2. C. Vanvoren, P. Homsi, B. Feve, B. Molinier, Y. Di Giovanni,
AP35: The latest high performance industrially available new cell
technology, in Light Metals (2001), pp. 207–212
3. O. Martin, J.M. Jolas, B. Benkahla, O. Rebouillat, C. Richard, C.
Ritter, The next step to the AP3X-Hale technology, in Light Metals
(2006), pp. 249–254
4. O. Martin, B. Benkahla, T. Tomasino, S. Fardeau, C. Richard, I.
Hugron, The latest developments of Alcan’s AP3X and ALPSYS®
technologies, in Light Metals (2007), pp. 253–258
5. O.Martin, L. Fiot, C. Ritter, R. Santerre, H. Vermette, AP30 toward
400 kA, in Light Metals (2009), pp. 445–450
6. P. Coursol et al., Impact of operations at low anode-cathode
distance on energy consumption and greenhouse gas emissions at
aluminerie alouette, in JOM, August (2011), pp. 109–115
7. S. Fardeau et al., Continuous improvement in aluminium reduction
cell process performance using the ALPSYS control system, in
Light Metals (2010), pp. 495–500
8. P. Thibeault, H. Mézin, O. Martin, Rio Tinto AP44 cell technology
development at alma smelter, in Light Metals (2016), pp. 295–300
 Part XIX
Cast Shop Technology:
Continuous Strip Casting
 Effect of Grain Refiners on Aluminum Twin Roll
Casting Process

Yu Matsui and Koichi Takahashi

Abstract
The purpose of this study is to investigate the effect of adding the Al–Ti–B grain refiner to
the aluminum twin roll casting. The authors analyzed the microstructure of the as-cast strip
produced by the twin roll casting based on several casting conditions. The results showed
that the amount of the TiB2 particles and the temperature gradient in the solidification area
are the key factors for enhancing the effect of the grain refining. Additionally, this study
simulated the behavior of the TiB2 particles in the aluminum melt. The temperature
distribution of the aluminum between the twin rolls was also calculated. The authors
clarified the relationship between the grain refiner particles and the temperature gradient for
the grain refining effect during the twin roll casting.

Keywords
Twin roll casting Strip casting Grain refining Cooling rate

Introduction [3]. However, the study for determining the behavior of

Twin roll casting (TRC) is the one of the casting methods for
aluminum sheets. This process can provide thin strips
directly from molten metal so that it requires no scalping and
hot-rolling which are required for direct chill (DC) casting
and has been accepted worldwide as a cost-effective method
for the past half-century [1]. In the TRC process, it is well
known that grain refinement is less effective than in the DC
casting. Two reasons are presumed for this effect. One of the
reasons is the high cooling rate, but this effect is poorly
understood, although several mechanisms have been sug-
gested [2]. Another one is the low metal flow rate. TRC’s
production rate is much lower than that of the DC casting so
that the metal flow rate is also very low and the TiB2 par-
ticles, which play a role for the heterogeneous nucleation
sites, settle in the metal during casting. A fluid flow analysis
has been done for optimizing the metal feeding uniformity
Y. Matsui (&)
K. Takahashi
Research and Development Division, UACJ Corporation, 3-1-12,
Chitose, Minato-ku, Nagoya, 455-8670, Japan
e-mail: matsui-yu@uacj.co.jp
particles has not been sufficiently examined.
For the mass production of a thin strip, it is necessary to
directly determine the effect of grain refiners on the TRC.
The purpose of this study is to clarify the factors for the
grain refining during the TRC.
Preliminary Experiment
Experimental Procedure
This study was conducted on cast strips of the 1050 alloy
(Al–Fe–Si) cast at 710 °C before the casting machine. The
chemical composition of the metal before adding the grain
refiners is listed in Table 1. A pilot caster (Fig. 1), which is
capable of casting 6-mm thick and 300-mm wide strips, was
employed to produce 500-mm length strips. The strips were
cast at three different grain refining conditions, namely,
no-added and Al–5Ti–1B, and two different casting speeds,
namely, 0.62 and 0.68 m/min. The grain refining conditions
are listed in Table 2.

© The Minerals, Metals & Materials Society 2017 803

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_97
804 Y. Matsui and K. Takahashi

Table 1 Chemical compositions Al Si Fe Cu Mn Mg Zn Cr Ti B V

of 1050 alloys (wt%)
Rem. 0.05 0.25 0.001 0.001 0.001 0.002 0.001 0.015 <0.001 0.014

Fig. 1 Pilot caster

Melting furnace
Metal head level Cooling roll
(dia.400mm)
Trough

Spout
Float

Tundish

Table 2 Experimental condition Grain refining condition Casting speed (m/min)

Grain refiner Addition rate (ppm Ti)
A1 – – 0.62
A2 0.68
B1 Al–5Ti–1B rod 30 0.62
B2 0.68
C1 130 0.62
C2 0.68

Results and Discussion TL  TS ½ C

The macrostructures of the longitudinal cross section of the
as-cast strips are shown in Fig. 2. Without adding a grain
refiner (A1, A2), feather crystals were observed at the two
different casting speeds and their observed areas were wider
in A1 than A2. With the sufficient Al–5Ti–1B rod, the whole
area was covered with very fine and equiaxed grains
regardless of the casting speed. The center of the strips,
however, was not refined and feather crystals were slightly
observed at the low addition rate. This result indicates that
feather crystals grow in the low Ti melt and at a low casting
speed.
It is presumed that giant grains, for example feather
crystals, tend to be formed when aluminum solidifies at a
high cooling rate, high temperature gradient and no distur-
bance of the metal flow [4]. The cooling rate is equal to the
product of the temperature gradient and
solidification-interface speed. Their relation is described as:
Cv ½ C=s ¼ G ½ C=mm  V ½mm=s
G ½ C=mm ¼ ð2Þ
l ½mm
where Cv is the cooling rate, G is the temperature gradient,
V is the solidification-interface speed, TL is the liquidus
temperature, TS is the solidus temperature, and l is the mushy
zone length.
Compared to the DC casting, the temperature gradient is
bigger in the TRC because the mushy zone length in the
TRC is shorter than that in the DC casting. The
solidification-interface speed, which is equal to casting speed
in the center of the strip thickness in the TRC, is then faster
than it in the DC casting. Moreover, the melt is more stable
than in the DC casting because the mushy zone length in the
TRC is shorter and the metal flow rate is lower than in the
DC casting. For these reasons, the TRC is the casting
method in which giant crystals easily occur.
The reason why the grains of B1, B2, C1 and C2 were
finer than those of A1 and A2 is that TiB2 particles in the
grain refiner rods played a sufficient role as heterogeneous
ð1Þ nuclei added to the melt of B1, B2, C1 and C2.
Effect of Grain Refiners on Aluminum Twin Roll Casting Process 805

Fig. 2 Macrostructure of
longitudinal cross section of the No-adding 30ppmTi 130ppmTi
as-cast strips cast at six different
conditions (A1) (B1) (C1)

0.62m/min

feather crystal
(A2) (B2) (C2)

0.68m/min

Casting direction

1mm

Nonhomogeneous nucleation in the molten metal occurs by
heterogeneous nuclei as the trigger. The number of TiB2
particles in C1 and C2 is about 4.3 times greater than in B1
and B2 such that the C1 and C2’s structure is finer than the
B1 and B2’s.
The solidification between the twin rolls is shown in
Fig. 3. We define the “solidification-interface” as the solidus
temperature line in this paper. When the casting speed
increased, the solidification-interface moves toward the roll
center line and the liquidus temperature line does not move
very much as the solidification-interface. The mushy zone
length then becomes longer than in the case of the low
casting speed. It seems that the solidification-interface speed
becomes faster, but the temperature gradient becomes
smaller. Therefore, the solidification structure changes from
anisotropy to equiaxed grains [5].

Fig. 3 Solidification between

Liquidus temperature Solidus temperature
twin rolls
(=Solidification-interface)

Casting tip Upper roll

Molten metal Strip

Bottom roll
Roll center line
806 Y. Matsui and K. Takahashi

To clarify if the mushy zone becomes wider by increasing To confirm this idea, we determined if the high casting
the casting speed, a calculation was carried out using the speed lowers the cooling rate and decrease the grain size.
thermal equation (Fig. 4).
The calculation indicates that the temperature gradient
and cooling rate monotonically decrease by increasing the Verification Experiment
casting speed. On the other hand, the measurement of the
dendrite cell size (DCS) has been done. It is known that Experimental Procedure
the dendrite cell size or the second dendrite arm spacing
(DAS) is in inverse proportion to the cooling rate [6]. The The verification experiment was conducted using cast strips
measurement proved that the cooling rate decreased by of the 1050 alloy (Al–Fe–Si) cast at 700 °C before the
increasing the casting speed in the range of the preliminary casting machine. The chemical composition of the metal
experiment. The measurement results then agree with the before adding the grain refiners is given in Table 3. A mass
above calculation result. production casting machine (Fig. 5), which is capable of
The preliminary experiment leads to the following casting 6-mm thick and 1500-mm wide strips, was employed
hypothesis: to produce 1000-mm length strips. The experimental con-
“A high speed casting makes grain refiners more effective ditions are given in Table 4. Strips were cast at four different
because the cooling rate decreases”. casting speeds, namely, 0.85, 0.95, 1.0, and 1.1 m/min.

Fig. 4 DCS measurement and

Dendrite cell size, μm

the casting parameters calculated 8.0

by thermal equation of the No-added
preliminary experiment
7.0 30ppmTi
130ppmTi
6.0

5.0
28 200

24 180
Solidification-interface speed, mm/s

160
Temperature gradient, C /mm

20
o

Cooling rate, C /s
140

o
16
120
12
100
8
80
Solidification-interface speed
4 60
Temperature gradient
Cooling rate (pilot caster)
0 40
0.45 0.55 0.65 0.75 0.85
Casting speed, m/min
Effect of Grain Refiners on Aluminum Twin Roll Casting Process 807

Table 3 Chemical compositions Al Si Fe Cu Mn Mg Zn Cr Ti B V

of 1050 alloys (wt%)
Rem. 0.12 0.27 <0.001 0.002 0.001 0.004 0.001 <0.01 <0.001 0.014

Grain refiner
Casting machine
Head box (Roll dia:650mm)

Melting furnace

Holding Rewinder
furnace
Degasser Filter

Fig. 5 Mass production casting line

Table 4 Experimental Grain refining condition Casting speed (m/min)

conditions
Grain refiner Rod speed (mm/min)
a Al–5Ti–1B rod rod 220 0.85
b 0.95
c 1.00
d 1.10

Fig. 6 Macrostructure of lateral

cross section of the as-cast strips Casting speed
cast at four casting speeds
0.85m/min 0.95m/min 1.0m/min 1.1m/min

(a) (b) (c) (d)

1mm
808 Y. Matsui and K. Takahashi

75 0.027 observed in the center of the strip (a). At the other casting
Grain size conditions at and above 0.95 m/min, the columnar crystals
70 0.025
Ti (headbox) disappeared and fine equiaxed crystals were observed in the
Ti (adding amount)
whole area (b, c, d).
Grain size,μm

65 0.023

Ti, wt%
The measurements of the grain size and Ti amount are
60 0.021
shown in Fig. 7. The best refined strip was cast at
0.95 m/min. The grain size becomes smaller in association
55 0.019
with the decreasing Ti amount, except at 0.85 m/min.
Though columnar crystals exist in the casting at 0.85 m/min,
50 0.017 the Ti amount is higher than 1.0 m/min. Hence, the reason
0.8 0.9 1.0 1.1 why the strip cast at 0.85 m/min was not refined is not fewer
Casting speed, m/min TiB2 particles, but an insufficient solidification condition.
The temperature gradient and the cooling rate were cal-
Fig. 7 Grain size and Ti amount versus casting speed
culated by the same thermal calculation used in the prelim-
The Ti composition and grain size of each strip were mea- inary experiment. The dendrite cell sizes were also measured
sured by an OES analysis and grain counting method. by the same method as in the preliminary experiment. The
measurement result is compatible with this calculation result
(Fig. 8).
Results and Discussion In the verification experiment, the temperature gradient
monotonically decreases when the casting speed increases
The macrostructures of the as-cast strips are shown in Fig. 6. the same as in the preliminary experiment. The cooling rate
When casting at 0.85 m/min, columnar crystals were does not monotonically decrease with the increasing casting

Fig. 8 DCS measurement and 8.0

Dendrite cell size, μm

the casting parameters calculated

by thermal equation of the Columnar grain
verification experiment 7.0

6.0

5.0
28 300

24 280
Solidification-interface speed, mm/s

260
Temperature gradient, C /mm

20
Cooling rate, Co/s
o

240
16
220
12
200
8
180
Solidification-nterface speed
4 Temperature gradient 160
Cooling rate (Mass production caster)
0 140
0.8 0.9 1 1.1
Casting speed, m/min
Effect of Grain Refiners on Aluminum Twin Roll Casting Process 809

speed. Therefore, if the temperature gradient is reduced, it is

easy to obtain a fine structure for strip casting whether the Distributor

cooling rate is high or low.

Casting tip

The Points of Grain Refining in the TRC

2.4m
As has been noted, we need to take care of the following
Headbox
points to make the area of the strip fine; Trough

1. An adequate amount of heterogeneous nuclei (for

example, TiB2 particles) which are obtained by adding TiB2 added position
grain refiners to the molten metal.
2. Low temperature gradient which is achievable by
Fig. 9 Calculated model of metal flow path
increasing the casting speed.

The Behavior of the TiB2 Particles
Figure 7 indicates that the TiB2 particles settle as sediment
during the casting. At each casting speed, the actual Ti
values are less than the theoretical values. The added yield at
0.85 m/min is 83.7% and it is the lowest in the four speed
conditions. Therefore, it is presumed that if casting at a low
speed, the amount of the grain refiners increases because of
adding at a uniform rod speed, but the heterogeneous nuclei
tend to settle and not reach the casting machine.
To clarify the behavior of the TiB2 particles, we calcu-
lated the number of particles which reach the casting
machine on the mass production model.
tip. A fluid flow analysis of the molten metal was performed
by employing specifically designed 3-dimensional finite
element software. The calculation condition is given in
Table 5 and the modeled metal flow path is shown in Fig. 9.
Results and Discussion
It was clarified that TiB2 particles collect where the metal is
stagnant, for instance, the corner in the headbox (Fig. 10).
Especially, bigger particles tend to collect.
The TiB2 particles of each size were then divided into
two groups. One is the effective particles which have
reached the casting machine and the other one is the

Numerical Simulation
TiB2 particles
Calculation Procedure 1μm
100μm
The goal of the present study is to analyze the behavior of
the TiB2 particles from the trough to the headbox and the

Table 5 Calculation condition

Fundamental equation Uncompressed Navier-Stokes equation
Turbulence model k-epsilon model
Calculation method Metal flow: steady analysis
Particle transport: transient analysis
Molten Al Density (kg/m3) 2350
Viscosity (Pa s) 0.001
TiB2 particles Density (kg/m3) 4510
Shape Sphere
Diameter (lm) 1, 10, 100
Adding number (parts/s) 100
Fig. 10 TiB2 particles which collect in the headbox
810 Y. Matsui and K. Takahashi

Fig. 11 Total added yield of 100 300

TiB2 particles
99

Number of nuclei, parts/kg-A

260
98

Total added yield, %

97 220
96

95 180
Total added yield
94 Number of nuclei (added to melt) 140
93
Number of nuclei (entering roll gap)
92 100
0.7 0.9 1.1 1.3 1.5 1.7
Casting speed, m/min

non-effective particles which have settled or collected
before the tip outlet. The total added yield of the TiB2
particles, which was calculated by the nucleus number of
the two groups, decreased when the casting speed decreased
(Fig. 11).
Conclusion
The following can be concluded from this investigation:
1. The proper amount of heterogeneous nuclei and low
temperature gradient are required to decrease the grain
size in the TRC.
2. A low temperature gradient is obtained by decreasing the
casting speed.
3. A low casting speed is likely to make the heterogeneous
nuclei settle or collect in the metal flow path.
4. The amount of heterogeneous nuclei, temperature
gradient and metal flow path should be optimized to
maximize the effect of the grain refiners.
References
1. E. Romano, C. Romanowski, Reinventing twin roll casting for the
21st century. Light Met. 895–900 (2009)
2. S. Ertan et al., The effect of casting parameters on twin roll cast strip
microstructure. Light Met. 667–666 (2000)
3. K. Sarioglu et al., Computer simulation of metal feeding system
used in twin roll casting. Light Met. 663–666 (2000)
4. Y. Murakami et al., (ed.), Basis and Industrial Technology of
Aluminum (in Japanese), (Japan Aluminum Association, 1985),
pp. 46–47
5. W. Kurz, D.J. Fisher, Fundamentals of Solidification, (Trans Tech
Publications, 1984), pp. 88–92
6. H. D. Merchant et al., (ed.), Continuous Casting of Non-Ferrous
Metals and Alloys (TMS, 1988), pp. 1–66
 Influence of Process Conditions
on Segregation Behavior in Twin-Roll
Casting of an AlFeSi-Alloy

Christian W. Schmidt, Dag Mortensen, and Kai-Friedrich Karhausen

Abstract
In twin-roll casting of aluminium the content of alloying elements is limited due to the
formation of segregations mainly at the centerline and the surface of the strip. Their
appearance, size and localization have a major influence on the final product quality.
AlFeSi alloys are well suited for this investigation as they are alloyed with iron far beyond
solubility. In casting experiments, casting speed is altered stepwise while all other casting
parameters are not actively changed. Naturally roll and strip temperatures are increasing
while separation force and strip thickness are reducing when casting speed is increased.
Basically with increased casting speed the liquid and semi-solid sump is growing and
contact time of the strip with the water-cooled roll is reduced. Hence both factors
influencing segregation behavior, namely solidification conditions and deformation of the
sump, are changing during the experiments. Experimental investigation is supported by
process simulation in Alsim.

Keywords
Twin-roll casting Aluminium Segregation AlFeSi

Introduction reached by relatively low casting speeds. The second limit-

Although strip casting technologies like twin-roll casting are
very resource efficient processes, the spectrum of alloys cast
via these technologies as well as the range of products
produced thereof is limited to low alloyed products with
medium surface requirements. The limitation in alloying
content mainly bases on two points. With increasing content
of eutectic forming alloying elements, the solidification
range widens considerably and especially the solidus tem-
perature decreases clearly. This implies that rather low
temperatures have to be achieved in the casting process to
solidify alloyed materials in time and this can only be
C.W. Schmidt (&)
K.-F. Karhausen
Hydro Aluminium Rolled Products, GmbH
Georg-von-Boeselager-Str. 21, 53117 Bonn, Germany
e-mail: christian.werner.schmidt@hydro.com
D. Mortensen
Institute for Energy Technology, P.O. Box 402027 Kjeller,
Norway
ing point are segregations, typically either located in the strip
center, close to the surface or within a central band of strip
gauge. The formation of segregations in twin-roll casting is
based on a rather complex interplay of metallurgical, thermal
and mechanical causes and as a direct experimental obser-
vation of the solidification process is impossible, simulations
are used to support experimental investigation of process
parameter and material properties.
Segregations in Twin-Roll Casting of AlFeSi
Alloys
The origin of segregations in twin-roll casting of AlFeSi
alloys is the directed solidification with high cooling rates in
this process in general as well as the high content of iron in
these alloys in special, which is far beyond maximum sol-
ubility in aluminium and makes them well suited for such an
investigation. Caused by the very high cooling rates, a

© The Minerals, Metals & Materials Society 2017 811

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_98
812
higher concentration of alloying elements remain in solid
solution compared to thermodynamical equilibrium [1].
Nevertheless, when the alloy solidifies, the alloying elements
partition in a certain relationship between the liquid and the
solid phase depending on actual temperature and cooling
rate. In the case of iron and silicon the concentration in the
remaining liquid phase is higher and hence the residual melt
is steadily enriched in these elements while solidification
proceeds. In the usual case of symmetric strip cooling, the
location where material solidifies last is the centerline of the
strip. Here the enriched interdendritic liquid finally solidifies
and eutectic colonies and large localized pre-eutectic pre-
cipitates can be formed depending on composition of the
alloy and parameter of the casting process. Because of the
mechanical pressure on the semi-solid sump during twin-roll
casting also other segregation patterns are observed in case
of rather hot casting conditions and thin strip. The segre-
gation patterns in twin-roll casting are categorized in surface
segregates or surface bleeds, centerline segregates, among
which channel and deformation segregates can be distin-
guished and banded structures [2, 3].
Surface Bleeds
Surface bleeds are pockets of solute-rich material on strip
surface containing a clearly increased concentration of
intermetallic precipitates. The structure can either appear
eutectic or very fine dendritic. Lockyer et al. [2–4] propose
that surface bleeds are a result of a small gap opening up
between the roll and the semi-solid sheet. This space gets
partially filled by solute-rich liquid, which immediately
solidifies when it contacts the roll. During solidification,
initially a thin semisolid film forms on roll surface. This film
is pushed towards the roll gap by metallostatic pressure. As
it approaches the roll gap, it meets material that is moving at
lower speed owing to backward slip, and the resultant dif-
ference in velocities causes the thin semisolid film to buckle.
The compressive forces acting on the semisolid material in
this region squeeze solute-rich liquid from in between the
solidified dendrite network into the gap now formed on the
surface, where it immediately solidifies in contact with
the roll in droplet shape. Throughout the following hot
deformation the surface bleed gets its typical saucer-like
shape [5]. The mechanism of surface segregate formation
was confirmed by Forbord et al. [6] investigating stop
samples in connection with simulations. That study revealed
that at relatively high casting speeds a low pressure zone
develops close to the roll providing the driving force for
enriched interdendritic liquid to flow towards strip surface.
High casting speed or low separating forces, thin strip
thickness, alloys with freezing ranges of 10–30 °C and
C.W. Schmidt et al.
reasonable amount of liquid present prior to completion of
solidification promote the formation of surface bleeds [4].
Centerline Segregates
Centerline segregates are a major problem in twin-roll
casting of long freezing range alloys. This, together with
reduced casting speed and high separating forces, makes
twin-roll casting of such alloys unattractive. Centerline
segregates are distinguished by their formation mechanism
and appearance in channel segregates and deformation seg-
regates [2, 3]. Channel segregates are cylindrical regions
with strongly enhanced content of eutectic forming alloying
elements and hence reduced melting point. They are aligned
in casting direction and occur at the plane in strip thickness,
were both solidified aluminium layers meet. In the usual case
of symmetric solidification they are positioned exactly at the
centerline. Their formation is related to deformation of the
mushy zone, which contains a network of solid dendrites and
enriched melt in interdendritic locations. When casting
conditions are comparably hot, meaning e.g. thin strip
thickness, high strip speed or poor cooling conditions, the
sump or solidification length grows and the mushy zone is
deformed by the pressure of the rolls. As the solid portion
deforms, the liquid portions are pushed back from the rela-
tively cold mushy zone upstream towards the hotter melt
zone. When liquid metal flows from a colder to a hotter area,
the liquid must change its composition and re-melts already
solidified material. The forced flow of liquid created by roll
pressure causes melting, that causes further flow and finally
channel formation. Usually the channels have an almost
constant spacing. When casting conditions become even
hotter, the appearance of centerline segregates becomes
more equiaxed and they are then distributed within a certain
band of the casting gauge [3]. This happens when in the
mushy zone solid and liquid are co-deformed rather than
liquid being squeezed back upstream, leading to the name
deformation segregates. Enhanced heat transfer, e.g. by the
use of copper shells, generally leads to a reduction of cen-
terline segregation [7].
Banded Structure
At very low separating forces, the structure does not any-
more vary continuously from the surface to the strip center.
There is a rather sudden change in dendrite arm spacing
(DAS) midway through the sample. Then a clear distinction
between a central band and two outer bands can be made.
The inner band has an extremely small DAS, while some
coarser areas can be found. Yun et al. [3] propose that the
Influence of Process Conditions on Segregation Behavior …
base of the sump becomes more U-shaped and hence the
interface between mushy zone and solid zone becomes flat.
As soon as there is solid throughout the casting thickness in
the mushy zone, pressure builds up by the rolls and con-
siderably increases heat transfer between strip and rolls. Due
to the flat U-shaped interface between mushy zone and solid
zone, there is a steep localized gradient in cooling rate and
hence in temperature.
Experimental
Alloy
For this investigation an AlFeSi alloy with the chemical
composition as shown in Table 1 was used, because the high
alloying level of iron in such alloys allows a comparably
easy observation of segregation effects. The melt interval of
this alloy of approximately 31 K is considered as compa-
rably large for twin-roll casting of aluminium. During
solidification of this alloy first a-AlFeSi and then b-AlFeSi
phases form.
Setup of the Casting Trials
The casting trials were performed on a SCAL 3CM Caster
with 956 mm outer roll diameter under standard production
conditions at the end of a production campaign. The casting
process was in a stable steady-state process and the only
active change to the process was in roll speed. After each
change, the casting process proceeded for 15 min until
manual measurements of roll surface temperature and strip
surface temperature were undertaken. For each casting speed
stable process data, strip profile measurement and tempera-
ture measurements were recorded.
Alsim Model for Twin-Roll Casting
Alsim is a finite element model including heat and fluid
flow coupled with stresses and deformations. A Coulomb
friction law is applied and by iterations on the mechanical
conservation equations the parts of the cast surface that are
either in slip or sticking mode against the roll shell are
determined and tangential forces are calculated. The results
include the roll force, the forward slip and the momentum
Table 1 Chemical composition of the applied alloy in wt%
Si Fe Cu Mn
0.858 0.759 0.001 0.042
813
on the rolls. A 2D finite element approach is applied, as the
heat flow in the width direction is assumed to be insignif-
icant and a plane strain-approximation is assumed to be
valid for a large part of the strip. More details about the
model can be found in [8], including the Arbitrary Euler
Lagrangian (ALE) formulation for the moving mesh. In this
study the model has been used also for segregation analysis.
In that case a volume-averaged two-phase model approach
is used for the flow. The model accounts also for the
solidification shrinkage (shrinkage flow). The flow of both
phases (liquid and solid) is calculated separately and cou-
pled with interfacial terms, more details about this model
formulation can be found in [9]. The weakest part of the
model are perhaps the assumptions on heat transfer coeffi-
cients between the strip and the roll shell. As direct tem-
perature measurements are difficult to obtain, the only
validation of this approach is the temperature on the strip
some distance away from the roll gap. The heat transfer
coefficients are tuned to fit against one of the experiments
and then the same heat transfer coefficients are used for all
cases. An ad hoc choice for the increase of the heat transfer
coefficients (HTC) was made—the HTC’s vary from 10,000
to 40,000 W/m2 K in the centre where the pressure is
highest.
Influence of Casting Speed on Other
Parameter of the Twin-Roll Casting Process
Although apart from roll speed no other casting parameter
was actively changed during the trials, of course as a reac-
tion to this, other parameter like e.g. strip thickness and
process temperatures change as well to a certain extent. The
influence of casting speed on those parameter is shown in
Fig. 1. Direct reaction to increasing casting speed is a shift
of the solidification front downstream, identical to an
increase in sump length because of a reduction of contact
time. This leads to a higher share of liquid metal in the roll
gap and hence to a reduction of separating force (see
Fig. 1a). These hotter casting conditions also directly lead to
a slight increase in roll surface temperature of 8 °C and
increased strip surface temperature at roll exit by 22 °C in
total. Besides these process parameter, the geometry of the
strip changes as well. Strip thickness as well as profile height
reduce with increasing casting speed. Forward slip does not
show a clear trend, most probably due to lack of precision in
the indirect measurement taken.
Mg Ti Al
0.006 0.011 98.329
814
Fig. 1 Influence of casting speed on other process parameter during the trial
Influence of Process Conditions
on Microstructure and Element Distribution
The microstructure of all specimens regardless of casting
speed shows a strongly deformed surface layer typical for
twin-roll cast material without any surface bleeds. Proceed-
ing towards strip center, there is a rather sudden transition in
the structure from elongated, deformed grains oriented in a
low angle to casting direction to rather equiaxed ones. In
bright field mode (see Fig. 2) it becomes obvious, that at this
transition a comparably high amount of intermetallics is
found, indicating a preferential segregation to this transition
area at low casting speed. With increasing casting speed, the
segregation becomes more and more dislocated in a band
around this transition from sheared grains to rather equiaxed
ones, while the transition between those bands becomes
C.W. Schmidt et al.
increasingly pronounced in terms of grain size and orienta-
tion (see Fig. 3).
Measuring the relative thickness of the two outer and the
central band (see Table 2) reveals that with increasing
casting speed the relative thickness of the central band
grows. The proportion of top and bottom band stays rather
constant, while the bottom band is always a bit thicker. The
thickness of the outer bands is decreasing with increasing
casting speed because of the shorter contact time between
strip and roll. Besides, with increasing casting speed the
depth of the sump increases and its shape transforms from
an arrow to a lying U [3]. Hence, the geometry of the
boundary between semi-solid and solid becomes flat and
causes the relative thickness of the central region to grow in
accordance with to the mechanistic argumentation of Yun
et al. [3].
Influence of Process Conditions on Segregation Behavior …
a) 1332 mm/min b) 1476 mm/min
Fig. 2 Longitudinal sections of as-cast material in bright field mode
While there are no surface bleeds on any of the samples
and there is a mild form of a banded structure with slightly
different appearance in each sample, there is also a distinct
centerline segregation in each sample. Both, appearance and
frequency of large centerline segregates requires a certain
amount of statistics. A clear trend cannot be identified from
the limited volume of metallography samples investigated
(see Fig. 3). At low casting speed, the centerline segregates
are present in form of channel segregates with a rather
constant width. At higher casting speeds, both, deformation
segregates as well as channel segregates are observed.
While in metallographic investigation the macroscopic
distribution of large precipitates was revealed, the distribu-
tion of the main alloying elements iron and silicon is mapped
with WDX. The maps in Fig. 4 show the macrosegregation
pattern caused by directed solidification with systematically
changing high cooling rates from strip surface to strip center.
The images show a longitudinal section from strip surface
(top) to centerline (close to bottom). Clearly visible are the
centerline segregations with large channel-like areas with
very high concentration of both elements. While close to the
surface, the distribution seems rather homogeneous, it
becomes more and more heterogeneous within the central
band.
A more detailed analysis is shown in Fig. 5, where the
recorded maps were aggregated to line profiles perpendicular
to strip surface by averaging across width of the maps. These
815
c) 1596 mm/min
profiles show clearly that iron and silicon are distributed in a
proportional way, as it is expected knowing that mainly
a-AlFeSi and b-AlFeSi phases are found in this alloy. Close
to surface the concentration of both elements is slightly
enriched although no large precipitates were detected in
metallographic examinations. This is a result of the very
high quenching rate in this surface-near regions of about
100–1000 K/s leading to enhanced solubility of iron [1] and
very fine precipitates. From surface onwards, the concen-
trations of both elements decrease steadily with low scatter
until the zone boundary with the inner band. Here both,
average concentration and local scatter of element distribu-
tion increase. This is in good accordance with the observa-
tion of large precipitates in this area. At lower speed this area
is found at larger distance to the surface and the scatter is
clearly higher, indicating a more severe tendency to segre-
gation towards this zone boundary. Within the central band
the absolute minimum of alloying element concentration is
observed until the centerline segregates are found.
Comparison of Experimental Results
with Alsim Simulations
Figure 6 shows the comparison of Alsim results with mea-
sured separating force and forward slip. The model captures
the trend in separating force although for the highest speeds
816 C.W. Schmidt et al.

a) 1332 mm/min

b) 1476 mm/min

c) 1596 mm/min

Fig. 3 Longitudinal sections at casting gauge at slow, medium and high casting speed

Table 2 Relative thickness of the respective bands at casting gauge

1332 mm/min 1476 mm/min 1596 mm/min
Top band (%) 32.2 29.6 21.7
Central band (%) 32.5 38.5 55.1
Bottom band (%) 35.3 31.9 23.2

the simulation results show too high forces. This might be
related to the variation in strip thickness—the strip gets
thinner as the speed increases (see Fig. 1b), while this effect
is not included directly in the model. The experimental
forward slip is generally higher than the simulated results.
This is also related to the ad hoc choice of friction coefficient
in the simulation (0.4 was used).
Figure 7 shows the normal stress component and the
shear stress component for the case with the lowest roll
speed of 1192 mm/min, identical to 1332 mm/min experi-
mental casting speed.
For the macrosegregation results a Scheil microsegrega-
tion model was used. The results will be strongly affected by
the local heat conditions in part of the strip close to the
meniscus and in the part where there is no large pressure
against the roll. The heat transfer coefficients are unknown
and the results must be interpreted as qualitative results
capturing the trends from observations. Figure 8 shows
results from the case with casting speed 1332 mm/min. The
segregation is oscillatory. The shrinkage contribution causes
a depleted centre (as is observed in extrusion ingots and
sheet ingots) but the inwards movement of mushy zone
Influence of Process Conditions on Segregation Behavior …
a) 1332 mm/min
b) 1596 mm/min
Fig. 4 WDX maps of longitudinal sections of as-cast material with different casting speed
a) 1332 mm/min
Fig. 5 Depth profiles of iron and silicon derived from WDX maps
material enriched with silicon (caused by external defor-
mation from the rolls) may cause positive segregation in the
centre if this effect is strong enough to override shrinkage
contribution. The forced fluid flow from the nozzle will
penetrate directly into the centre and also sweep some of the
enriched liquid away from the centre (but this flow does not
817
b) 1596 mm/min
penetrate all the way to the bottom of the mushy zone), this
effect explains the maximum at some distance away from the
centre. The balance of the forced fluid flow, permeability,
shrinkage flow and deformation of the mush will decide
where the segregations appear. Regarding the simulation
results, these have to be assessed carefully. In such a
818 C.W. Schmidt et al.

a) b)

Fig. 6 Comparison of: a measured separating force and b measured forward slip with simulation results as function of roll speed

Fig. 7 a Normal stress component from −400 to +40 MPa in step 40 MPa and b shear stress component from −100 to 50 MPa in step 15 MPa

Fig. 8 Concentration of silicon in wt% from 0.75 to 1.05 in step 0.03 wt%. Blue areas are depleted in Si. The mushy zone is visible to the left.
The shrinkage flow causes the mixture concentration to appear depleted down to the fully solid

complex model also numerical effects may play a role and it
is a time consuming process to validate each part of the
model and the complex interaction of different physical
mechanisms.
Summary
Twin-roll casting trials with alteration of only the casting
speed were performed with an AlFeSi alloy. Reactions of
other process parameter were recorded and microstructure,
segregations and distribution of the main alloying elements
were measured. Supporting the experimental investigation,
the Alsim model was used with a Scheil microsegregation
model to visualize related effects and understand influencing
factors on the final element distribution and segregation
pattern in such an alloy out of the twin-roll casting process.
By increasing casting speed, the solidification front is
shifted downstream leading to an increase in process tem-
peratures and a reduction of separating force, strip thickness
and profile height. While no surface bleeds are found, a
certain extent of centerline segregation is always present. Its
appearance changes from purely channel-like to a mixture of
channel and deformation segregates with increasing casting
speed. Generally, a mild form of a banded structure is
observed, wherein the central band grows with increased
speed. The local concentration of main alloying elements
decreases steadily from strip surface presumably due to a
decrease of cooling rate until the zone boundary, where a
preferential segregation spot is observed. Within the central
Influence of Process Conditions on Segregation Behavior …
band the global minimum in concentration is found before a
clear localization in centerline segregates.
The Alsim model is not yet perfectly calibrated for the
present case and hence results have to be interpreted with
care, but it confirms the trends in process parameters and
provides insights into preferential sites and critical parameters
for the localization of segregates. These are the balance of
the forced fluid flow, permeability, shrinkage flow and
deformation of the mush.
Acknowledgements The authors are thankful for the joint execution of
casting trials and the fruitful discussions with the experienced team of
Hydro Aluminum Karmøy Rolling Mill as well as for material testing,
metallography work and fruitful discussions at Hydro R&D Bonn.
References
1. I. Miki, H. Kosuge, K. Nagahama, Supersaturation and decompo-
sition of Al–Fe alloys during solidification. J. Jpn. Inst. Light Met.
25, 1–9 (1975)
819
2. S. Lockyer, M. Yun, J. Hunt, D. Edmonds, Micro- and macrode-
fects in thin sheet twin-roll cast aluminum alloys. Mater. Charact.
37, 301–310 (1996)
3. M. Yun, S. Lockyer, J. Hunt, Twin roll casting of aluminium alloys.
Mater. Sci. Eng., A 280, 116–123 (2000)
4. M. Yun, S. Lockyer, J. Hunt, The formation of surface bleeds in
twin-roll cast aluminium sheets. Int. J. Cast Met. Res. 13, 255–261
(2001)
5. C. Gras, M. Meredith, J. Hunt, Microdefects formation during
twin-roll casting of Al–Mg–Mn aluminium alloys. J. Mater. Pro-
cess. Technol. 167, 62–72 (2005)
6. B. Forbord, B. Andersson, F. Ingvaldsen, O. Austevik, J. Horst, I.
Skauvik, The formation of surface segregates during twin roll
casting of aluminium alloys. Mater. Sci. Eng., A 415, 12–20
(2006)
7. G. Hugenschütt, D. Kolbeck, H.G. Wobker, Copper shells for twin
roll casting, Light Met. (2006) 859–863
8. D. Mortensen, H.G. Fjær, D. Lindholm, K.F. Karhausen, J.S.
Kvalevåg, Modelling of the twin roll casting process including
friction, Light Met. 1243–1247 (2015)
9. D. Mortensen, M.M’Hamdi, K. Ellingsen, K. Tveito, L. Pedersen,
G. Grasmo, Macrosegregation modelling of DC-casting
including grain motion and surface exudation, Light Met.
867–872 (2014)
 Effect of Magnesium Content
on Microstructure and Mechanical Properties
of Twin-Roll Cast Aluminum Alloys

Onur Meydanoglu, Cemil Işıksaçan, Hatice Mollaoğlu Altuner,

Mert Günyüz, and Onur Birbaşar

Abstract
High magnesium containing aluminum alloys are preferred in applications where high
strength and good formability are of importance. However, enhanced Mg content in AlMg
alloys leads to increased solidification range which makes these systems difficult to be
produced by twin-roll casting. In this study, AlMg alloys were produced by twin-roll
casting with different Mg contents up to 5.2 wt% and processed to obtain soft annealed
1 mm thick samples. The effect of Mg content on the microstructural evolution during
twin-roll casting as well as downstream processes and mechanical properties of soft
annealed 1 mm thick samples was investigated. Addition of Mg leads to coarser grain
structure in as-cast strips and finer grain structure after intermediate annealing as well as
soft final annealing. At the same time, enhanced Mg content provides higher yield and
tensile strengths as well as lower elongation.

Keywords
High magnesium aluminum alloy Twin-roll casting

Introduction aluminum alloys can be enhanced by adding magnesium.

Formability of a cold rolled metal sheet is characterized in
terms of vertical (R) and planar (Δr) anisotropy coefficients
which are derived by plastic anisotropy ratios (r-value)
obtained by tensile tests [1]. Lower R and higher Δr values
of face-centered cubic metals such as aluminum when
compared to those of body-centered cubic metals lead to
inferior formability [2–4] and limit their widespread use in
automotive industry [5, 6].
However, due to global warming reducing the emissions
of vehicles has been gaining much attention. At this point,
the use of light metals such as aluminum has been of
importance. On the other hand, poor formability of
O. Meydanoglu (&)
C. Işıksaçan
H. Mollaoğlu Altuner

M. Günyüz
O. Birbaşar
ASSAN Aluminum, Yayla Mh. D-100 Karayolu Ruya Sk. No.2,
34940 Tuzla, Istanbul, Turkey
e-mail: onur.meydanoglu@assanaluminyum.com
Aluminum-magnesium alloys, known as 5xxx aluminum
alloys series, possess a combination of high
strength-to-density ratio and reasonable formability together
as well as high corrosion resistance and recyclability [2, 7–
10]. However, magnesium addition into aluminum results in
larger solidification range which makes their production
difficult by twin-roll casting where molten metal solidifies
between two water-cooled rotating caster rolls within a very
short time. In other words, larger solidification range
becomes a disadvantage for twin-roll casting due to limited
dwell time of liquid metal between caster rolls [6]. For this
reason, lower specified magnesium limits of 5xxx aluminum
alloys are preferred for twin-roll casting which turns out
minimum specified strengths of these alloys [6].
In this study, high magnesium containing aluminum
alloys were produced by twin-roll casting at two different
magnesium weight contents and the effect of magnesium
content on the microstructural and mechanical properties of
soft annealed 1 mm thick sheets was investigated.

© The Minerals, Metals & Materials Society 2017 821

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_99
822
Experimental Studies
Within the scope of this study, high magnesium containing
aluminum alloys were cast with two different magnesium
weight contents of 2.75 and 5.20 by industrial scale Novelis
twin-roll caster. Table 1 lists the chemical compositions of
the samples used in this study.
5.5 mm thick as-cast strips were processed to achieve
1 mm thick O temper samples with an intermediate
annealing process. Intermediate annealing was conducted on
2.5 mm thick strips at 350 °C for 6 h in a batch type
industrial scale furnace. After intermediate annealing, strips
were cold rolled to 1 mm and soft annealed at 350 °C for
4 h to achieve O temper.
Characterization of samples were carried out by micro-
scopic investigations and mechanical tests. Microscopic
examinations were conducted by optical microscope under
polarized light on the cross-sections of as-cast as well as
1.0 mm thick soft annealed samples after preparing the
specimens according to the standard metallographic methods
and etching with Barker’s solution. Grain size of samples were
measured based on circular intercept method. For this purpose,
a circle with a radius of 290 µm was placed on the etched
optical microscope images and the number of grain boundaries
intersecting the circle were counted. And then the average
grain sizes were calculated dividing perimeter of circle by the
number of grain boundaries intersecting the circle.
Mechanical properties of samples were determined by
hardness measurements and tensile tests. Micro hardness
tests were made on polished cross-sections of as-cast strips
with a Vickers indenter under a load of 10 g and a dwell
time of 10 s.
Tensile tests were performed on as-cast strips and 1.0 mm
soft annealed samples at room temperature on Zwick tensile
test machine at a nominal crosshead speed of 20 mm/min
with a 50 mm extensometer. In order to determine plastic
anisotropy ratios and strain hardening exponent, longitudinal
and transverse strain gauges were utilized during tensile tests
of soft annealed 1.0 mm thick rectangular dog-bone samples
prepared in 0°, 45° as well as 90° to the rolling direction.
Plastic anisotropy ratios and strain hardening exponent
Table 1 Chemical compositions Element (wt%)
of the alloys
Si Fe
0.10 0.18
0.09 0.18
Table 2 Mechanical properties Mg content (wt%) Yield strength (MPa)
of as-cast strips
2.75 174
5.20 212
O. Meydanoglu et al.
values were measured at plastic strains between 4 and 6%.
Results of tensile tests were evaluated by averaging the
results of 10 successive tensile tests.
Results and Discussion
Tensile test and hardness measurement results of as-cast
strips are listed in Table 2. Mechanical tests conducted on
as-cast strips have revealed that increased Mg content leads
to enhanced strengths and hardness.
Cross-sectional optical micrographs of etched as-cast
strips are presented in Fig. 1. Microscopic investigations
have shown that 5.20 wt% Mg added alloy exhibits coarser
grain structure when compared to that of 2.75 wt% Mg
added alloy in as-cast state. On the other hand, due to nature
of twin-roll casting, a gradually increase in grain size from
outermost surfaces to mid-plane is expected with a
super-saturated region at the outermost surfaces. However,
as can be seen in microstructures of as-cast strips, 5.20 wt%
Mg added alloy exhibits almost no super-saturated region
probably due to larger solidification range when compared to
that of 2.75 wt% Mg added alloy and thus insufficient
cooling rate provided by water-cooled rotating caster rolls.
The microstructures of 2.5 mm thick strips after inter-
mediate annealing and 1.0 mm thick strips after soft
annealing are given in Figs. 2 and 3, respectively. Typical
etched microstructures of strips have revealed that 5.20 wt%
Mg added alloy exhibits a much fine grained structure after
both intermediate annealing and soft annealing in contrast to
as-cast state. It can be concluded that further Mg addition
into Al encourages grain refinement during annealing.
Grain size measurements performed based on circular
intercept method have shown that after intermediate
annealing 2.75 wt% Mg and 5.20 wt% Mg added alloys
exhibit a grain size of 18.40 and 16.20 µm, respectively. On
the other hand, after soft annealing 2.75 wt% Mg and 5.20
wt% Mg added alloys show a grain size of 26.40 and
18.40 µm, respectively.
The results of tensile tests conducted on 1 mm thick soft
annealed samples at room temperature are presented in
Mn Mg Cr Ti
0.06 2.75 0.07 0.04
0.07 5.20 0.07 0.02
Tensile strength (MPa) Hardness (HV0.01)
231 71 ± 4.5
281 84 ± 9.9
Effect of Magnesium Content on Microstructure … 823

Fig. 1 Typical etched

cross-sectional optical
microscope images of as-cast
strips a 2.75 wt% Mg added alloy
and b 5.20 wt% Mg added alloy

Table 3 with plastic anisotropy ratios (r) and strain harden-
ing exponent values (n).
Significant increase in strength was detected upon further
Mg addition into Al. This result can be attributed to the
further solid solution hardening of Mg.
For 2.75 wt% Mg added alloy, there is an inverse relation
between tensile strength and elongation and samples possess
maximum strength and total elongation values at 0° and 45° to
rolling direction, respectively. This trend is comparable with
those reported by Jain et al. [4]. On the other hand, r-value of
824 O. Meydanoglu et al.

Fig. 2 Microstructures of
2.5 mm thick strips after
intermediate annealing conducted
at 350 °C for 6 h a 2.75 wt% Mg
added alloy and b 5.20 wt% Mg
added alloy

Fig. 3 Microstructures of
1.0 mm thick strips after soft
annealing conducted at 350 °C
for 4 h a 2.75 wt% Mg added
alloy and b 5.20 wt% Mg added
alloy

Table 3 Tensile test results with r and n values

Mg Direction Yield Tensile Uniform Total r n Rvertical Rplanar
content strength strength elongation A50 elongation A50
(wt%) (MPa) (MPa) (%) (%)
2.75 0 95 ± 2.6 210 ± 4.9 17.0 ± 1.52 20.1 ± 1.80 0.81 0.30 0.6575 0.2950
45 93 ± 2.1 203 ± 2.3 20.1 ± 1.94 22.7 ± 0.89 0.51 0.29
90 96 ± 0.8 207 ± 1.4 18.3 ± 1.22 20.9 ± 1.48 0.80 0.30
5.20 0 139 ± 3.7 296 ± 4.4 18.0 ± 1.48 19.8 ± 1.44 0.69 0.30 0.6725 −0.0550
45 135 ± 3.7 278 ± 8.5 15.0 ± 3.17 16.3 ± 3.21 0.70 0.30
90 137 ± 1.9 265 ± 8.6 10.7 ± 1.99 11.2 ± 2.05 0.60 0.30

samples taken at 45° to rolling direction are much lower than
those taken at 0° (parallel) and 90° (perpendicular) to rolling
direction. This observation indicates that samples taken at 0°
and 90° to rolling direction are more resistant to thinning when
compared to 45° and samples taken at 45° to rolling direction
experience higher thinning during tensile test. Lower r-values
of samples taken at 45° to rolling direction are in good
agreement with those reported by Jain et al. [4] and Abedrabbo
et al. [11], who studied forming performance of 5754 Al alloy.
However, in contrast to 2.75 wt% Mg added alloy, for
5.20 wt% Mg added alloy, there is direct relation between
tensile strength and elongation. 5.20 wt% Mg added alloy
exhibits maximum strength and elongation at 0°, 45° and
90°, respectively. Further Mg addition into Al results in
lower r-values at 0° and 90° where higher r-value at 45°
when compared to those of 2.75 wt% Mg added alloy. Also,
it should be noted that r-values of samples taken at 0° and
45° to rolling direction are very close to each other and much
higher than that of samples taken 90° to rolling direction for
5.20 wt% Mg added alloy.
When vertical (Rvertical) and planar (Rplanar) anisotropy
coefficients are calculated, it is found that 5.20 wt% Mg
added samples have slightly higher vertical and significantly
lower planar anisotropy coefficients indicating that increased
Mg contents provides resistance to thinning and earing
during forming.
Effect of Magnesium Content on Microstructure …
Conclusions
The results of this study can be summarized as follows:
Increased magnesium content leads to enhanced strength
and coarser grain structure at as-cast strip thickness.
Increased magnesium content results in much fine grained
structure after both intermediate annealing and soft anneal-
ing. It can be concluded that further magnesium addition into
aluminum encourages grain refinement during annealing.
Further magnesium addition into aluminum alloy results
in significant increase in strength which can be attributed to
the further solid solution hardening of magnesium.
For 2.75 wt% Mg added alloy, r-values of samples taken
at 45° to rolling direction are the lowest indicating that
samples experience higher level of thinning at 45°. Further
magnesium addition into aluminum alloy lowers r-values at
0°, 90° and enhances r-values at 45°. Increased magnesium
content results in slightly higher vertical and significantly
lower planar anisotropy coefficients which are favorable for
thinning and earing, respectively.
Acknowledgements Authors wish to thank Mr. Nihat Yılmaz, tech-
nician of Assan Alüminyum Laboratory, for his valuable help with
metallographic studies.
10. G. Zhu, X. Hu, J. Kang, R.K. Mishra, D.S. Wilkinson, Deforma-
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Asymmetric rolling of thin AA-5182 sheets: modelling and
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3. S.J. Hashemi, H.M. Naeini, G. Liaghat, R.A. Tafti, F. Rahmani,
Forming limit diagram of aluminum AA6083 tubes at high
temperatures by bulge tests. J. Mech. Sci. Technol. 28(11), 4745–
4752 (2014)
4. M. Jain, J. Allin, M.J. Bull, Deep drawing characteristics of
automotive aluminum alloys. Mater. Sci. Eng. A 256, 69–82
(1998)
5. S.G. Son, H.K. Kim, J.H. Cho, H.W. Kim, J.C. Lee, Differential
speed rolling of twin-roll-cast 6xxx Al alloy strips and its
influence on the sheet formability. Met. Mater. Int. 22(1), 108–
117 (2016)
6. A. Tewari, S. Vijayalakshmi, S. Tiwari, P. Biswas, S. Kim, R.K.
Mishra, R. Kubic, A.K. Sachdev, Influence of microstructure on
uniaxial strain localization in AA5754 aluminum sheets produced
by various processing routes. Metall. Mater. Trans. A 44A, 2382–
2398 (2013)
7. N.S. Barekar, S. Das, X. Yang, Y. Huang, O.E. Fakir, A.G.
Bhagurkar, L. Zhou, Z. Fan, The impact of melt conditioning on
microstructure, texture, and ductility of twin roll cast aluminium
alloy strips. Mater. Sci. Eng. A 650, 365–373 (2016)
8. Z. Yu, Z. Lin, Y. Zhao, Evaluation of fracture limit in
automotive aluminium alloy sheet forming. Mater. Des. 28,
203–207 (2007)
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separation force in horizontal twin roll casting of aluminum alloys.
J. Mater. Process. Technol. 218, 48–56 (2015)
tion inhomogeneity in large-grained AA5754 sheets. Mater. Sci.
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and AA5754-O at elevated temperatures using coupled
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875 (2007)
 Influence of Sticking on the Roll Topography
at Twin-Roll Casting of Aluminum Alloys

Olexandr Grydin, Florian Nürnberger, and Mirko Schaper

Abstract
The formation of strips at twin-roll casting depends on the state of the roll surface. The
processing conditions, which are characterized by high metal-tool interface temperatures
and compression stresses, provoke sticking between the cast material and the rolls. This
effects changing of the tool’s topography, impairment of the strip’s surface quality and
interference of its flatness. In the scope of this study the evolution of roll’s topography at
twin-roll casting of 3 mm thick strips of aluminum alloys EN AW-1070 and EN AW-6082
without any release agents was experimentally analyzed using laboratory casting unit. The
effect of repetitive tool’s self-cleaning during processing of the EN AW-6082 alloy was
observed, whereas aluminum of technical purity showed intensive sticking on the roll
surface. In the last case micro-profiling of the tool’s surface is not more efficient and release
agents have to be used for improvement of the strip’s formation conditions.

Keywords
Twin-roll casting Thin strip Aluminum alloys Sticking Roll topography

Introduction
A micro-profiling of twin-roll casting rolls strongly influ-
ences the heterogeneous nucleation conditions in the melt as
well as the heat transfer between the cast material and the
tool. These factors are very important for a stable formation
of thin defect-free metallic strips directly from a melt within
some tenth of a second. Thus, an optimization of the roll
surface topography allows improving the solidification
conditions and the product quality. Different approaches for
a micro-profiling of rolls have been proposed. E.g., Furuza
O. Grydin (&)
M. Schaper
Chair of Materials Science, Paderborn University, Warburger Str.
100, 33098 Paderborn, Germany
e-mail: grydin@lwk.upb.de
M. Schaper
e-mail: schaper@lwk.upb.de
F. Nürnberger
Institut Für Werkstoffkunde, Leibniz Universität Hannover,
An der Universität 2, 30823 Garbsen, Germany
e-mail: nuernberger@iw.uni-hannover.de
et al. [1] and Minamida et al. [2] suggested shaping the roll
surface with a lot of single local cavities of a depth between
5 µm and 100 µm. Within the patents of Yukumoto et al.
[3] and Mahapatra et al. [4] a series of continuous grooves
with of a depth more than 10 µm was proposed; while in the
first work the grooves’ direction should be parallel to the
roll’s axis, the second suggested a tangential
micro-profiling. An analysis of the interaction between a
melt and micro-profiled rolls, which were water-cooled on
the inside, was conducted by Badowski [5] and Lauscher [6]
regarding nucleation and shell growth during solidification.
However, there is no information about the sleeves’
topography evolution at twin-roll casting due to sticking of
the processed material on the tool surface. In general,
sticking is characteristic for metals which are processed with
compressive stresses and with high interface temperatures
between the tools and semifinished products or components.
Thus, the problem of sticking is well-known for twin-roll
casting, in particular when manufacturing alloyed aluminum
strips [7].

© The Minerals, Metals & Materials Society 2017 827

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_100
828
Reducing adhesion of the processed metal to the rolls can
be achieved by continuously spraying a thin lubricant film
on the sleeves’ surfaces [7, 8] though the release agent layer
decreases the heat transfer from the melt to the water-cooled
rolls as well as the rate of the metallic shell growth. This
impacts negatively on the process productivity and on the
possibility to produce strips with an increased thickness. The
aim of the study is an experimental analysis of the principles
of the tool’s topography evolution at twin-roll casting of thin
strips of a technical pure aluminum as well as the alloy EN
AW-6082 of the Al–Mg–Si-system without a release agent
application.
Experimental Procedure
The experiments were carried out using a twin-roll caster of
the Chair of Materials Science of the Paderborn University.
The laboratory unit is equipped with two assembled rolls
with sleeves manufactured of a hot-work tool steel
X38CrMoV5-3 (1.2367). The sleeves have an outer diameter
of 370 mm, a barrel length of 200 mm and a wall thickness
of 15 mm. The water cooling is realized on the inside sur-
face of the sleeves. To facilitate the solidification conditions
at the melt-tool interface, the working surfaces of both
sleeves were micro-profiled with continuous tangential
screw-line grooves of a depth about 10 µm and a width
Fig. 1 Topography
characterization on the sleeve’s
working surface between
twin-roll casting trials by means
of a mobile digital confocal
microscope Keyence VHX-100 K
O. Grydin et al.
about 300 µm. Further features of the laboratory twin-roll
caster are described in [9].
Measurements of the rolls’ topography were realized by
means of a mobile digital confocal microscope Keyence
VHX-100 K equipped with a zoom lens with focal length
factor ranging between 20 and 200. This microscope
allows to characterize surface reliefs with an accuracy of
0.1 µm. The measurements were conducted before and after
the twin-roll casting experiments at a specified surface area.
For an accurate positioning of the observation area two
indentations on the working surface one of the rolls were
placed. The measurements were performed between the
marks. The mobile digital confocal microscope in the posi-
tion for the topography scanning is depicted in Fig. 1.
The first series of twin-roll casting experiments regarding
the micro-relief evolution were carried out at the example of
strips with a thickness of 3 mm and the aluminum alloy EN
AW-6082. The main alloying elements are magnesium, sili-
con and manganese. The content of the later can reach up to
1%. The additional alloying of alloys of the Al–Mg-Si-system
with manganese decelerates recrystallization during hot
deformation and provides a fine-grained microstructure for-
mation. Due to this fact, thin strips of the alloy EN AW-6082
feature a tensile strength over 310 MPa after an
age-hardening treatment. The main parameters of the
twin-roll casting were a melt temperature of 700 °C, a casting
speed of 3.5 m/min and a set-back length of 45 mm. Further
Influence of Sticking on the Roll Topography at Twin-Roll … 829

parameters and conditions of the twin-roll casting are Generatrix

described in detail in [10, 11]. The twin-roll casting was
realized in vertical plane without a release agent or lubricants. a
The lengths of the cast strip as well as the sleeve’s micro-relief
were measured after each twin-roll casting. A chemical
cleaning of the tools’ surface was provided before the first

Tangent
experiment in a series by means of a 15%-NaOH solution.
A removal of the adhesive aluminum layer from the sleeves in
between the experiments was not carried out.
The second series of experiments was conducted at the
example of strips of a thickness of 3 mm and the commer-
cially pure aluminum EN AW-1070. In contrast to the alloy
EN AW-6082, the commercially pure aluminum is frequently
industrially processed by twin-roll casting. The conditions of 250 μm
the twin-roll castings as well as the experimental procedures
were identical to the first series of experiments. 0 Х
Generatrix
Results b

Twin-Roll Casting of the Aluminum Alloy EN

AW-6082

Information about the micro-relief of the sleeve’s surface can
be obtained by digital confocal microscopy of the zone of
interest or by graphs of relief’s height changing along some
arbitrary traced lines. Exemplarily, the sleeve’s surface pic-
tures before and after twin-roll casting of 3 mm thick strips
of the EN AW-6082 alloy are depicted in Fig. 2.
The magnified pictures in Fig. 2 show a well-observable
periodical relief of the tool surface both before the experi-
ments and after twin-roll casting of strips with a total length
of 16 m. This observation is representative for all the pic-
tures obtained in the experiments of the first series. A minor
quantity of aluminum on the roll’s surface before the
twin-roll casting experiments can be seen in Fig. 2a. One
possible cause might be an insufficient chemical cleaning.
The representative results of the sleeve’s topography
measurements along the red-marked lines (s. Fig. 2), which
were traced parallel to the barrel’s axis, are shown in Fig. 3
for the first series of experiments.
The quantified results depicted in Fig. 3 confirm that the
sleeve’s micro-relief is periodic and this character remains
after the melt-tool interaction. The width of a micro-relief
element amounts to about 300 µm. The grooves’ depth
ranges for the cleaned roll’s surface between 6.3 µm and
10.6 µm, whereas its mean value amounts to 7.9 µm. After
twin-roll casting of strips of the alloy EN AW-6082 with a
total length of 23.54 m the grooves’ depth deviates in the
observation area from 8.1 µm up to 25.8 µm. The mean
value increases to 11.54 µm.
The generalized results of the first series of experiments
represented by a graph of the sleeve’s micro-relief evolution
Tangent
250 μm
0 Х
Δh
Fig. 2 Sleeve’s micro-relief in the observation area before the first
experiments series (a) and after twin-roll casting of strips of the alloy
EN AW-6082 with a thickness of 3 mm and a total length of 16 m (b)
versus the twin-roll cast strips length are depicted in Fig. 4.
The upper curve in the Fig. 4 corresponds to the maximal
measured grooves’ depth values, while the lower curve relates
to the mean values. Therefore, the values could be considered
analog to Rz and Ra roughness values, respectively.
An analysis of the evolution of both maximal and mean
characteristics of the sleeve’s micro-relief shows that the
roll’s topography changing has a cyclic character due to
sticking of the processed material. A so-called
“self-cleaning” of the tool working surface occurs. This
effect is caused by a local growth of the stuck aluminum
layer to some critical value. If the stuck aluminum layer
thickness reaches the critical value, the adhesion strength
between the formed strip and the stuck material on the
830 O. Grydin et al.

Height of micro-relief, μm 20 Thus, micro-profiling the sleeves’ surfaces can be efficient to

improve the solidification conditions at twin-roll casting of
17.5
strips of the aluminum alloy EN AW-6082 with a thickness
15 of 3 mm. Auxiliary operations of an intermediate mechani-
12.5 cal or chemical roll cleaning are not required.
10
7.5
Twin-Roll Casting of the Commercially Pure
5 Aluminum EN AW-1070
2.5
0 Some different mechanisms were observed when realizing
0 300 600 900 1200 1500 the second series of experiments, i.e. twin-roll casting of
a X-coordinate in observation area, μm strips of commercially pure aluminum EN AW-1070. In this
case, the sleeve’s topography evolution characterization
revealed at the specified observation area a much more
30 intensive sticking of the pure aluminum to the roll’s surface
Height of micro-relief, μm

27.5
25 in comparison with the alloy EN AW-6082. The magnified
22.5 pictures of the sleeve’s surface show that the periodic
20 micro-relief is almost completely covered with stuck alu-
17.5 minum. A representative picture taken by digital confocal
15 microscopy is depicted in Fig. 5a. Comparison of Fig. 2a
12.5
10 and Fig. 5a illustrates the contrast between both processed
7.5 materials and of the melt-tool interaction mechanisms.
5 Characteristic results of the roll’s topography measurements
2.5 along the red-marked line (s. Fig. 5a) conducted between the
0 twin-roll casting experiments of the second series is shown
0 300 600 900 1200 1500 in Fig. 5b. In comparison with results of the first experi-
b X-coordinate in observation area, μm mental series (s. Fig. 3), the curve features a minor relief
height. The mean value of the groove’s depth in the obser-
Fig. 3 Roll’s topography in the observation area before the experi- vation area amounts to 4.08 µm. A periodic character of the
ments (a) and after twin-roll casting of strips of the alloy EN AW-6082
roll’s topography, which is not recognizable at 200 mag-
with a thickness of 3 mm of a total length of 23.54 m (b)
nification (s. Fig. 5a), can be detected by corresponding
peaks on the micro-relief curve (s. Fig. 5b). However, some
30
Height of micro-relief, μm

other local maxima on the curve make its identification

25
20
15
10
5
0
0 5 10 15 20 25 30 35
Total cast strip length, m
Fig. 4 Evolution of the roll topography for twin-roll casting of the
aluminum alloy EN AW-6082
sleeve’s surface exceeds the bonding strength of the later to
the water-cooled steel roll. Thus, the stuck aluminum alloy is
periodically removed from the tool. A similar mechanism of
a cyclic self-cleaning of die bearing surfaces when extruding
aluminum alloys was described by Valberg and Malvic [12].
difficult. In general, the distribution of peaks and cavities
seems to have a stochastic character. The same melt-tool
interaction behavior was observed during further roll’s
max topography measurements when twin-roll casting strips of
mean commercially pure aluminum with a thickness of 3 mm.
Discussion
The noticed differences in sticking of aluminum alloys EN
AW-6082 and EN AW-1070 to the surface of micro-profiled
sleeves can be explained by a stronger adhesion of pure alu-
minum to steel compared with aluminum alloys. On the other
hand, the age-hardening aluminum alloy EN AW-6082 is the
strongest material in the 6xxx-alloy’s group and features
strength values which are several times higher than the
strength of commercially pure aluminum. These two reasons
can cause the different interaction mechanisms between the
processed metal and the roll’s surface where some stuck
Influence of Sticking on the Roll Topography at Twin-Roll …
Generatrix
a Within the scope of this study the evolution of the rolls’
Tangent
250 μm
0 Х
10
Height of micro-relief in μm
7.5
5
2.5
0 1. T. Furuya et al., Method and apparatus of continuously casting a
0 300 600 900 1200 1500
X-coordinate in observation area, μm
b thin cast piece; device for and method of forming dimples on
Fig. 5 Sleeve’s micro-relief (a) and roll’s topography (b) in the
observation area after twin-roll casting of strips with thickness of 3 mm
of a total length of 11.57 m; pure aluminum EN AW-1070
aluminum alloy particles are already present. Due to high
temperatures and normal stresses in the roll gap a local cohe-
sive fusion between the stuck particles and the formed strip
occurs during their contact. When the strip outlet cross-section
is reached, tensile stresses appear in the outer strip layers and in
the bonding zone between the stuck metal and the steel sleeves.
These stresses growth until either fracture of the adhesive joint
between the tool and the processed metal occurs or fracture of
the cohesive joint in the outer strip layers. The later mechanism
is possible, if the tensile stresses exceed the material’s strength.
In this case the stuck metal layer thickness on the sleeve’s
surface stays unchanged or even increases. It’s clear that the
interaction of the high-strength aluminum alloy EN AW-6082
with the micro-profiled working tool’s surface corresponds to
the first scenario with a characteristic self-cleaning of the
sleeve’s micro-relief. The commercially pure aluminum
interacts with the tool during twin-roll casting by the second
mechanism. An intensive sticking of the EN AW-1070
aluminum alloy to the rolls requires some auxiliary opera-
tions of a continuous tool cleaning or usage of release agents.
831
Conclusions
topography at twin-roll casting of 3 mm thick strips of
commercially pure aluminum EN AW-1070 and the
age-hardening aluminum alloy EN AW-6082 without any
release agents was experimentally analyzed using a labora-
tory casting unit and a mobile digital confocal microscope
for the micro-relief measurements. During processing the
alloy EN AW-6082 a repetitive self-cleaning of the roll’s
surface was observed. The periodic roll’s micro-relief
remained efficient regarding the melt solidification condi-
tions. In contrast, twin-roll casting of EN AW-1070, i.e. pure
aluminum, resulted in an intensive sticking of the processed
material on the roll’s surface. For that case micro-profiling of
tools is not efficient and release agents or some auxiliary
continuous tool cleaning has to be applied to improve the
strip formation.
Acknowledgements The authors would like to thank Dr.-Ing. Gregor
Mroz for supporting the micro-relief topography measurements.
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finishing treatment of thin strips of the hardening aluminum alloy
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12. H. Valberg, T. Malvic, Metal flow in die channels of extrusion
investigated by an experimental grid pattern technique. Paper
presented at the 5th International Extrusion Technology Seminar
(Chicago, Illinois, 19–22 May 1992), p. 31
 Material Surface Roughness Change in Twin
Roll Casting of Aluminium as Cast Sheet
Product

Ceyhun Kuru, Sadık Kaan İpek, Eda Dağdelen, Özgür Özşahin,

and Ali Ulus

Abstract
Continuous casting of aluminum sheet products has so many advantages due to its short
production route. These advantages can be listed as low production cost, low investment
cost and short delivery time. However, this method has some technical insufficiencies that
are mostly related with quality issues. These disadvantages can be listed as low alloy range,
mechanical properties and surface quality. The most critical issue is surface quality. To
improve casted sheet surface quality, cold mill performance of continuous cast coils and
final surface properties; some operational applications are needed to guarantee for a
sustainable process parameters and repeatable measuring method. With this work, it is
aimed to evaluate the surface quality in terms of surface roughness changes with casting
and cold rolling operations. Besides material’s roughness, change in casting shell and work
roll roughness, in-going material roughness and planning parameters of casting and cold
rolling operations are involved.

Keywords

Twin roll casting Cold rolling Roll roughness As cast sheet surface Work roll
surface Aluminum strip roughness Friction

Introduction is the surface properties is a key parameter for production.

If we compare the casting methods of aluminum, Twin Roll
Casting (TRC) method is one of the most common used,
because of low initial investment, high quality final product,
fast and continuous production. Aluminum alloys which has
a narrow solidification range are preferred to produce with
twin roll casting and direct chill casting due to productivity
[1]. Flat finished product’s market share, which is manu-
factured for different thickness with cold rolling operation,
increase day by day.
Manufactured product’s surface texture is very critical for
end-use customers. The characteristics of the final product
operations specifications are determined by the customer
requests. Surface texture analysis should be examined where
Depending on the application, desired surface features can be
variable. Desired surface texture can be change with appli-
cation areas also. If we consider two using areas of aluminum
sheet such as composite panel industry and lithographic
offset industry, these two-different applications desire dif-
ferent surface quality and surface properties for their final
products. If we consider this situation, desired sheet metal
surface roughness of composite panel should be higher than
lithographic offset plate. Because of the desired adhesion
amount of ink and paint is changeable on the surface of sheet
metal. In addition to this mechanism, all equipment that
interacts with the contact interface (e.g. casting roll, pinch
roll, bridle roll, cold rolling mills, back up rolls, leveler rolls)
has an impact on the quality of the final surface texture.

C. Kuru
S.K. İpek
E. Dağdelen
Ö. Özşahin
A. Ulus (&)

Teknik Alüminyum A.Ş Çorlu, Tekirdağ, 59880, Turkey
e-mail: ali.ulus@teknikaluminyum.com.tr

© The Minerals, Metals & Materials Society 2017 833

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_101
834
Crack Formation Mechanism on TRC and Cold
Rolling Operation
Generally, lubricants are used for prevention of adhesion for
liquid metal on roll surface. Graphite is used as an antiad-
hesive interface area of aluminum casted strip and steel shell
surface. There is always water in the mixture of graphite
solution. Graphite and liquid metal are combined on the roll
surface. Therefore, cast rolls work under the thermal shocks.
Deformation force is applied with rolls to the nearly solidi-
fied sheet. After applied mechanical force on the roll,
deformation has occurred on casting strip while casting
operation. Some cracks are formed on surface of roll and
casting strip with thermal shock mechanism. These cracks
are increasing with working tonnage. Because of cracks
propagation on the casting roll surface, roughness of casting
strip increase in time. Because of raised number of cracks,
casting roll should be change also in time. On the cold
rolling operations, surface cracks form weak points because
of residual internal tensions of surface oxides. In this time,
this zones is breaking while enters of roll bite. Longitudinal
and transverse crack on the shell surface can be seen in
Fig. 1a and stretching of surface oxide between the interface
of cold mill and rolling strip can be seen in Fig. 1b, c.
All these studies have been worked about understanding
roughness changes during casting and cold rolling opera-
tions. In this study, roughness average values changes
(Ra) were investigated in casting and consecutive passes
performed material with the use of same casting and rolling
parameters. Furthermore, casting roll, material and work roll
of cold mill roughness changes with working length of
material has been investigated. Other parameters are kept
constant while examination of roughness changes relating to
working tonnage and passes changes.
Fig. 1 a Longitudinal and transverse crack on the shell surface b theoretical basics of surface oxide formation between the cold rolling bite,
c surface oxide formation after cold rolling [2, 3]
C. Kuru et al.
Experimental Studies
In this study, change of roughness is examined according to
the working tonnage of casting and cold rolling mills.
Samples are taken at the beginning and the end of the casted
alloys and after the roll change operation. In addition to one
sample was taken every one hundred ton of same alloys
casting campaign. Thus, the ratio of roughness was exam-
ined in the same alloys. In addition, investigations of
roughness were compared between 2 identical features
Fata-Hunter lines. The measurements have been taken from
the central part of the upper and lower surfaces of the sheets.
Ra values are examined after measurements of casting strips.
MahrSurf PS 1 digital profilometer is used for measure-
ment of surface roughness level of casted and cold rolled
strips. Measurements were transferred to the computer with
MahrSurf XR 20 software. During all measurements were pay
attention to the specified operation conditions [4]. Following
acquisition of the corresponding values, measurements were
made in the regions specified below Fig. 2 after cold rolling.
Received data from casting operation were analyzed with MS
Office Excel. Also, cold rolled strip data were analyzed by
MINITAB® 17 statistical analysis program.
For the cold rolling measurements, material and roll
surface were examined separately. Which is specified with
a–b–c–d and (1–2–3–4) regions represents the surface area
of the roll. Also 5 pieces of the roll surfaces represents the
working distance. Region which is specified number 1 is
represents the operator side, on the other hand, region which
is specified with number 5 represents the drive side. Mea-
surements are taken from each ninety-degree surface area
and each of five regions of this surface area of the work roll
measurements. Two measurements were taken from each
region of the work roll measurements.
Material Surface Roughness Change in Twin Roll Casting …
Fig. 2 The areas sampled by the work roll and material surface
Under all these circumstances;
• Samples are taken at the start and end of the all casting alloys
after change of the casting roll. In addition to one sample
was taken every one hundred ton of same alloys. Thus, the
ratio of roughness was examined in the same alloys.
• Casting sheets roughness are compared between the 2
identical features Fata-Hunter lines.
• Aluminum strip surface roughness and work roll rough-
ness changes of cold rolling work roll were examined
along the 98,000 km. Working alloy and percentage of
deformations are AA3003 and 33–35%.
• Average of roughness changes was compared from the
work roll, casting and rolling strips surfaces. Micro
images have taken and compared.
• Ra changes were examined which is only changing
variables are number of passes and amount of applied
deformation on material.
Results and Discussion
Roughness of the sheets were measured on the Novelis line
along the 3-casting roll change operation. Additionally,
roughness of the sheets was measured at each Fata Hunter
Graphic 1 Ra change (upper surface)—alloy and ra change (bottom surface)—alloy (Novelis line 1st cast campaign)
835
lines along the 1-casting roll change operation (Graphics 1,
2, 3, 4, 5, 6, 7, 8, 9 and 10).
If we consider the all casting series, increasing surface
roughness can be related to the amount of increasing
alloying elements or changes in the operational factors
which are performed depends on the different alloys while
casting operations. Graphite concentration is increased
approximately 20% while casting of aluminum strip which is
containing high concentration of alloy. This situation
decreases the thermal shock resistance of the roll surface.
Thus, crack formation increases on the rolling surface.
Normally this situation expected to increase the roughness
level of as cast strip. However, surface roughness is reduced
in all examined series. If we consider the other parameters
which is effects on strip roughness, piston pressure decreases
with increasing alloying elements because of increasing
mechanical strength of aluminum strip. Visual defects are
realized with decreasing surface roughness level. Because of
this situation, surface defects of aluminum strips become
evident. Due to the worsening of the surface properties,
casting roll should be change.
If we look at the highest and lowest values of the work
roll surface roughness, it appears to lose roughness level
during operation. Before and after images in Fig. 3 shows us
the changes of the work roll surface roughness level.
Roughness values of the work rolls change with operation in
836 C. Kuru et al.

Graphic 2 Ra change (upper surface)—roll tonnage and Ra change (bottom surface)—roll tonnage (Novelis line 1st cast campaign)

Graphic 3 Ra change (upper surface)—alloy and Ra change (bottom surface)—alloy (Novelis line 2nd cast campaign)

Graphic 4 Ra change (upper surface)—roll tonnage and Ra change (bottom surface)—roll tonnage (Novelis line 2nd cast campaign)

Graphic 5 Ra change (upper surface)—alloy and Ra change (bottom surface)—alloy (Novelis line 3rd cast campaign)
Material Surface Roughness Change in Twin Roll Casting … 837

Graphic 6 Ra change (upper surface)—roll tonnage and Ra change (bottom surface)—roll tonnage (Novelis line 3rd cast campaign)

Graphic 7 Ra change (upper surface)—alloy and Ra change (bottom surface)—alloy (Fata-Hunter line)

Graphic 8 Ra change (upper surface)—roll tonnage and Ra change (bottom surface)—roll tonnage (Fata-Hunter line)

Graphic 9 Ra change (upper surface)—alloy and Ra change (bottom surface)—alloy (Fata-Hunter line)
838 C. Kuru et al.

Graphic 10 Ra change (upper surface)—roll tonnage and Ra change (bottom surface)—roll tonnage (Fata-Hunter line)

Fig. 3 Statistical analysis of roughness of the work roll before and after cold rolling operation

comparison between before and after is approximately
20–43%. Both graphs about before and after comparisons in
the bottom rolling mills are seen lower roughness level than
top rolling mills (scale values are different). The change of
roughness values depending on the changing working meter
graphs was given in Figs. 4, 5 and 6.
The operation of each process in quantities of sampled
parameters of lubrication, roll status and material region
has tried to keep similar. Average parameters of cold
rolling during the process can be seen in Tables 1 and 2.
Only examination was carried out with depending on the
work surface feature. If we compare the cold rolling mill
and material surface roughness changes, it was seen that
start and finish roughness values are correlated with each
other. Bertrandie and Tornicelli has worked about surface
roughness changes with work roll working meter and
Material Surface Roughness Change in Twin Roll Casting …
Fig. 4 Image analysis on the measured area of worn cold rolling mill
Fig. 5 Roughness changes with working meter. Similar process occurs continously without stopping while cold rolling operation (excluding coil
change time)
they have found similar results with high reduction and
high speed, coefficient of friction decrease [5]. If roll
roughness decrease after working meter, working speed
and reduction is expected to decrease due to the forward
slip, it is the exact opposite where nominal reduction is
low [5, 6].
If we compare roughness level of aluminum strip with
changing deformations (Figs. 7 and 8, casting thicknesses
and nominal reductions of strip were similar), second passes
839
roughness of the bottom surface strip was examined higher
than the first passes. This situation was not observed on the
top surface. Several studies could be evaluated on this
subject. In contrast to the Mr. Beik and Denghani study [7],
second pass surface roughness was examined to be higher
values according to the first passes.
In this situation, coefficient of friction has to be higher on
second pass of bottom surface. If we estimate this situation,
the bottom oil film thickness between the interface of cold
840 C. Kuru et al.

Fig. 6 Roughness changes between the first and second passes (same amount of deformation between first and second passes) (43–41%)

Table 1 Average process Percentage deformation Mill speed (m/min) Roll force (kN)
parameters while operating
A3003 aluminum last pass 33–35% 125–291.8 2709.3–2
processing with new work roll Percentage bending Rolling oil temperature (°C) Percentage rolling oil flow rate
73.6% 30.1 54.0%

Table 2 Starting process Percentage deformation Mill speed m/min Roll force (kN)
parameters while operating
A1050 aluminum each pass 33–35% 10.2–18.3 2.884–2.910
processing with new work roll Percentage bending Rolling oil temperature (°C) Percentage rolling oil flow rate
98.3–99.7 27.8 54.0%

rolling mill and aluminum strip must be lower than the top
surface interface. The amount of the surface oil grab would
not be the same due to the flow direction of oil on the top
and bottom strip surface. The reason of the lack of roughness
changes of the top surface strip’s on first and second passes
could be described with oil grab and flow mechanism
changes due to the high surface roughness of the casting
strip. According to taken the surface micro-cracks images
before and after rolling operation’s study of H.R. Le and
Sutcliffe, surface oxide fracture could be deformation entry
and exit bite of the roll. Surface oxide could not breake
unstable on entry bite of the cold rolling roll, if thickness of
the oxide formation is too high on the aluminum strip [3].
For this reason similar results has been taken in first pass of
the casting strip on both side of the roll. Lubrication could be
hydrodynamic effect between the interface of the mill and
aluminum strip. But in the second pass, the aluminum strip
surface oxide has been broken and strip roughess is closer to
Material Surface Roughness Change in Twin Roll Casting …
/1 – Cast Strip
/1 - Top
/1 - Bottom
Fig. 7 The comparison of roughness changes between casting and cold rolling first pass surface
the roll roughness. In this time oil bearing capacity of the the
aluminum strip surface was decreased. Samples in Table 5
were processed in low speed (10.2–18.3 m/min). Whereas
desired oil thickness could be provided on the top interface,
on bottom interface could not be provided because of the
low process speed. The reason of the higher roughness level
of second pass is considered to be lubrication changes.
Comparison of the surface roughness changes macroscopic
841
/2 – Cast Strip
/2 - Top
/2 - Bottom
images can be seen in Fig. 8 (Magnification: 250x). If we
focus on the Fig. 8a images, we could see the surface
roughess changes on the bottom side. Also subjects of
lubricating effects on strips has been studied by K. Dick and
J.G. Lenard. For the better understand of changing rough-
ness level of the bottom strip and bottom roll surface should
be examined with samples are taken from high rolling speed
zones.
842
Fig. 8 a Comparison of aluminum surface roughness changes image of casting strip, first and second pass, b comparison of aluminum surface
roughness images of first and second passes (Magnification 250x)
Conclusion
1. 1050 alloy has the highest surface roughness of Novelis
and Fata-Hunter casting lines.
2. Surface of some samples in 1050 alloy castings of
Novelis line is the rougher. The estimated reason is
reduction of the pressure piston.
3. Roughness changes in the same alloy was examined. If
the amount of graphite is decreased, the roughness of the
sheet increase. If the amount of graphite is increased, the
roughness of the sheet decrease.
4. Rolls are cleaned while castertip changes in the casting
line. Therefore, surface roughness scale down.
5. Surface of some samples in 3105 alloy of Fata-Hunter
line is the rougher. The estimated reason is reduction of
the pressure piston.
6. 1050 alloy in the Fata-Hunter line has a higher casting
speed. Therefore, roughness of sheet raise.
7. Surface roughness level of twin-roll casting strip was
examined the decrease after first pass close to the cold
rolling mill surface roughness level. Cast strip surface
roughness was not detected the important effect on final
surface roughness except that upper and lower applica-
tion limits of cold rolling process parameters.
8. According to the cold rolling mill and aluminum strip
surface analysis which was graphed from 1650 roughness
average data of AA3003 twin-roll cast aluminum strip, cold
rolling mill and aluminum strip surface average roughness
C. Kuru et al.
level was examined to decreases with roll working meter
with specified rolling parameters. Closing the 80 km the
roll and material surface roughness decreasing approxi-
mately 43% with specified operation parameters.
9. Average roughness changes depending on the amount of
deformation was examined. However, it is observed that
first and second pass surface roughness is changing due
to the low rolling speed and insufficient oil film thickness
between the interface area.
References
1. Z. Sirel, M. Usta, Ö. Keleş, M. Dündar, Grain Growth In AA3XXX
Series Alloy Produced By Twin Roll Casting Method, 3 (Aluminum
symposium, Gebze, 2007)
2. M. Dündar, B. Beyhan, O. Birbaşar, H.M. Altuner, C. Işıksaçan,
Surface Crack Characterization of Twin Rol Caster Sheels And
Influence On As-cast Strip Surface Quality. Light Met. 2013, 491–
496 (2013)
3. H.R. Le, M.P.F. Sutcliffe, P.Z. Wang, G.T. Burstein, in Surface
Oxide Fracture in Cold Aluminium Rolling (Acta Materialia, 2004),
pp. 911–920
4. Mahr GmbH, Catalogue No: 3757977 Göttingen, pp. 8–9
5. K. Dick, J.G. Lenard, The effect of roll roughness and lubricant
viscosity on the loads on the mill during cold rolling of steel strips.
J. Mater. Process. Technol., 16–24
6. J.G. Lenard, The effect of roll roughness on the rolling parameters
during cold rolling of an aluminum alloy. J. Mat. Process. Technol.
152, 144–153 (2004)
7. H.A. Ali Beik, K. Dehghani, irregularity in friction hills durin the
cold roling of materials. Int. J. Mater. Form., 343–346 (2008)
 Twin-Roll Casting of Aluminum-Steel Clad
Strips: Static and Dynamic Mechanical
Properties of the Composite

M. Stolbchenko, O. Grydin, and M. Schaper

Abstract
The manufacturing of thin aluminium-steel clad strips by means of twin-roll casting is a
prospective trend of the progress in the light metals sheet production. The resulting
composite possesses high bonding strength due to the presence of a continuous thin layer of
intermetallic phases at the bonding interface of metallic constituents. At the same time, for
the application of twin-roll cast clads, the evaluation of their properties is of great
importance. In order to determine the behavior of twin-roll cast aluminum-steel clad strips
under loading, monotonic tensile and fatigue tests were carried out. Therefore, strips in the
as-cast condition as well as after a heat treatment, stimulating the growth of the
intermetallic phases, were subject for the characterization. In addition, the specimen’s
fracture surfaces were analyzed using scanning electron microscopy to obtain information
on the type of fracture, the location and source of the crack nuclei.

Keywords
Twin-roll Casting Clad strip Aluminum-steel Fatigue

Introduction
Clad products made of dissimilar materials finding a wide
application in the different branches of modern industry.
Among them can be highlighted the transport machine
building, chemical industry, offshore and civil building. The
main feature of clad materials is a set of properties typical for
its constituents combined in a single product. In case of
aluminum-steel composite these properties are high strength
and ductility, excellent corrosion resistance, and heat and
electric conduction, good weldability.
Besides the well-known technologies for production of
flat clad products, such as roll bonding, explosion bonding
M. Stolbchenko (&)
O. Grydin
M. Schaper
Chair of Materials Science, Paderborn University,
Warburger Str. 100, 33098 Paderborn, Germany
e-mail: stolbchenko@lwk.upb.de
O. Grydin
e-mail: grydin@lwk.upb.de
M. Schaper
e-mail: schaper@lwk.upb.de
and welding, the twin-roll casting [1] can be used to man-
ufacture clad strips directly from the melt. This technology is
used over the last years for production of strips of different
steel grades [2], aluminum [3, 4], magnesium [5] alloys and
other metals. The main advantage of twin-roll casting is
possibility to exclude the intermediate heating steps from
the thin strip production chain. This allows reducing of
construction and production costs, energy and material
consumption as well as decreases harmful pollutions.
Application of the twin-roll casting for production of clad
strips gives in turn additional advantage consisting in min-
imization of surface treatment of bonding materials.
Nowadays, the manufacture of clad strips by means of
twin-roll casting is limited on the laboratory scale. The
investigations of this process are mostly carried out for the
one group of materials or for materials having similar
melting points. In this case, all the layers of clad strip are
consequently twin-roll cast from their melts. Haga et al. [6, 7]
show the use one-, twin- and triple-roll casters for production
of clad strips consisting of different aluminum alloys.
Two- and three-layer strips are produced at the casting

© The Minerals, Metals & Materials Society 2017 843

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_102
844
speeds up to 40 m/min. The strips have a good bonding
strength due to the thermal activation of diffusion processes
between aluminum alloys during the casting.
In [8] a manufacture of clad strip of high manganese steel
with an austenitic stainless steel by means of twin-roll
casting is shown. A sound bonding between the strip layers
is reached by partial melting of material at the contact
interface. The application of dissimilar materials for manu-
facturing of clad strips by means of twin-roll casting is
demonstrated in [9]. Molten magnesium alloy was fed
between two 50 µm thickness foils of pure aluminum in a
horizontal twin-roll caster. Metallographic analyses showed
the presence of a layer of intermetallic phases at the interface
of the heterogeneous materials and a partial melting of the
aluminum foils occurred. The first studies on cladding of
materials with significantly different melting points by means
of twin-roll casting were carried out by Grydin et al. [10].
Thin aluminum-steel clad strips possessing a total thickness
of 3 mm were produced using a vertical twin-roll caster.
Analysis of the metals bonding zone showed the presence of
a thin continuous layer of intermetallic phases. Bonding
strength exceeding 70 MPa were measured based on tensile
adhesive strength tests results.
Along with the properties of the composite layers the high
characteristics of the product are ensured by the tough
bonding between them. This allows the layers to resist
together under different loading conditions during produc-
tion and service life. For the complex characterization of
new composite material and evaluation of its application
potential the mechanical tests have to be carried out. The
tensile tests can give conclusions about material’s use limits
determining the ultimate strength and elongation at fracture.
In turn, the testing under cyclic loading can complement the
material characterization while in application dynamic loads
are usually dominant.
The fatigue resistance is one of the most important fea-
tures of construction materials. For conventional materials,
such as aluminum and steel, this has already been exten-
sively studied, for example in works [11, 12]. However, the
combination of two different materials in a flat product under
cyclic loading differs substantially from the theoretical pre-
diction and the behavior of the individual materials. Such
effect was mentioned in works dedicated to the investigation
on fatigue behavior of multilayer structures [13–17]. The
composition of materials as usual has higher mechanical
characteristics than its constituents apart. Evaluation of ser-
vicing features, i.e. the fatigue strength and life prediction,
for the multimaterial structures made by means of thermal or
deformational methods is seen to be one of the important
tasks in modern science [18, 19].
It was investigated [20] that the structure of bonding zone
between two steel grades in an explosive bonded strip car-
dinally changes the character of crack propagation in the
M. Stolbchenko et al.
clad under the cyclic loading. The growth of the inter-
metallic phases on the bonding interface between dissimilar
materials also leads to changes in the crack propagation
mechanism. On the example of friction-stir welded alu-
minum and steel plates was shown [21] that the layer of
Fe–Al intermetallics plays a decisive role in the strength
of the joint. Moreover, dependent on the layer thickness of
intermetallics the crack propagated either in the bonding
zone or in the base material. The intermetallic phases of
Fe–Al system [22–24] due to their brittleness can initiate the
formation of cracks at the inner surfaces of the strip layers
[25]. Moreover, in aluminum-steel joints the crack will
probably propagate through the brittle layer of intermetallic
phases than across the base material [26]. Pores, inclusions,
inhomogeneity and other defects at the contact surface
between the bonded metals can serve as nuclei for the for-
mation of cracks [15, 27, 28]. On the other hand the soft and
ductile interlayer can serve as a crack stopper in multilayer
structures [13, 14].
An investigation of the fatigue behavior of roll bonded
strips of 6016 aluminum alloy and FeP06 steel was carried
out in [29]. The properties of clads were tested under static
loading as well as under low- and high-cycle fatigue. The
fatigue life of the composite was established comparing with
its basic materials. The clad strip showed higher fatigue
strength than the predicted value based on the rule of mix-
ture. In all the tests the crack grew in steel from the bonding
zone between two metals.
The microstructure of the aluminum layer also signifi-
cantly affects the properties of the composite. First of all, the
residual cast structure and casting defects that are charac-
teristic for the twin-roll cast strips serve as crack nuclei and
have a negative influence on the fatigue strength [11, 30].
Against this background, the more intensive study of the
mechanical properties and fatigue behavior of the twin-roll
cast aluminum-steel clad strips are of great scientific
importance.
Experimental Procedure
Two-layer aluminum-steel clad strips were utilized for the
experimental investigation. As strip materials technical pure
aluminum EN AW-1070 and austenitic stainless steel 1.4301
were used. The strips were twin-roll cast using vertical caster
of the Chair of Materials Science at Paderborn University
[31]. The laboratory caster had two steel rolls, each with a
diameter of 370 mm and a 200 mm barrel length. The
experimental unit was additionally equipped with an
uncoiler for the steel substrate, a device for its feeding, as
well as with a puller for the finished clad strip. During the
experiments, the melt of pure aluminum was fed into the
twin-roll caster together with a solid substrate of stainless
Twin-Roll Casting of Aluminum-Steel Clad Strips …
austenitic steel clasped to one of the casting rolls (see
Fig. 1). After the complete solidification of the aluminum
layer between two internally cooled rolls, the clad strip was
plastic strained in the deformation zone (see Fig. 1) and left
the caster. The main parameters of the twin-roll casting used
in the experiment are listed in Table 1.
The twin-roll cast aluminum-steel clad strip with con-
tinuous bonding of layers and without significant casting
defects was taken for the further analysis. The specimens for
mechanical testing as well as for metallographic analysis
were sampled from the clad strip at a distance of about 6 m
from its emerging end. A section of the clad strip was sub-
jected to heat treatment to initiate the diffusion between the
aluminum and steel layers. Thus the composite material was
annealed in a furnace at 400 °C for 2 h utilizing a protective
gas atmosphere and subsequently cooled on the air. The
annealing temperature was chosen based on the results of
[32, 33]. Here the range between 400 and 450 °C was
determined as a start temperature for the growth of Fe–Al
Fig. 1 Basic schematic of the
twin-roll casting of
aluminum-steel clad strips
Table 1 The main twin-roll Process parameter
casting process parameters
Initial temperature of the steel substrate (°C)
Aluminum melt temperature (°C)
Steel substrate thickness (mm)
Total thickness of the clad strip (mm)
Casting speed (m/min)
Clad strip reduction in twin-roll caster (%)
Coolant flow rate (l/min)
Coolant temperature (°C)
845
intermetallic phases. At the same time the range of sensiti-
zation temperatures for austenitic stainless steel lies above
400 °C [34]. To avoid the reduction in the properties of steel
layer, the lowest temperature of the diffusion process start
range was chosen for the heat treatment.
For the characterization of intermetallic bonding between
the clad strip’s layers the microsections in the rolling
direction were prepared both in the as-cast condition as well
as after the heat treatment. The samples were stepwise
grinded and fine polished using 1 µm silicon dioxide paste at
the final stage. The prepared samples were analyzed using
scanning electron microscope (SEM) Zeiss Ultra Plus,
equipped with a secondary electron (SE) and energy-
dispersive X-ray spectroscopy (EDX) detectors.
Evaluation of mechanical properties of the composite was
carried out by means of uniaxial quasi-static tensile tests as
well as fatigue tests. All the tests were performed at a room
temperature using small dog-bone specimens having a width
and a length of machined section of 3 and 8 mm
Value
20
700
0.5
2.1
5.1
40
110
14
846
Fig. 2 26 mm length dog-bone specimen used in the mechanical
testing: RD, TD rolling and transversal direction at twin-roll casting
respectively. The specimens were sampled from the clad
strip sections by means of electro-discharge machining. The
loading direction of all specimens coincided with the initial
twin-roll casting direction (see Fig. 2). In order to remove
surface unevenness and defects, the edges of samples were
ground down to a grit size of 5 lm prior to the actual
experiments. The tests were conducted on a MTS 858 table
top system allowing maximal loading of 15 kN in both
tension and compression directions.
In the first series of experiment the tensile tests at a
constant strain rate of 0.001 s−1 were carried out. The
specimens of the clad strip in as-cast condition and after
the heat treatment were tested. For the comparative analysis,
the specimens of constituent materials, twin-roll cast pure
aluminum and austenitic steel 1.4301, were also subjected to
the tensile testing.
In the second series of the experiments the strain-based
low-cycle fatigue analysis of the clad strips was made. The
specimens in as-cast conditions and after the heat treatment
were used in the series. The fully reversed cycle loading with
R = 0 at a constant strain rate of 0.006 s−1 was applied to the
specimens. The total strain amplitude De/2 was equal to
±0.25 and ±0.5%.
In the third series the stress-based high-cycle fatigue
analysis of the clad material was performed. The specimens
were tested using relation R = rmin/rmax = 0, so the stress was
fluctuating from zero to its maximum. Such relation was
conditioned by the unstable behavior of thin strip material
under the high values of compression loading. The stress
amplitude ra was varied from 50 to 90 MPa during the
experiments. The frequency of cyclic loading amounted 5 Hz.
After the quasi-static and fatigue tests the fracture surface
of the specimens was analyzed by means of electron
microscopy. The scanning electron microscope Zeiss Ultra
Plus with SE-detector was used for this purpose.
Results and Discussion
Twin-Roll Casting of Clad Strips
The SEM microsection in Fig. 3a obtained using
SE-detector shows the bonding zone of the clad strip after
the twin-roll casting. Neither large oxide particles in the
M. Stolbchenko et al.
fusion zone nor any delamination between the layers are
discernable. Corresponding distribution of the relevant
chemical elements, as determined by EDX, is shown in
Fig. 4. The EDX analysis of bonding zone reveals presence
of a thin uniform layer with a thickness less than 1 µm in the
interface, indicative of an intermetallic phase of the Fe–Al.
Such bonding character indicates on the good interaction
between aluminum and steel and ensures a high bonding
strength between the strip layers [10]. The microsection of
the strip after the heat treatment is depicted in Fig. 3b. As
can be seen, no delaminations or active growth of the
intermetallic phases observed in the bonding zone compar-
ing with a strip in as-cast condition. It can be concluded that
for the intensive growth of the Fe–Al phases between pure
aluminum and stainless steel 1.4301 the temperatures above
400 °C are strongly required. At the same time the negative
effect of formation of the brittle intermetallics layer above
5 µm thickness by annealing at 400 °C can be excluded.
Quasi-Static Tensile Testing
The influence of the heat treatment on the mechanical
properties of the clad strips was analyzed during the tensile
tests. The averaged values of mechanical properties of the
strips in as cast condition and after the heat treatment are
given in Table 2. The corresponding stress-strain curves of
the composite material in the both conditions as well as of its
constituents are shown in Fig. 5.
An atypical form of the initial section of the stress-strain
curves of composite material can be noticed in Fig. 5. The
transition from the elastic to plastic strain passes in two
stages. At a low stress the both layers are elastic strained
together. After reaching the ultimate tensile strength of
aluminum the curve makes a deviation and passes into
another straight section. This section corresponds to the
beginning of the plastic strain in the steel layer. After
reaching of yield strength of the steel the curve flows further
showing strain hardening of the whole composite to the
maximum values of 228 MPa of tensile strength and 39%
elongation at fracture. The heat-treated material shows a
slightly lower strength but simultaneously a higher ductility.
This can be explained as withdraw of work-hardening in
composite during annealing.
The fracture surfaces of the specimens in as-cast as well
as annealed conditions after the tensile tests obtained using
SEM are shown in Fig. 6a, b.
The fractured surface of both layers have characteristic
dimple path indicating the ductile fracture. A difference
between the end cross section prior to the fracture of spec-
imen can be also mentioned. Such necking in the annealed
material ensures its higher elongation at fracture measured
during the experiments. At the same time, a clear
Twin-Roll Casting of Aluminum-Steel Clad Strips … 847

a Steel b Steel

10 μm Al 10 μm Al

Fig. 3 SEM micrographs of the bonding zone of the twin-roll cast clad strip: a in as-cast and b in annealed condition

Fe/Cr/Ni
Al/Fe/Cr
5 μm Al

Fig. 4 Distribution of the chemical elements in the bonding zone between the layers of clad strip in as-cast condition obtained using EDX analysis

Table 2 Mechanical properties of the twin-roll cast strips obtained during the tensile tests
Specimen condition Yield strength (MPa) Ultimate tensile strength (MPa) Elongation at fracture (%)
As-cast 86 228 48
Cast and annealed 63 220 56

700

600

Steel 1.4301
500
Composite, as-cast
Stress, MPa

400 Composite, annealed

Aluminum EN AW-1070
300

200

100

0
0 10 20 30 40 50 60
Strain, %

Fig. 5 Stress-strain diagram of the twin-roll cast strips and their constituent materials under the monotonic tensile loading

a Steel b Steel

Al Al

Fig. 6 Fracture surface of the composite material after the tensile test in as-cast (a) and annealed (b) conditions
848 M. Stolbchenko et al.

delamination of the strip layers can be seen on the both outer surface to its core. Moreover, numerous striations were
specimens. However, the propagation of delamination crack detected indicating the crack propagation in aluminum layer
is restricted only in the fracture zone and the clad material in towards the bonding zone (see Fig. 9). Simultaneously, with
whole retains its stability. cracks that overcame the bonding zone they origin from

a Steel
Low-Cycle Fatigue Testing

For the investigation of material behavior under cyclic

loading in the range above the yield strength the low-cycle
fatigue tests were performed. The obtained hysteresis loops
at the half-life cycles for the material in as-cast and annealed
condition are shown in Fig. 7.
The annealed material shows poorer ductility that can be
seen from the hysteresis loop width. During the initial stage
of LCF tests the specimens showed facility to the strain
hardening. In the second stage, approximately after reaching Al
of half-life loading cycle all the specimens softened and
broke showing ductile fracture behavior.
b Steel
In order to determine the crack initiation point as well as
crack propagation direction a fracture surface analysis was
performed using the specimens after the fatigue tests. The
specimens in as-cast condition after the LCF-tests with total
strain amplitude of ±0.25 and ±0.5% are shown in Fig. 8a, b
correspondingly. The areas of both fatigue and forced
fracture can be detected on the specimens’ surfaces. In both
samples in Fig. 8 the crack in the steel layer was initiated at
the edge of the bonding interface with aluminum layer. No
delamination occurred in the clad material prior to the forced
Al
fracture. Due to the tough bonding in the specimens in as-cast
condition the crack overcame the bonding zone and propa-
gated simultaneously in the both layers. Analyzing the form
of striations in aluminum layer, the crack growth direction Fig. 8 Fracture surface of the composite in as-cast condition after the
was determined. The striations on the fracture surface of low-cycle fatigue test with total strain amplitude of De/2 = ±0.25%
aluminum show the crack propagation from the specimen’s (a) and De/2 = ±0.5% (b)

150

100 Bonding interface

50
Stress, MPa

0
-0,5 -0,3 -0,1 0,1 0,3 0,5

-50
As-cast ε/2 = ±0.25%

-100 Annealed ε/2 = ±0.25%

As-cast ε/2 = ±0.5%
-150 Annealed ε/2 = ±0.5%
Al
Strain, % 50 μm

Fig. 7 Half-life hysteresis loops for the aluminum-steel composite in

as-cast and annealed conditions under cyclic loading with total strain Fig. 9 Striations on the fractured surface of aluminum layer showing
amplitudes of De/2 = ±0.25% and De/2 = ±0.5% the crack propagation towards the bonding zone
Twin-Roll Casting of Aluminum-Steel Clad Strips … 849

numerous sources on the aluminums’ outer surface. Ana-
lyzing the form of fractured specimens, it was established that
the forced fracture occurs first in the aluminum layer and at
least in the steel layer.
An intensive delamination between the layers can be
observed in the annealed clad strips (see Fig. 10) comparing
with the specimens in as-cast condition. This affected the
independent crack propagation in each of the strip layers.
The crack in steel layer grew from the bonding interface,
whereas the cracks in the aluminum layer started from the
outer surface of the specimen. Analogous to the as-cast
strips, the fracture of steel layer followed after the complete
partition of aluminum layer.
The crack sources and their growth direction were studied
in detail. The image in Fig. 11 shows the bonding surface in
the specimen in as-cast condition fractured under cyclic
loading with stress amplitude of ±0.25%. From Fig. 11a can
be seen that the transversal crack in the steel layer served as
an additional fracture initiator. In Fig. 11b numerous crack
propagations into the steel layer from the bonding interface
can be observed.
So the intermetallic bonding layer between the clad strip
layers can serve as a source for cracks under the cyclic
loading. At the same time, a delamination between the layers
during loading leads to the independent crack propagation in
the strips layers. So influencing the thickness and mor-
phology of the bonding layer, and consequently the bonding
strength, the conditions for minimal crack initiation and joint
resistance of the layers to the loading can be achieved in the
clad strips.
High-Cycle Fatigue Testing
Further material characterization was made under the cyclic
loading with low stresses. Due to the minor change in the
properties of composite after annealing only strips in
the as-cast condition were subject of this experiment. On the

a Steel

Al

b Steel

Al

Fig. 10 Fracture surface of the composite in annealed condition after the low-cycle fatigue test with total strain amplitude of De/2 = ±0.25%
(a) and De/2 = ±0.5% (b)
850 M. Stolbchenko et al.

Fig. 11 Fractured surface near

the bonding zone of the clad strip a b Steel
in as-cast condition after the
cyclic loading with strain
amplitude of ±0.25%.
a Transversal crack, b crack
sources

Al

180
90 during the low-cycle fatigue testing. The as-cast strips show
170 higher strength than the ones in annealed condition. The
Stress amplitude σa, MPa

160
80 fracture surface analysis showed that in the as-cast strips
150 the crack propagates in the both layers consequently. In the
70
140 annealed strips due to the lamination between the layers the
130 cracks grow independent in the steel and aluminum layer.
60
120 The sources of the crack initiation were found in a bonding
110
layer as well as at the aluminum surface. The fatigue limit
for the twin-roll cast clad strip determined during high-cycle
50
100
1E+04
10 4 1E+05
10 5 1E+06
106 1E+07
10 7 fatigue tests corresponds to stress amplitude of 51 MPa.
Cycles to failure (log)
Acknowledgements The authors would like to thank the German
Fig. 12 S-N diagram of aluminum-steel composite under pulsating Research Foundation (DFG) for their financial support for the scientific
tensile stress work carried out here within the scope of the project SCHA1484/21-1
“Production of aluminum-steel clad strips by means of twin-roll casting”.

results of performed HCF-tests the S-N diagram was built

(see Fig. 12).
As can be seen from the S-N diagram, the fatigue life of
composite increases with reduction of stress amplitude and
at ra = 51 MPa material reaches the fatigue limit by
N = 107 load cycles.
Conclusions
Two-layer aluminum-steel clad strips were manufactured by
means of twin-roll casting. The strips have a continuous
strong bonding between the layers provided by thin diffusion
layer on the bonding interface. The properties of the bonding
layer can be influenced during heat treatment at the tem-
peratures of 400 °C and higher. Under the tensile tests the
clad strips reached the highest ultimate tensile strength at
228 MPa in as-cast condition. At the same time, the best
value of elongation at fracture at 56% was reached by
composite after annealing. The same tendency was observed
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 Part XX
Cast Shop Technology:
Foundry and Shape Casting
 Multi-Component High Pressure Die Casting
(M-HPDC): Influencing Factors on the Material
Temperature During the Joining
of Metal-Plastic-Hybrids

Patrick Messer, Uwe Vroomen, and Andreas Bührig-Polaczek

Abstract
M-HPDC is an In-Mold manufacturing process combining High Pressure Die Casting
(HPDC) and Injection Molding (IM) within one manufacturing plant. The biggest influence
within a metal-plastic-bond realized by micro bracing is ascribed to a suitable temperature
management in the die. Therefore a suitable temperature control concept for a sample die,
made to manufacture an overlap shear tensile sample, will be presented. In order to
investigate the temperature influence, the die provides several options to influence the
actual temperature. A number of independent cooling circuits, an alternating temperature
management unit and a contour adapted heating cartridge are integrated. Besides that, the
temperature within the joining area can be raised by exchangeable die inserts for the usage
of either an inductor or a heating ceramic. For the purpose of quantification, the temperature
will be monitored by thermocouples close to the actual cavity surface. The die concept and
first results of the simulative approaches will be shown.

Keywords
Hybrid Multi-Component Process combination Joining method

Introduction
Innovative products often request innovative materials. For
various applications, material specifications are demanded,
that cannot be provided just by one material, with the result,
that different materials need to be combined. In order to use
the favorable properties of different materials, joining pro-
cesses are necessary, that allow combining both materials.
In-Mold-Assembly and Post-Mold-Assembly
Joining processes for plastic-metal-hybrids can generally be
divided in In-Mold-Assembly (IMA) and Post-Mold-
Assembly (PMA) processes. During the PMA-process, the
production of both joining members is conducted independent
of the actual joining process as for example gluing, welding or
riveting. Regarding the IMA-process on the other hand, the
P. Messer (&)
U. Vroomen
A. Bührig-Polaczek
Foundry-Institute, RWTH Aachen University, Aachen, Germany
e-mail: p.messer@gi.rwth-aachen.de
primary shaping of the second component is also used for the
joining of both components. In this way, the process chain is
shortened by one step and more extensive designs become
possible. However, the effort for the manufacturing of the first
component is still high, since mostly sheet metal stamped parts
are used, which necessitate several process steps up to the
point at which they are prepared for joining with the second
component. Typical applications range from small items with
overmolded conduction parts up to bumpers of the front end in
cars [5]. Analogously, the IMA of sheet metal inserts with the
HPDC-process is possible as well [3, 7].
Multicomponent technologies, combining the primary
shaping of two or more plastic components within one die,
already are state of the art and are used for series applica-
tions [2, 4]. Die technologies as e.g. turning or index plates
are used for multicomponent applications and are well
established on the market. This way, two or more plastic
components can be primary shaped and joined in the same
die using a multistage process. Comparable applications for
exclusively primary shaped plastic-metal-hybrids, which are
ready for series production, still do not exist.

© The Minerals, Metals & Materials Society 2017 855

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_103
856
Restrictions of Current Processes
Due to high investment costs for permanent molds and
machinery, both HPDC and IM are usually just economic for
high quantities. Therefore, permanent molds often need to
sustain more than 100,000 cycles [2].
M-HPDC: Combining High Pressure Die
Casting and Injection Molding
In order to raise the productivity, the effort for the manufac-
turing and handling of the first component needs to be mini-
mized. A promising possibility regarding large scale
production is the combination of high pressure die casting
(HPDC) and injection molding (IM) within one process. Both
are well automatable processes for large scale production
series and are well established on the market. Furthermore the
basic setup of IM- and HPDC-machines has several analogies.
M-HPDC, a combination of IM and HPDC, is the con-
sequent continuation of the shown state of the art in indus-
trially established manufacturing processes. In terms of the
Cluster of Excellence “Integrative Production Technology
for High-Wage Countries” the M-HPDC process is being
developed at the Foundry-Institute of RWTH-Aachen
University, Aachen, Germany. M-HPDC is based on a
HPDC-machine, extended by an injection molding unit
mounted in L-position. An exemplary HPDC-machine
extended by an IM-unit is shown in Fig. 1.
Process Operation
Alike the extension of the machinery, the process cycle of
the HPDC process needs to be extended by an IM process.
IM-Unit
Fig. 1 HPDC-machine extended by an IM-unit
P. Messer et al.
die opened
ejection slider movement
(HPDC position)
die opened
injection molding spraying
die closed
slider movement
(IM position) die filling
Fig. 2 Cycle of the M-HPDC-process
Figure 2 shows the cycle of the M-HPDC process which will
be used for the planned die.
Starting from the open die, the slider first moves to the
HPDC-position. After applying the separating agent by
spraying, the die closes and the aluminum cavity gets filled.
In order to move the slider towards the IM-position, the
locking force of the HPDC-machine needs to be reduced. As
soon as the IM-position of the slider is reached and the
locking force is applied again, the plastic gets injected by the
IM-unit, whereby the bond is generated. Finally, the die
opens and the specimen gets ejected, which conclusively just
needs to be separated from the aluminum and plastic runners.
Challenges due to the Combination of HPDC
and IM
Besides several similarities between HPDC and IM, differ-
ences occur especially with regard to the processing tem-
perature for plastic and aluminum melts and the required die
temperatures. The injection temperature of aluminum is
usually kept between 700 and 750 °C, while thermoplastics
(PA6) are mostly processed between 260 and 290 °C. Fur-
thermore, the die temperatures for the processing of alu-
minum (100–300 °C) are usually higher than for plastics
processing (PA6: 40–100 °C) [6].
These differing demands regarding the temperature need to
be integrated in one die in order to realize the M-HPDC pro-
cess. The developed concept and the results of the first simu-
lative approaches will be shown in the following chapter.
Temperature Control Concept
Recent researches, using the specimen geometry of an
“Erlanger Träger” (Hybrid-II) prompted questions regarding
the influencing factors on the bond strength. The investiga-
tions indicated that the major impact is given by the tem-
perature in the joining area [1]. In consequence, the
Multi-Component High Pressure Die Casting (M-HPDC) … 857

specimen geometry of the new Hybrid-III die is kept as Circuit C

simple as possible in order to focus on this fact. Since
multiple possibilities are integrated to influence the tem-
perature of die and specimen, a brief overview of the general Circuit B
die setup will be given first, before going into the details of
the temperature management setup.
Circuit A

General Setup of the Die

Isolation Circuit C
The die is set up modular, basically consisting of the die
frame and die inserts (Figs. 3 and 4). Furthermore a modular Fig. 4 Detailed view of die inserts and positioning of the cooling
slider with exchangeable cavity plates is integrated in the circuits in the movable (left) and fixed die half (right)
movable die half and a sub insert is provided in the fixed die
half. By this setup, the qualification of a heating ceramic and
an inductor can be tested by using individual die inserts in
the fixed die half, adapted for the particular application. Circuit B Circuit B
These heating possibilities are used in order to raise the
temperature of the joining area just before the actual joining
process. Furthermore, changes of the cavity geometry as
well as changes of the contour adapted temperature control
circuits become possible without any great effort. Inductor Heating
Ceramic

Arrangement of Tempering Possibilities

As already mentioned, the die has several tempering possi- Fig. 5 Sub insert with inductor (left) and heating ceramic (right)
bilities in order to realize a defined adjustment of the tem-
perature in the joining area. Figure 4 shows the positions of
the four cooling circuits. One is positioned in the movable (B) and one in each half of the slider (C and D). Two of the
die half (A), one in the sub inserts of the fixed die half cooling circuits (B and C) can be fueled with water, which
allows a faster heat removal compared to oil. Since the
maximum temperature of water is limited due to the vapor
Additional Runner for
pressure, circuits A and D definitely need to be fueled with
Cavity Additional Cavity oil. Furthermore, every circuit can be set independently,
(Aluminum) (Plastic) allowing a precise adjustment towards the differing demands
Plastic Cavity of plastics and aluminum.
The temperature in the joining area can be raised locally
using heating elements. Therefore, two exchangeable sub
inserts provide either a heating ceramic or an inductor
(Fig. 5) and a contour adapted heating cartridge is integrated
in the vertical slider underneath the aluminum cavity
(Fig. 6).

Heat Input of the Melt

Besides inductor, tempering circuits, heating cartridge and

heating ceramic, another crucial factor is the heat input by the
Aluminum
Cavity Locking Mechanism for Silder
plastic and aluminum melt itself. Due to the size of the shot
chamber and the IM-unit, for both, aluminum and plastic, an
Fig. 3 General setup of Hybrid-III: movable (left) and fixed die half additional cavity is necessary in order to keep the shot weight
(right) on a level, which can be processed reproductively by the
858 P. Messer et al.

available machinery. Each cycle, around 1500 g of aluminum
and around 40 g of plastics are processed, so that the heat
input especially of the aluminum melt cannot be neglected.
The additional aluminum cavity is kept as far away from the
specimen as possible in order to minimize the influence.
Notch for Thermocouples Circuit C
Groove for Contour
Circuit D Adapted Heating Cartridge
Fig. 6 Setup of the slider with an integrated contour adapted heating
cartridge
Simulation of Heat Distribution
Since multiple possibilities are integrated in the die to
influence the temperature, a simulation of the heat distribu-
tion is essential. MAGMA 5® is used for the simulative
description of the die and the aluminum component, because
especially the thermal conditions of the joining area are of
interest during the moment the plastic melt first comes in
contact with the aluminum component.
The parameters shown in Table 1 lead to a temperature
distribution, which meets the particular local requirement of
both materials. The simulation shows, that an inlet temper-
ature of 150 °C (circuit A) is sufficient to suppress the
thermal influence of the additional part towards the actual
specimen. In this way, just 25 s after injecting the aluminum,
a sufficient solidification of the mass concentration in the
additional part is reached, with the result that the locking
force can be reduced for the slider movement. Taking into
account that the plastic component can be injected around
10 s later, the temperature distributions of the specimen after
25 and 35 s are shown in Fig. 7. The figure shows, that the
temperature in the entire joining area of the specimen is
around 170 °C after 35 s even without using any of the
additional heating possibilities. Since the results, shown in

Table 1 Parameters of the Circuit A B C D

tempering circuits
Medium Oil Oil Water Oil
Inlet temperature (°C) 150 150 90 150

Fig. 7 Temperature distribution

of the aluminum component 35 s
after filling (left) and 25 s after
filling (right)

Joining Area
Multi-Component High Pressure Die Casting (M-HPDC) …
Brecher et al. [1], suggest that a joining temperature of
180 °C or more leads to good bonds, the value of 170 °C
constitutes a reasonable temperature as the lower initial
value. Furthermore, Brecher et al. [1] also show, that the
substrate around the joining area has to be kept on a similar
high temperature level as well, to suppress a heat flow away
from the joining area. According to Fig. 7 this is also
achieved.
Conclusion and Outlook
For the intended bond, the major impact on the bond
strength is given by the temperature management. The die
has a wide range of integrated tempering possibilities,
allowing a precise adjustment of the local temperature dis-
tribution. The results of the first simulative approaches show,
that the temperature drop of the specimen between HPDC
and IM is kept in reasonable limits, even without using the
additional heating possibilities.
Based on the current status, further simulations will be
used to define the necessary power and the final shape as well
as the final position of the heating ceramic and the inductor.
Furthermore, the accurate placement of the thermocouples
needs to be determined in order to enable a validation after
manufacturing the die and to use those for the quantification
of the temperature in the joining area during testing.
859
Acknowledgements The authors would like to thank the German
Research Foundation DFG for the kind support within the Cluster of
Excellence “Integrative Production Technology for High-Wage Countries”.
References
1. C. Brecher, S. Kozielski, L. Schapp, Integrative Produktionstechnik
für Hochlohnländer. (Springer, New York, 2011). doi:10.1007/978-
3-642-20693-1
2. A. Bührig-Polaczek, W. Michaeli, G. Spur, Handbuch Urformen.
(Carl Hanser Verlag GmbH & Co. KG, 2014)
3. B. Lao, Druckgegossene Metallhybridstrukturen für den Leichtbau-
Prozess, Werkstoffe und Gefüge der Metallhybriden. (RWTH
Aachen University, 2013)
4. W. Michaeli, O. Grönlund, A. Neuss, u. a, Mehrkomponententech-
nik: Neuer Prozess für Kunstoff-Metall-Hybride. Kunststoffe 9/2010
5. N.N., Kombinierte Automobil-Bauteile durch Metall-Tiefziehen
und Spritzgießen Frontendfertigung in Hybridtechnologie.
Plastikverarbeiter 51(12) (2000)
6. G. Schenke, New hybrid molding process for good adhesion and
increased functions of metal/plastic composite parts. Paper pre-
sented at the TMS 2014 annual meeting and exhibition, San Diego,
USA, 15–22 Feb 2014
7. G. Schenke, D. Joop, A. Bührig-Polaczek, Hybride Fertigungsver-
fahren zur Umsetzung gussintensiver Leichtbaukonzepte - Grund-
lagenforschung und Prozessentwicklung am Giesserei-Institut der
RWTH Aachen University. Paper presented at the
Verbundwerkstoffe/Werkstoffverbunde (2013)
 X-Ray Computed Tomographic Investigation
of High Pressure Die Castings

Shouxun Ji, Douglas Watson, and Zhongyun Fan

Abstract
The porosities and intermetallic phases in a high pressure die cast Al–Mg–Si–Mn alloy was
investigated using 3D X-ray computed tomography with different scanning resolutions. The
experimental results demonstrated the porosity level and phase detection of dependency
upon voxel sizes. The porosity levels were 0.4, 0.5 and 0.8% and the intermetallic phases
were 0.3, 0.4 and 0.6% when the same casting sample was scanned at 15 lm/vox,
7.2 lm/vox and 2.1 lm/vox, respectively. However, the structural parameters should be
assessed to determine the necessary and/or possible image quality, weighing factors such as
scan time, field of view, and voxel sizes.

Keywords
Aluminium alloys High pressure die casting NDT X-ray CT Porosity Intermetallics

Introduction structure because of poor control over design allowable for

High pressure die casting (HPDC) is widely used in manu-
facturing industry for thin-wall components with complex
geometries, net-shape, minimum machining, and relatively
more economical compared to other casting methods. This is
particularly important for massive production of components
used in automotive industry. However, it also has some
disadvantages like limitations on mechanical properties,
which is mostly caused by various casting defects or
imperfections because of the uncertainty in melt flow during
die filling under pressure. The defects generally include
surface defects such as blow, scar, blister, drop, scab, pen-
etration and buckle; and internal defects such as blow/gas
holes, shrinkage/porosity, inclusions, dross, etc. Therefore,
high pressure die castings cannot be used as primary
S. Ji (&)
Z. Fan
Brunel Centre for Advanced Solidification Technology (BCAST),
Brunel University London, Uxbridge, Middlesex, UB8 3PH, UK
e-mail: shouxun.ji@brunel.ac.uk
D. Watson
Engineering Centre, Jaguar Cars Ltd., Abbey Road, Coventry,
CV34 4LF, UK
the material strength and ductility. However, they can be
used as secondary structure when including significant safety
factors—usually between 3 and 6. The safety factor increa-
ses the overall weight of the castings, which defeat the cost
and weight savings that thin-wall castings can offer.
The effect of casting defects on the mechanical perfor-
mance can further be divided into two classes in terms of
micro-size defects and macro-size defects, while micro-size
refers to defects that are not visible without magnification,
and macro-size are that large enough to see with the unaided
on non-destructive graphic inspection [1]. Most surface
defects of die castings are readily to be found even by
unaided eye, and can be easily corrected by some industry
technology such as shot-blast cleaning or grinding [2]. But
the internal casting defects such as internal porosity cannot
be detected with unaided eye and even general product
quality control test, for example water pressure explosion
test. Therefore, the detection of internal defects have been an
important topic of researches to distinguish micro and macro
porosities both quantitatively and automatically. This is
critical to investigate the processing-microstructure-property
relationships since changes in processing parameters will
affect porosity differently.

© The Minerals, Metals & Materials Society 2017 861

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_104
862
Fig. 1 a Experimental setup for
the X-ray CT, and b sample a b
mounting detail for scanning
X-ray source
Sample stage
Previous works along these lines have used quantitative
metallography approaches and X-ray radiographic imaging
[3]. However, as porosities are complex 3D objects and
many of them are very fine in high pressure die castings, the
results from x-ray radiographic imaging and metallography
are general 2D and are always inaccurate. X-ray computed
tomography (X-ray CT) is a relatively new technology to
study defects in castings [4, 5]. Ferrie et al. [6] applied high
resolution synchrotron X-ray CT to characterize porosity in
cast alloys. The application of X-ray CT allowed the accu-
rate non-destructive 3-D reconstruction of pores within a
volume of aluminium alloy (i.e. distribution, size and mor-
phology). X-ray CT was also used to study the early stages
of fatigue crack nucleation and growth from pores [7]. The
application of X-ray CT in comparison to metallography on
cast aluminium parts has been discussed briefly in [8].
Clearly, X-ray CT has made it possible the three dimensional
characterization of microstructure and fine porosity How-
ever, 3D X-ray CT used to visualize the internal
microstructure and defects of materials depends obviously
on the accurate of scanning [9, 10]. In the present paper, we
report the 3D X-ray CT with different scanning voxel sizes
to examine the phases and porosities in high pressure die
castings.
Experimental
The alloy to make aluminium samples consisted of 5 wt%Mg,
2 wt%Si, 0.6 wt%Mn, 0.15 wt%Ti, unavoidable impurity,
and balanced aluminium (Al–Mg–Si–Mn hereafter). Samples
for porosity and microstructural characterization were made
by a 4500 kN cold chamber high pressure die casting machine,
during which the alloy was melted, degassed, and dosed into
S. Ji et al.
Objective
Turret
the shot sleeve at 700 °C to cast six ASTM standard samples
with three ∅6.35 mm round samples and three rectangular
samples in each shot. However, only one round sample was
used to assess the alloy’s porosity in the present study. The
sample was 120 mm long and the scanning dimensions were
at the centre part of ∅6.35  50 mm.
X-ray CT scans were carried out using a micro-CT sys-
tem (Zeiss Xradia 410 Versa, Carl Zeiss X-ray Microscopy,
Pleasanton, CA) with a spatial resolution of 0.9 lm and
minimum voxel (volume element) size of 100 nm. Varying
scan areas and resolutions can be obtained using different
objective lenses and scans per revolution respectively. An
X-ray filter to block specific wavelengths was implemented
in the system. Our 410 Versa model is the high energy
model, where the voltage and power ratings are 40–150 kV
and up to 10 W respectively. The experimental setup is
shown in Fig. 1. The sample shown in Fig. 1b was located
between the X-ray source and the objective turret. In order to
capture the sample at different resolutions, the voxel sizes
were separately set at 15, 7.2 and 2.1 lm in the particular
geometrical configuration of source and lens. The corre-
sponding energies and powers were 70 kV with 10, 10 and
8 W, respectively. The detail settings for voxel, working
voltages, power scan areas at different resolutions are sum-
marized in Table 1.
Creating a 3D profile of the sample using the micro-CT
system involved two separate processes: imaging and
reconstruction. During image acquisition, 1100 projection
images were obtained for each sample and they were
reconstructed to generate 2D slices of each sample at dif-
ferent voxel sizes of 2.1, 7.2 and 15 lm. During recon-
struction, absorption contrast was used in the reconstruction
of 3D microstructure and porosities. Absorption tomography
was used to measure the linear absorption coefficient of each
X-Ray Computed Tomographic Investigation of High Pressure … 863

Table 1 The experimental Voxel size (lm/vox) Field of view (mm) Energy/power (kV/W) Total scan time (h)
details in X-ray CT with different
voxel sizes 15 15  15 70/10 1
7.2 7.2  7.2 70/10 2
2.1 2.1  2.1 70/8 6.5

a b c

500μm 500μm 500μm

Fig. 2 The 2D projection images scanned at different resolutions, a 15 lm/vox, b 7.2 lm/vox and c 2.1 lm/vox

ray through the object, and the linear absorption coefficient
was set to be the attenuation of all local absorption coeffi-
cients where each local coefficient could be approximated
for each voxel.
Post-processing of each stitched scan was done by ORS
Visual SI software package for image processing and anal-
ysis, which facilitates the visualization, transformation,
manipulation, and analysis of large volumetric datasets, and
provides qualitative and quantitative data for the details and
properties of 3D structures originating from scans of objects.
ORS Visual SI also includes 2D and 3D image filtering
segmentation with 3D reconstruction and the data treatment
for the visualization and measurement of properties,
including areas, volumes, counts, distributions, and orien-
tations. The image processing steps were as follows:
(a) noise reduction with a 2D non-local means filter;
(b) segmentation of the different phases; (c) 3D hole filling;
(d) subtraction of c and b to obtain internal porosity and
different phases; (e) size and shape classification.
Results and Discussion
The die casting sample was about 150 mm long and
6.35 mm in diameter of the middle part, making them quite
suitable for CT examination. Figure 2 shows the 2D pro-
jection images for the relative size in the scanned samples at
different resolutions. Clearly, the scanning with the voxel
sizes of 15 lm/vox and 7.2 lm/vox could cover all the
diameter, but it only covered part of the sample when using a
voxel size of 2.1 lm/vox. Therefore, the sample could be
fully scanned under a multiple scanning because the full
view was only 2.1  2.1 mm for each scan at 2.1 lm/vox.
Figure 3 shows the scan overview and relative position
for the reconstruction of 3D microstructure from 2D slices.
Each of the quadrants represented a different orthogonal
virtual slice. The colored and dash lines with different fea-
tures corresponded to the slices with the same border
color/feature. By the combination of different projection
images, 3D images could be obtained and the visualization
of porosity and microstructures with different phases could
be observed and measured by volume value.
In order to examine the minimum porosities that could be
detected by the X-ray CT, the virtual oblique slices and the
maximum magnification for the detectable porosity and
phases in the microstructure are shown in Fig. 4. The CT
slices showed that the porosities were clearer when smaller
voxel sizes were applied. It is also seen that the porosity
were randomly distributed on the matrix. In the meantime,
the intermetallic phases were clear in the images obtained
with three different voxel sizes. However, the other phases
observed by other techniques in Refs. [11–13] could not be
seen in the scanned images. In particular, the eutectic Si and
the secondary intermetallics were not observed in the scan-
ned images even with the small voxel size. In Fig. 4, it is
also shown the maximum magnification to detect the mini-
mum size of porosity in the microstructure. It was found that
the minimum size of porosity was 22.4, 13.3 and 6.6 lm in
864 S. Ji et al.

Fig. 3 Full FOV of scan overview and reconstruction route from 2D slices

a b c

d e f
Intermetallics Intermetallics

Intermetallics

porosity

porosity

porosity
porosity

200μm

Fig. 4 The images a, b and c show the virtual oblique slices and d, e and f show the maximum magnification that can detect the minimum size of
porosity and phases in the microstructure
X-Ray Computed Tomographic Investigation of High Pressure … 865

Fig. 5 The images show a the 3D renderings of scanned area with 2.1 intermetallics (blue) in 3D renderings within the scanned area by
voxel size, b pores (blue) and iron-rich intermetallics (red) within the ORS Visual SI. Color figurer online
scanned area; and c the segmented pores (red) and iron-rich

Table 2 The volume fraction of Voxel size 15 lm/vox 2.1 lm/vox 7.2 lm/vox
porosities and intermetallic phase
from the scanned images and after Scanned images Porosity (%) 3.9 5.1 6.3
segmentation by ORS Visual SI Intermetallic (%) 3.4 4.2 4.8
After segmentation Porosity (%) 0.4 0.5 0.8
Intermetallic (%) 0.3 0.4 0.6

corresponding to the voxel size of scanning at 15, 7.2 and
2.1 lm. Clearly, the smaller voxel size of scanning could
detect finer porosity in the microstructure. However, it is
also clear that the fine intermetallic phases formed in the shot
sleeve and the phases with smaller contrast with aluminium
were not detectable from the X-ray CT images.
Figure 5a shows the 3D image of the sample scanned
with 2.1 lm voxel size. The reconstructions from volumetric
measurements at the voxel size of 15, 7.2 and 2.1 lm were
compared to assess the influence of voxel sizes. The visu-
alization of the porosities and the intermetallics among the
different voxel sizes at 15 and 2.1 lm were also studied and
the typical one for 2.1 lm voxel size is shown in Fig. 5b.
The scanned images were further treated with ORS Visual SI
for the segmentation of the porosities and intermetallics. The
results are shown in Fig. 5c. The detailed analytic results are
summarized in Table 2. The effect of voxel sizes on the
detectable levels of intermetallics and porosities is clearly
indispensable. The underestimation did appear to be signif-
icant for the voxel sizes of 15 and 7.2 lm, which revealed
that the underestimation was increased at the larger voxel
sizes. Meanwhile, the images became less sharp as the voxel
size was increased and the smaller porosities became less
visible on the images obtained with 15 lm voxel size.
Therefore, increasing the acquisition resolution with smaller
voxel size clearly improves the detection of microstructure
and porosities in the high pressure die castings. Moreover,
for the results obtained at 2.1 lm/vox, the levels of inter-
metallic phase were much higher than the experimental
results obtained in previous publication [11–13]. However, it
was close to the experimental results after segmentation
analysis. From the results, it is noted that the post processing
of scanned images play a critical role in determining the final
results.
Conclusions
The experimental results demonstrated the porosity level and
phase detection of dependency upon voxel sizes, indicating
that it is a non-trivial factor affecting quantitative porosity
and phase analysis. The sensitivity of the structural param-
eters to changes in voxel size suggests that higher magnifi-
cations is necessary to consistently detect the smaller
porosities and fine phases in high pressure die castings. The
porosity levels are 0.4, 0.5 and 0.8% and the intermetallic
phases are 0.3, 0.4 and 0.6% when the same casting sample
is scanned at 15, 7.2 and 2.1 lm, respectively. However, this
should not be viewed as discouraging the use of larger voxel
sizes because it is still valid to observe porosities in the
castings made by other processes. The structural parameters
should be assessed to determine the necessary and/or pos-
sible image quality, weighing factors such as scan time, field
of view, and voxel sizes.
866
Acknowledgements Financial supports from EPSRC for the future
LiME hub and from HAFCE, UK are gratefully acknowledged. The
helps from M. Terada and D. Edwards at ZEISS Ltd. are appreciated.
References
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(2005)
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3. A. Balasundaram, A.M. Gokhale, Quantitative characterization of
spatial arrangement of shrinkage and gas (air) pores in cast
magnesium alloys. Mater. Charact. 46, 419–426 (2001)
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raphy vs. metallography for pore sizing and fatigue of cast
Al-alloys. Procedia Eng. 2, 547–554 (2010)
5. G. Nicolettoa, R. Konečnáb, S. Fintovab, Characterization of
microshrinkage casting defects of Al–Si alloys by X-ray computed
tomography and metallography. Int. J. Fatigue 41, 39–46 (2012)
6. E. Ferrie, J.Y. Buffiere, W. Ludwig, 3D characterization of the
nucleation of a short fatigue crack at a pore in a cast Al alloy using
high resolution synchrotron microtomography. Int. J. Fatigue 27,
1215–1220 (2005)
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7. C. Verdu, J. Adrien, J.Y. Buffiere, Three-dimensional shape of the
early stages of fatigue cracks nucleated in nodular cast iron. Mater.
Sci. Eng., A 483, 402–405 (2008)
8. P. Powazka et al., Computed tomography—an alternative and
complement to traditional metallographic investigations of poros-
ity in cast aluminium, in Proceedings of 2nd Fatigue Symposium,
Leoben, pp. 51–66 (2008)
9. T. Marrow, J. Buffiere, P. Withers, G. Johnson, D. Engelberg,
High resolution X-ray tomography of short fatigue crack nucle-
ation in austempered ductile cast iron. Int. J. Fatigue 26, 717–725
(2004)
10. M. Wicke, M. Luetje, I. Bacaicoa, A. Brueckner-Foit, Character-
ization of casting pores in Fe-rich Al-Si-Cu alloys by microto-
mography and finite element analysis, in 21st European
Conference on Fracture, ECF21, 20–24 June 2016, Catania, Italy
11. S. Ji, W. Yang, F. Gao, D. Watson, Z. Fan, Effect of iron on the
microstructure and mechanical property of Al-Mg-Si-Mn and
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12. S. Ji, Y. Wang, D. Watson, Z. Fan, Microstructural evolution and
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(2014)
 The Comparison of Intensive Riser Cooling
of Castings After Solidification in Three Classic
Metals

Haolong Shangguan and Jinwu Kang

Abstract
The cooling of castings especially heavy steel castings was usually very slow and
nonuniform after solidification, which results in low production efficiency and great
residual stress or deformation. Furthermore, great thermal gradient appears across their
thick sections and between the thick and thin areas, which may cause significant residual
stress or deformation or even cracks. So as to solve this dilemma, we come up with a new
method to make the riser useful and realize the castings rapid, inside-out and uniform
cooling. It was named the post solidification intensive riser cooling technology (PSIRC). In
this paper, the effect of PSIRC was investigated for three different alloys GS38 carbon steel,
H13 alloy steel and A356 aluminium alloy by using stress frame castings. The results show
that PSIRC could improve production efficiency and temperature uniform of the castings
made of these three materials. For the improvement of cooling rate, it ranks from GS38
carbon steel, H13 alloy steel to A356 Al alloy. While for improving temperature uniform,
the order is A356 Al alloy, GS38 carbon steel and H13 alloy steel. The effect of PSIRC
mainly depends on the thermal conductivity of castings, high thermal conductivity means
more cooling efficiency.

Keywords
Casting Riser Cooling Heat transfer

The cooling of castings especially heavy steel castings is
usually very slow, it greatly reduces the production effi-
ciency, increases the cost. It usually by forced cooling to
speed the casting cooling after solidification. Shang et al. [1]
proposed a forced cooling way by adding cold iron around
cast iron and using statistical method to optimize the position
and usage of the external iron chill. Zhao et al. [2–4] pro-
posed a forced cooling way by adding ventilation pipe in the
main sand core with compressed air or water in it. These
H. Shangguan
J. Kang (&)
Key Laboratory for Advanced Materials Processing Technology,
School of Materials Science and Engineering, Tsinghua
University, Beijing, 100084, China
e-mail: kangjw@tsinghua.edu.cn
H. Shangguan
e-mail: sghl14@mails.tsinghua.edu.cn
forced cooling methods could improve the cooling rate
however they increased the temperature gradient and low-
ered temperature uniformity. Li et al. [5] proposed a better
cooling rate to make temperature more uniformity for X80
pipe line. The cooling rate was 15–20 °C/s. It improved the
temperature uniformity of X80 but reduced the cooling rate
and improved the production cost. Jinwu Kang proposed
PSIRC, a new forced cooling way of put compressed air or
water on riser after solidification, and it was verified on the
specimens of blade and stress frame. PSIRC could improve
the cooling rate and make temperature uniformity at the
same time [6, 7]. However, the effect of PSIRC on different
materials remains unsolved yet.
In this paper, the cooling effect by PSIRC was investi-
gated for three different alloys, carbon steel, alloy steel and
aluminum alloy. Their physical property parameters were
different, therefore it was necessary to reveal the different
effect of PSIRC on these materials.

© The Minerals, Metals & Materials Society 2017 867

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_105
868
(a) front view (b) side view
Fig. 1 Model of stress frame and points of sampling, a front view,
b side view
Heat Transfer in Specimen Castings
of Different Materials Under the Condition
of PSIRC
To better reflect the difference of cooling effect and the effect
of stress and deformation in future study, the stress frame
shape was selected for research. The stress frame had two
thin rods and a thick rod, its dimension was shown in Fig. 1.
The solidification and cooling process of this casting of
different materials were simulated by using ProCast. Three
materials were GS38 carbon steel, H13 alloy steel and A356
Al alloy. Their thermal conductivity coefficient and enthalpy
Fig. 2 The curve of the relationship between heat conductivity coefficient and temperature for three materials
Table 1 Density of these
materials 3
Density/(kg/m )
H. Shangguan and J. Kang
were quite different, as shown in Fig. 2. The density of these
materials was shown in Table 1.
PSIRC was to enhance the riser top heat transfer coeffi-
cient by blowing air or water spray, was shown in Fig. 3, the
red face was the surface of the casting. Under natural con-
vection condition, the heat transfer coefficient between riser
and air was 5–25 W/m2 K, in this paper it was taken as
20 W/m2 K in simulation. The medium was usual or spray
mist, the heat transfer coefficient was about 20–200 W/m2 K
for compressed air cooling, 200 W/m2 K was taken, the heat
transfer coefficient of spray mist was 1000–6000 W/m2 K, it
was taken as 2000 W/m2 K, when the cooling water density
was 11 L m−1 min−1 [8].
Biot number was an index of the ratio of the heat transfer
capability inside and at the surface of a body. As the Biot
number was more than 1, the heat transfer was mainly
controlled by the thermal conductivity, i.e. The equation was
hl
Bi ¼ ð1:1Þ
k
where k was the thermal conductivity, l was the effective
length from the riser surface to the hot spot core, h was the
riser top interface heat transfer coefficient.
PSIRC Effect Analysis
The Effect of Forced Cooling Intensity on Cooling
Rate
The heat transfer coefficient of the riser top surface with the
ambient were 20, 200, 2000 W/m2 K, corresponding to
GS38 H13 A356
7850 7250 2550
The Comparison of Intensive Riser Cooling of Castings After … 869

Applying PSIRC

Riser -Carbon steel

Fig. 3 The applying plane of the PSIRC

simulate natural convection cooling, compressed air and

spray mist. The cooling curves of the riser center, thick rod
and thin rod of the stress frame (as shown in Fig. 1) were
compared in Fig. 4.
From Fig. 4 it could be seen that PSIRC could improve
the cooling rate after the solidification of the casting. The
bigger of the heat transfer coefficient the faster cooling rate it
was. When P1 point reached shakeout temperature 300 °C,
the time of GS38 carbon steel was 8500, 4800,1300 s for 20,
200, 2000 W/m2 K. The cooling rate improved 44% for Thick -Carbon steel
GS38 carbon steel between applied compressed air and no
PSIRC, while the spray mist improved 85%. When P2 point
reached shakeout temperature 300 °C, the time of GS38
carbon steel was 8600, 6700, 4900 s. The cooling rate
improved 22% for GS38 carbon steel between applied
compressed air and no PSIRC, while the spray mist
improved 43%. When P3 point reached shakeout tempera-
ture 300 °C, the time of GS38 carbon steel was 7200, 6000,
4600 s. The cooling rate improved 17% for GS38 carbon
steel between applied compressed air and no PSIRC, while
the spray mist improved 36%.
When P1 point reached temperature 300 °C, the time of
H13 alloy steel was 11,000, 6700, 2700 for 20, 200,
2000 W/m2 K. The cooling rate improved 39% for H13
alloy steel between applied compressed air and no PSIRC,
while the spray mist improved 75%. When P2 point reached Thin bar-Carbon steel
temperature 300 °C, the time of H13 alloy steel was 11,300,
9400, 7900 s. The cooling rate improved 19% for H13 alloy Fig. 4 Cooling curves of the three materials
870 H. Shangguan and J. Kang

Applying PSIRC

Applying PSIRC

Riser-Alloy steel Riser-Al alloy

Thick-Alloy steel Thick-Al alloy

Thin bar-Alloy steel Thin bar-Al alloy

Fig. 4 (continued)
The Comparison of Intensive Riser Cooling of Castings After …
steel between applied compressed air and no PSIRC, while
the spray mist improved 30%. When P3 point reached
temperature 300 °C, the time of H13 alloy steel was 9700,
8500, 7400 s. The cooling rate improved 12% for H13 alloy
steel between applied compressed air and no PSIRC, while
the spray mist improved 24%.
When P1 point reached temperature 300 °C, the time of
A356 Al alloy was 2300, 1700, 1000 s for 20, 200,
2000 W/m2 K. The cooling rate improved 26% for A356 Al
alloy between applied compressed air and no PSIRC, while
the spray mist improved 56%. When P2 point reached
temperature 300 °C, the time of A356 Al alloy was 2300,
1900, 1400 s. The cooling rate improved 17% for A356 Al
alloy between applied compressed air and no PSIRC, while
the spray mist improved 39%. When P3 point reached
temperature 300 °C, the time of A356 Al alloy was 1600,
1500, 1330 s. The cooling rate improved 6% for A356 Al
alloy between applied compressed air and no PSIRC, while
the spray mist improved 17%.
The comparison of three materials on improving cooling
rate was listed in Table 2. The result showed that the
applying PSIRC on GS38 carbon steel had the largest effect
on improving cooling rate, and then it was H13 alloy steel,
finally it was A356 Al alloy. The reason was that A356 had
the highest conductivity. The conductivity played a leading
role in heat transfer, so the changing of heat transfer coef-
ficient had little effect for it, while GS38 carbon steel and
H13 alloy steel had the lower conductivity. In GS38 carbon
steel and H13 alloy steel, H13 alloy steel had the higher
conductivity but the conductivity of GS38 carbon steel made
a great difference between the high temperature and low
temperature, while it was almost the same for H13 alloy
steel, therefore the applying PSIRC on GS38 carbon steel
was larger effect than H13 alloy steel on improving cooling
rate. On riser, thick rod, and thin rod, we could find that the
riser was the largest effect section for PSIRC and then it was
Table 2 The comparison of GS38
three materials on cooling rate
improving Improving cooling
rate/%
Riser Thick
Compressed air and 44 22
none
Spray mist and 85 43
none
871
thick rod, finally it was thin rod. Therefore, for improving
cooling rate, the effect of PSIRC from big to small on three
materials was GS38, H13 and A356. The reasons were
related to the heat flow as well.
The Heat Flow in the Stress Frame Casting
The process of heat transfer could be expressed through the
direction of heat flow. Three materials under three different
heat transfer coefficient showed the same results. The pic-
tures of heat flow under three heat transfer coefficient were
shown in Fig. 5. The red arrow expressed the direction of
heat flow.
At the beginning of casting process, the casting was
suddenly cooled by the sand mold, so the heat flux was
pointing to the mold across the casting and mold surface. As
the procession of the cooling, heat transfer from casting to
mold came to be very slow, the heat inside of the casting
mainly flew from the center of riser to the bottom of the
casting, only little heat flew from the riser center to its top
sidewall. As PSIRC was adopted, the hot spot shifted from
the riser center to the middle of the casting, so the heat flew
from the hot spot toward the top surface of the riser, and
some heat still flew to the bottom of the casting. Comparing
the heat flow charts of 20, 200 and 2000 W/m2 K which
were shown in Fig. 5, we could find that the heat flow
direction was mainly from riser through thick rod to thin rod
under 20 W/m2 K. The heat flow direction turned around on
riser and thick rod while the thin rod remained the same
under 200 W/m2 K. The heat flow direction of three mate-
rials under 2000 W/m2 K was all from thin rod through
thick rod to riser. Riser became the final cooling channel.
When the hot section reached the thin rod, thin rod was
solidification at last. For thin rod was small volume, it was
easy to feeding. Therefore it could reduce the casting defects
H13 A356
Improving cooling Improving cooling
rate/% rate/%
Thin Riser Thick Thin Riser Thick Thin
17 39 19 12 26 17 6
36 75 30 24 56 39 17
872 H. Shangguan and J. Kang

such as shrinkage and cavity and improve the performance

of the casting.
Because the PSIRC applied made the direction of heat
flow turn around, riser was the most affected by heat flow
turn around and the most heat flow went through, therefore
the riser was the most serious effect section for PSIRC. The
less heat flow went through thick rod than riser therefore the
thick rod was less effect by PSIRC, while the least heat flow
went through thin rod, the heat inside of the casting mainly
flew through the thick rod and riser, so the thin rod was the
least effect by PSIRC. The direction of heat flow could be
reflected by the influenced depth of PSIRC as well.

The Influenced Depth of PSIRC

(a) 20 W/m2 ∙ k
The influenced depth of PSIRC meant the distance l between
hot spot and riser surface, which was shown in Fig. 6. The
relationship between the influenced depth and time of three
materials were shown in Fig. 7. The color was the temper-
ature distribution.
At the beginning, the influenced depth increased slowly.
When it was applied by PSIRC, the distances increased
obviously, the increasing rate and the maximum distance
were different for the three heat transfer coefficient.
2000 W/m2 K was larger than 200 W/m2 K, at last was
20 W/m2 K. The three materials showed the same rule.
From the Fig. 8 we could find that the influenced depths of
20 W/m2 K of three materials were all below 120 mm which
was the maximum distance of riser. Therefore the heat flow
would go from hot spot on riser through thick rod to thin rod
(b) 200 W/m2 ∙ k under 20 W/m2 K. When they were under 200 W/m2 K, the
influenced depths were all below 250 mm which was the
maximum distance from surface of riser to beam. Therefore
the heat flow would go from thermal section on beam
through thick rod to riser, which made the heat flow direc-
tion turned around except for thin rod. When they were
under 2000 W/m2 K, the influenced depths could reach the
distance of thin rod. Therefore the heat flow would go from
thermal section on thin rod through thick rod to riser, which
made the whole heat flow direction turned around.

(c) 2000 W/m2 ∙ k

Fig. 5 The heat flow direction in stress frame at different heat transfer
coefficient for three materials Fig. 6 The influenced depth of PSIRC
The Comparison of Intensive Riser Cooling of Castings After … 873

The Temperature Uniformity

The comparison of the temperature distribution of the stress

frame specimen on different heat transfer coefficient and three
materials was shown in Fig. 8. It could be seen that the
cooling of the casting with PSIRC was faster than that
without PSIRC. Meanwhile, the temperature distribution was
more uniform, and the color blocks of stress frame became
more uniform with the heat transfer coefficient improving.
The temperature difference of the thick and thin bars on
different heat transfer coefficient of three materials was
shown in Fig. 9. From the curves above, we could see that
PSIRC made the temperature of stress frame more uniform,
the temperature gradient between thick rod and thin rod
(a) Carbon steel became lower. The temperature gradient of three materials
all showed a trend of slowly decline at the beginning. With
the heat transfer coefficient improving, the trend of decline
was faster. Therefore the effect of PSIRC on carbon steel,
alloy steel and Al alloy was obvious.
The temperature difference of the thick and thin bars on
different heat transfer coefficient of three materials under
300 °C was shown in Table 3. We could find that A356 Al
alloy was affected to be the best uniformity by PSIRC, then
was GS38 carbon steel, at last was H13 Alloy steel. The
reason could be related to the Biot number that A356 had the
highest conductivity, then was GS38, at last was H13. When
the Biot numbers of them were reached the same value, the
heat transfer coefficient of A356 should be larger than GS38,
GS38 should be larger than H13. Therefore, for temperature
uniformity the effect of PSIRC from big to small on three
materials was A356, GS38 and H13.
(b) Alloy steel

Experimental Validation

The stress frame specimens were poured into resin bonded

sand mold in workshop with Al–Si alloy. The pouring
temperature was 700 °C. Ni–Cr thermocouples were used to
measure the temperature. A pair of castings was poured, the
first one was cooled by the traditional way under atmo-
spheres, the other one was cooled by compressed air through
a pipe with diameter of 8 mm at air speed 25 m/s, 10 min
later than pouring when the casting was estimated to have
totally solidified. And 42 min after pouring the forced
cooling was suspended for 25 min. The onsite experiment
was shown in Fig. 10a. The numerical simulation was set as
(c) Al alloy the same condition, the comparison between experimental
result and simulation result was shown in Fig. 10b. It could
Fig. 7 The relationship between the distance and time for three
materials be seen, they were basically in agreement.
874 H. Shangguan and J. Kang

Fig. 8 The typical temperature

contours of three materials under
20, 200, 2000 W/m2 K at 2000 s,
a Carbon steel, b Alloy steel, c Al
alloy

(a) Carbon steel (b) Alloy steel (c) Al alloy

The Comparison of Intensive Riser Cooling of Castings After … 875

Table 3 Temperature difference of the thick and thin bars on different

heat transfer coefficient of three materials under 300 °C
GS38 (°C) H13 (°C) A356 (°C)
2
20 W/m K 40 46 33
200 W/m2 K 23 30 20
2000 W/m2 K 10 18 8

(a) Carbon steel

(a) Onsite pouring experiments

(b) Alloy steel

(b) Comparison of the cooling curves

Fig. 10 Comparison of experiments and numerical simulation, a onsite

pouring experiments, b comparison of the cooling curves

(c) Al alloy

Fig. 9 The curves of the relationship between temperature difference

and time for three materials
876
Conclusion
(1) The effect of PSIRC on the stress frame of GS38 carbon
steel, H13 alloy steel and A356 Al alloy was researched.
The PSIRC could quicken the cooling process of the
whole casting inside out, and make the cooling of the
casting more uniform. Finally, it could improve pro-
duction efficiency and temperature uniform of the three
materials in article.
(2) For improving cooling rate, the effect of PSIRC from big
to small on three materials was GS38 carbon steel, H13
alloy steel and A356 Al alloy. While for improving
temperature uniform, the effect of PSIRC from big to
small on three materials was A356 Al alloy, GS38 car-
bon steel and H13 alloy steel.
Acknowledgements This work was financially supported by the
Project of Major Specific Innovation Platform Construction
(No. 2012ZX04012011).
H. Shangguan and J. Kang
References
1. Z. Shang, B Wei, The application statistic of cold iron in cast iron
wheel parts. Foundry Technol. 29(10), 1316–1318 (2008)
2. C. Zhao et al., Design and manufacturing process of 600 MW steam
turbine high pressure main steam control valve body. Foundry
Technol. 4, 3–5 (1997)
3. C. Zhao et al., Forced cooling in the application of large steel
castings production. Foundry Technol. 10, 20–22 (1996)
4. C. Zhao et al., Large castings forced cooling process design. China
Foundry Mach. Technol. 4, 31–32 (2000)
5. Y. Li, X80 pipeline steel temperature field simulation and
temperature control process of cooling uniformity. Ph.D. thesis,
Yanshan University, 2010
6. J. Kang et al., Intensive riser cooling of castings after solidification.
J. Mater. Process. Technol. 215, 278–286 (2015)
7. J. Kang et al., A cooling method to speed and equilibrium of large
steel. Chinese Patient. 101700569 (2010)
8. F. Jia et al., Heat transfer coefficient of spray cooling for aluminum
alloy continuous casting. Chin J Nonferrous Metals 11(5), 39–43
(2001)
 Sequential Gravity Casting in Functionally
Graded Aluminum Alloys Development

Mario Rosso, Silvia Lombardo, and Federico Gobber

Abstract
Aluminum alloys are widely used in the automotive field, for the excellent relationship
between mechanical strength and lightness. In the recent years, the request for cleaner,
lighter and more powerful engines, has led to the design of components subjected to higher
thermo-mechanical stresses. Demanding exercise conditions can imply the presence of
different properties that are never fulfilled by a single, homogeneous material. Various
solutions have been developed using composites, surface modification techniques and
Functionally Graded Material (FGM). This study has applied FGM concept to the
traditional casting technology, in order to obtain a more performing product. To reach this
goal, two different alloys were sequentially poured by gravity casting, each one delivering
locally its properties to a specific volume of the casting. Beyond the morphological and
microstructural analysis of the contact interface between the two alloys, the mechanical
testing has shown promising results for future applications.

Keywords
FGMS Aluminum alloy Piston Sequential casting

Introduction main characteristic of FGMs is the presence of more phases

Functionally graded materials (FGMs) were developed to
answer the new performance requests that came from the
aerospace and nuclear fields [1–3], such as the
multi-functionality of components. Thanks to the big
potential of FGMs, different and wide applications have
been developed and investigates during the last years [4],
even if the definition of FGMs continue to be: a two phase
component constituted by different materials with gradual
and continuous changings in composition and microstruc-
ture, in conformance with the requested properties [5]. The
M. Rosso (&)
Department of Applied Science and Technology, Politecnico di
Torino, 24 C.so Duca degli Abruzzi, Turin, 10129, Italy
e-mail: mario.rosso@polito.it
S. Lombardo
F. Gobber
Department of Applied Science and Technology, Politecnico di
Torino sede Alessandria, 5 V.le Teresa Michel, Alessandria,
15121, Italy
that create a gradient of composition and microstructure that
can confer very different properties to the material at the
same time that are impossible to obtain in an homogeneous
material [6]. Passing from a zone to the other a gradual
variation of composition and morphology in the volume
occurs, leading to a reduction of property discrepancy [7].
The transition between the two phases is a problem of main
concern in designing FGMs; the interface has to be contin-
uous with a gradual modification of composition and prop-
erties. The fascinating characteristics and potentialities of
FGMs have interested different areas of engineering. From
the first applications for aerospace [8, 9], new areas have
been investigated, such as energy, biomedicine and auto-
motive [10, 11].
In this last area, pistons are very critical components due
to the high temperatures and wear conditions, which they
have to withstand during service. Temperatures as high as
200 °C are reached on the head of the piston which is
exposed to the heat of combustion generated in the

© The Minerals, Metals & Materials Society 2017 877

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_106
878
combustion chamber, a steep temperature gradient along the
piston skirt [12] induces cyclic thermal stresses. High
resistance and acceptable ductility properties are hardly
coupled in castings, for this reason many studies were done
to try matching these properties together; many of them
include the use of FGMs [13, 14].
Temperature resistance is conferred by numerous alloying
elements that reduce the ductility of aluminum alloys. This
behavior can be problematic on the skirt part that is sub-
jected to fatigue stresses and can easily fail [15, 16]. In this
study the concept of using two different aluminum alloys
sequentially poured, was developed for future application in
piston gravity casting. A eutectic high temperature resistant
alloy with high strength and wear resistance was casted with
a hypoeutectic Al–Si alloy with superior elongation.
Materials and Methods
Two different aluminum alloys were used to realize the
castings: EN AB 48,000 which is an aluminum-silicon alloy
with a complex chemical composition commonly used in the
production of pistons and EN AB 42100 which is a
hypoeutectic aluminum-silicon alloy principally constituted
of aluminum, silicon and magnesium. The chemical com-
position of the two alloys is reported in Tables 1 and 2. No
modification or refining were performed during the melting.
The molten EN AB 48000 alloy was degassed in order to
avoid gas porosity, one of the main defects encountered in
aluminum castings.
A steel mould for gravity casting has been used for the
sequential casting. The first alloy, EN AB 42100, has been
purred from the bottom of the component, while the second
alloy, EN AB 48000, from a second entrance, in order to full
the entire mould. The casting temperature was set at 710 °C
for the EN AB 42100 and 750 °C for the EN AB 48000 (the
increasing temperature, compared with the foundry casting
condition, is principally due to laboratory scale casting
problems).
The mould was previously coated with a refractory
powder and subsequently preheated to an inner surface
Table 1 Chemical composition Element Si Fe
of piston alloy EN AB 48000
(wt%) Min[%] 10.5 – 0.8
Max[%] 13.5 0.7
Table 2 Chemical composition Element Si Fe
of the hypoeutectic aluminum
alloy EN AB 42100 (wt%) Min[%] 6.5 – –
Max[%] 7.5 0.19
M. Rosso et al.
temperature of 250 °C in order to facilitate the complete
filling of the mould by the molten metal. One of the main
parameters is the elapsed time between pouring the first and
the second alloy. In fact, the first alloy has to present a
temperature already below the liquidus curve to avoid the
mixing of the two alloys, but at the same time has to be over
to the solidus curve. If the temperature is too low, the risk is
to have a discontinuity between the two alloys after solidi-
fication. A thermal analysis was performed with differential
scanning calorimetry (DSC) technique in order to evaluate
this part of the process, using a Setaram TGA-DSC 9216.18
calorimeter.
The optimization of the interface has been developed in
antecedent works, analyzing the main parameters of the
process: temperatures of the two alloys, waiting time
between the sequential castings, order of casting of the
alloys. The temperature of the molten alloy has to be suffi-
ciently high to have a good fluidity avoiding, the presence of
elevated quantities of hydrogen in the bath (due to the high
solubility of hydrogen in the molten alloy). The waiting time
between the two castings also depends on the mould
geometry.
The first alloy to be poured was the hypoeutectic alloy,
due to a larger gap between the solidus and liquidus tem-
peratures; this larger gap could permit a certain barrier effect
due to the solidification of the alfa phase, to avoid the
mixing of the two alloys, while the presence of a certain
percentage of melted material (silicon - rich phase) allows an
easier local melting of the interface. The mould was
instrumented with thermocouples to control the process and
pour the second casting in the right range of temperature.
The component has been cut, polished and observed
through an optical microscope (MeF4 Reichart-Jung). Two
different image analysis software have been employed for
the analysis of specific areas of the microstructure, QWin
and Image J. An EMCO-TEST 250 with Vickers penetrator
was used for hardness testing, the measurements were made
on polished samples applying a load of 5 kg for 15 s. The
tensile test has been performed on a specimen obtained
following the Standard ASTM B 557-02, Fig. 1 and Table 3.
The machine used for the tensile test is a ZWICK ROELL.
Cu Mn Mg Ni Zn Ti Al
– 0.8 0.7 – – Balance
1.5 0.35 1.5 1.3 0.35 0.25
Cu Mn Mg Zn Ti Al
– 0.25 – – Balance
0.05 0.10 0.45 0.07 0.25
Sequential Gravity Casting in Functionally Graded … 879

Fig. 1 Round tension test

specimen

Table 3 Dimensions for the Dimensions

specimen for the tensile test
Nominal diameter 0.50 [inches] (8.89 [mm])
G—Gage length 1.40 [inches] (35.56 [mm])
D—Diameter 0.50 [inches] (8.89 [mm])
R—Radius of fillet ¼ [inches] (6.35 [mm])
A—Length of reduced section 1 ¾ [inches] (44.45[mm])

The test has been performed applying a test rate of 0.008 1/s,
till the rupture of the specimen.
Half of the specimen is constituted of hypoeutectic alloy
and half of piston alloys. The interface is located in the
middle of the samples, although it has to be taken into
account that the joining of the two alloys is not completely
linear, influencing the quantity of specific alloy in the
specimen. Each alloy should be present in the speciment
50% in volume, however a certain deviation from this value
will influence the final properties of the material. In this
study the shape of the interface has been considered negli-
gible because the linearity issue is correlate with the die
shape and will be optimized in future for the specific piston
case.
Fig. 2 DSC curve of 42,100, as cast, showing dissolution and melting,
A scanning electron microscope (SEM) Leo 1450VP has
endothermic peaks
been used for the analysis of fracture surfaces.

Results and Discussion

DSC Analysis

In order to have a superior knowledge of the thermal history

of this sequential casting process, the two alloys have been
analyzed performing a thermal analysis technique with DSC.
This method permits the study of reactions like precipitation,
dissolution, recrystallization and melting. The quantity of
material analyzed is 7.4 g for the piston alloy and 12.6 g for
the hypoeutectic alloy. Both alloys were heated with a
15 K/min heating rate from room temperature to 730 °C.
The DSC curves of 48,000 and 42,100 alloys are reported
in Figs. 2 and 3, and have to be considered as semi quan-
titative because of the heat capacities difference of sample Fig. 3 DSC curve of 48,000, as cast, showing the endothermic peak
and reference and the baseline variability. associated to the melting point at the eutectic
880
The hypoeutectic alloy, 42,100, presents at lower tem-
peratures, close to 500 °C, an endothermic tendency, due to
the dissolution of the alloying elements in the matrix. The
curve presents two relevant peaks: one is related to the
eutectic temperature, when the interdendritic phase starts to
melt and the second to the liquidus temperature, 615 °C,
where the alloy is completely melted. The hypereutectic
alloy does not present these two peaks in its curve because it
has a eutectic composition, close to 579 °C (the eutectic
temperature of pure Al and pure Si occurs at 577.6 °C [17]).
The DCS curves give two important types of information to
optimize the process. First of all, the melting interval tem-
peratures of the alloys are precisely defined. The range of
temperature from the beginning to the complete solidifica-
tion of the 42,100 alloy, is the one in which has to fall the
second casting, in order to have the remelting of the inter-
face. The second information given by the thermal analysis
is the solution temperature of the alloy. Thanks to this
information it is possible to optimize a future heat treatment,
to strengthen and increase the elongation of the FGM.
Microstructural Analysis
After the sequential casting, the material has been polished
ad observed with the optical microscope. The microstructure
reported in Fig. 4 shows the passage between the hypoeu-
tectic and hypereutectic aluminum alloys. The interface is
clear from defects at the interface (no concentration of
porosity, oxides, and shrinkages) and the component appears
Fig. 4 Microstructure of the
interphase of the two materials
after sequential casting. 42,100
alloy is the one on the left and
48,000 alloy the one on the right
M. Rosso et al.
as a single and compact piece, with regions with different
characteristics.
In Fig. 5 it is clear the “line” where the two alloys meet,
but at the same time the 42,100 alloy, casted first, presents in
its microstructure elements belonging to the 48,000 alloy.
This suggests that the 48,000 alloy, poured second, pene-
trated into the interdendritic channels for a determined depth.
In order to have a quantification of this transitional
region, the fraction of area of the eutectic phase was cal-
culated through an image analysis software, In Fig. 5 it is
possible to observe how the silicon phase and the inter-
metallic compounds enrich the interdendritic channels when
the second casting remelts the interface. The passage from
one region to the other is gradual but at the same time
limited on a very local area. The thickness of the remelted
part is equal to 1.50 mm for this specific cast condition.
Hardness Behavior
The hardness testing was performed following a line
orthogonal to the interface indenting progressively from the
42,100 to the 48,000. Figure 6 shows the increasing ten-
dency of the hardness profile, when passing from one alloy
to the other. The curve can be compared with the one rep-
resenting the fraction area of the silicon phase, Fig. 5,
because the silicon content is closely correlated to the
hardness of the alloy. The average hardness value of the
hypoeutectic as—cast alloy is 68 HV while it is equal to
100 HV for the piston alloy.
Sequential Gravity Casting in Functionally Graded … 881

Fig. 5 Fraction of area of the

eutectic phase from the 42,100
alloy to the 48,000 alloy, passing
through the interface

120 of 155.00 MPa with a superior value of 161.00 MPa. The

100 sample that reached a final strength of 161.00 MPa had a
80
maximum elongation of 3.3%, Table 4. Although the
HV 5

material had many defects linked to the bifilm effect [18, 19]
60
(due to the laboratory conditions) the FGM presents a tensile
40 resistance that is not far from the one of the piston alloys,
20 that are the most resistant, but with an elongation that can
0 reach maximum 3% of the initial length. This result is really
1 2 3 4 5 6 7 interesting taking into account that pistons alloys always
Distance from the edge [mm]
present an elongation percentage which is inferior to 1%
Fig. 6 Vickers hardness curve performed on the sequential casting, (0.3–0.5%).
passing from the hypoeutectic alloy to the eutectic alloy (crossing the The material presents a certain level of ductility, given by
interface, point 4) the 42,100 alloy. Half of the sample is constituted by the
48,000 alloy, that has an intrinsic fragility due to the pres-
The most encouraging and promising fact deriving from ence of elevated quantities of silicon phase and intermetallic
this analysis is that no evidence of loss in hardness at the compounds that enhance the tribological resistance of the
interface was detected. The fact that one region can reach a material and its resistance to high temperatures. The other
superior hardness without the weakening of the other part of half of the specimen is the one that has a superior elongation
the sample can be useful for future applications of this and should represent the skirt of the piston.
technology on a piston, whose head is subjected to high
temperature and wear.
Fracture Analysis

Tensile Testing
The mechanical properties of the material have been ana-
lyzed performing tensile tests. All the ruptures happened in
the 42,100 alloy, which is the one with lower mechanical
strength. None of the samples broke at the interface.
The average yield strength is equal to 96.02 MPa as can
be seen in Table 4, and the higher value reached is
101.00 MPa. The final strength arrives to an average value
Fracture surfaces were analyzed after the tensile testing to
observe which kind of fracture mechanisms occurred during
the tensile testing. The lower values of tensile resistance have
been justified with the presence of oxides and shrinkage
porosity. As can be seen in Fig. 7a, the presence of oxides in
the melting bath has caused the formation of bifilms that did
not permit the interdendritic channels to be completely filled
by the melted material. The result is a weakening of the
component because the resisting section is extremely
882 M. Rosso et al.

Table 4 Yield strength, ultimate tensile test and elongation averages and standard deviations of the sample submitted to the tensile test
Rp0.2 (MPa) RB (MPa) A%
Average 96.02 155.20 2.10
Standard deviation 4.57 4.74 0.74

Fig. 7 a SEM photography of the bifilm present on a shrinkage porosity b Fractography of the sample that reached the highest ultimate tensile
strength

reduced. The specimen free from shrinkage and oxide
presented a rising of the 8% for the ultimate tensile strength,
compared with the one presenting bifilm. Also the percentage
elongation consequently changes from 1.4 to 3.3%.
Figure 7b shows the SEM fractography for the 42,100
alloy (all samples broke in this region). As the fracture (2) The morphological analysis has shown a compact
surface exhibits very few dimples, almost the totality of the
fracture shows cleavage morphology. The silicon particles
create flat zones which in turn act as stress concentrators.
Two distinct failure modes are observed in Fig. 7b; (i) a
brittle fracture due to microcracking of brittle phases,
shrinkage and gas porosity; and (ii) a ductile failure of the
matrix phase. Brilliant ridges indicate necking in Fig. 7b.
Conclusions
(1) The sequential casting process was optimized, obtaining
the right waiting time between the two pouring alloys.
This result has been possible thanks to the thermal
analysis performed on the two materials that highlighted
different melting intervals. The results obtained are a
good input also for the optimization of the thermal
treatment of the FGM.
material, without defects at the interface. The study on
the fraction of area of the eutectic phase supports the
decision to cast first the hypoeutectic alloy in order to
remelt easily the surface in contact and create a better
connection with the piston alloy taking advantage of
interdendritic channels.
(3) The mechanical tests also confirmed the strength of the
interface. The change in hardness was confined to the
interface region and during the tensile tests all the
specimens broke on the weakest alloy part, not on the
interface.
(4) The values of mechanical strength reached are interest-
ing if compared to those of the single alloys. The
elongation to rupture is one order in magnitude higher in
the sequentially casted pieces than that of piston alloys.
Sequential Gravity Casting in Functionally Graded …
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 Assessment of Eutectic Modification Level
in Al–Si Alloys Via Thermal Analysis

Maiada S. Abdelrahman, Mahmoud T. Abdu, and Waleed Khalifa

Abstract
The modification level (ML) of A356, A319, and A413 Al–Si alloys was investigated via
thermal analysis (TA) and microstructural investigation. The modification treatment was
carried out using different levels of Sr in the form of Al-10 wt% Sr master alloy. The melt
was poured into three different types of molds to give different cooling rates (CRs) to
simulate the actual casting conditions. Increasing the level of Sr improved the ML of the
eutectic Si. Slower CRs required higher additions of Sr to produce the same ML obtained
from the higher CRs. An attempt was made to assess the ML at the high CRs with the aid of
the TA parameters measured at the slow CR. Thermal analysis was found to provide
successful quantitative measure for the modification level in A356. In A319 and A413,
thermal analysis could provide successful quantitative measure of ML when the ML was
below 4.0. It could provide only qualitative indication of the occurrence of modification
when the ML was 4–6. The latter findings were found independent of cooling rate.

Keywords
Thermal analysis Sr level Cooling rate Microstructure

Introduction The volume fraction of the eutectic structure increases with

Aluminum–silicon alloys are known for their suitability in
myriad of applications for casting domestic, military,
automotive, and aerospace components [1, 2]. Existence of
Si as a major alloying element in these alloys imparts low
shrinkage and high fluidity which result in good castability
and weldability, allowing for producing intricate casting
geometries. In addition, higher Si content in hypoeutectic
Al–Si alloys increases the hardness and slightly increases the
strength with a concomitantly pronounced decrease in
ductility [3].
Silicon has a very limited solubility in aluminum. The
maximum solid solubility of Si in a-Al is about 1.5 wt% and
occurs at the eutectic temperature (577 °C). Al–Si compo-
sitions in excess of 1.5 wt% Si contain Si in a eutectic form.
M.S. Abdelrahman
M.T. Abdu (&)
W. Khalifa
Mining, Petroleum, and Metallurgical Engineering Department,
Cairo University, Giza, 12613, Egypt
e-mail: mahmoud.t.abdu@gmail.com
increasing the Si content of the hypoeutectic alloys. During
solidification, eutectic silicon assumes faceted acicular
morphology which results from the simultaneous growth of
the eutectic phases [4]. This acicular morphology of Si
adversely affects the fluid flow during the final stages of
solidification and hence controls the efficiency of liquid
metal feeding into die cavities. Feeding efficiency in turn
influences shrinkage, which may cause porosity, and
chemical segregation in the cast parts [5, 6].
The eutectic silicon can be refined in size by increasing
the cooling rate, but the polyhedral geometry of Si particles
remains unaffected [1, 7]. Fortunately, the problems asso-
ciated with eutectic silicon size and morphology can be
remedied by chemical modification in which trace elements
such as Sr are added in the form of master alloys to the
hypoeutectic Al–Si melts [8]. The addition of Sr modifies the
acicular, plate-like (flake) morphology of the eutectic Si to a
fine fibrous (coral or seaweed-like) form [9]. This morpho-
logical transformation provides better feeding characteristics

© The Minerals, Metals & Materials Society 2017 885

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_107
886
and better distribution of shrinkage in castings [10]. These
result in an appreciable improvement in ductility with a
limited increase in strength.
Monitoring of the success of the chemical modification
process was being made using metallographic examinations
according to the guidelines of the American Foundry Society
(AFS). These examinations are tedious, time-consuming,
expensive, subjective, inaccurate, and cannot be applied
during melt processing. The more recent alternate means of
monitoring the modification efficiency is the use of thermal
analysis of molten alloys [10, 11].
Thermal analysis has been practiced since the 1980s and
is gaining more attention on the foundry floor for predicting
the modification level (ML) in Al–Si alloys [7, 10–13]. It has
been found that not only does the addition rate of Sr control
the ML, but also the cooling rate plays an important role in
affecting the ML [7, 8]. This means that different casting
techniques, which are normally associated with different
cooling rates, can have an influence in dictating the modi-
fication efficiency during liquid metal solidification [8]. It is,
therefore, the purpose of the present paper to report how the
thermal analysis can be used to predict the modification level
in three different Al–Si alloys with the employment of three
different molding conditions. The molding conditions used
in the present investigation, namely, are heated graphite
mold (heated to 700 °C), cold graphite mold, and cold steel
mold. These molding conditions are made to approximately
simulate the actual casting conditions obtained from sand
casting, permanent mold casting, and die casting, respec-
tively. Through the work we attempted to predict the
modification level at the rapid cooling rates with the aid of
the thermal analysis parameters measured at the slow
cooling rates.
Experimental Procedures
Three different Al–Si alloys were used in the present
investigation: A356, A319, and A413. These alloys were
prepared by mixing pure Al (99.5 wt% Al) with Si and/or
Cu. The chemical compositions are shown in Table 1.
During the addition, a loss factor of 10 wt% was made to
account for the losses in Si, and Cu. The alloys ingredients
were melted in silica-based crucibles in electric resistance
furnace. After melting, complete mixing, and skimming, the
Table 1 Nominal chemical Element, wt% Si
composition of the used Al–Si
alloys A356 6 –
A319 6 3.5
A413 11
M.S. Abdelrahman et al.
molten metals were degassed using pure Argon at 750 °C.
The unmodified specimens were then heated to 750 °C and
poured in three different molds. Two of the molds were
graphite molds. One of the two graphite molds was heated to
700 °C and the other was kept at the ambient temperature.
The third mold was a steel mold kept at ambient tempera-
ture. The graphite molds dimensions were cylindrical cups
having 50 mm outer diameter, and 50 mm height. The wall
thickness of the mold was 10 mm. The utilized steel mold
was also cylindrical cup having 50 mm outer diameter and
70 mm height. The wall thickness was 7 mm.
Modification of the above mentioned alloys was carried
out using Sr in the form Al-10 wt%Sr master alloy ingots.
Three addition rates were employed in the present study: 50,
150, and 300 ppm Sr. Similar to Si and Cu, a loss factor of
10 wt% was made to account for the losses in Sr. After
complete melting, and skimming, degassing treatment was
conducted using pure argon gas (99.99999%) and the flow
rate was 1.5 ml/min. After degassing, the melt was skim-
med; temperature was adjusted to 750 °C; and the Al–Sr
master alloy was added to the melt in an aluminum foil,
immersed into the melt, and stirred gently using graphite rod.
All modification additions were supplied to the melts at
750 °C. The contact time after Sr addition was maintained at
10 min. After the elapse of the contact time, the alloys were
skimmed again and stirred gently using graphite rod. The
melt was poured at 750 °C in the three molds described
above for the unmodified alloys.
Thermal analysis was carried out using k-type
thermocouples located in the center of the mold. The
thermocouples were placed in holes drilled in the bottom
of the molds. The data acquisition was made using a
commercial software package (Quick DAQ 2014). The
acquisition rate was maintained at 10 Hz. After complete
solidification, the produced samples were cut, ground using
SiC paper, and polished using diamond paste for metallo-
graphic examination. The metallographic examinations
were carried out on polished surfaces of the specimens
using Olympus optical microscope. The Si particles were
then analyzed using ImageJ. The analysis of Si particles
was conducted using five fields of each condition (there
were 36 conditions in total). The analysis was made in
terms of the Si particles size (particle area and particle
perimeter) and shape descriptors (particle circularity and
particle aspect ratio).
Cu Fe Al
0.5 Bal.
0.5 Bal.
– 0.5 Bal.
Assessment of Eutectic Modification Level in Al–Si Alloys …
Results
Thermal Analysis Data
Figure 1 shows the different cooling curves acquired for the
different addition levels of Sr during cooling in heated gra-
phite molds. Figure 1a–c pertain to the Al-6Si (A356), the
Al-6Si-3.5Cu (A319), and the Al-11Si (A413) alloys,
respectively. Figure 2a, b show the procedures used to
determine the thermal analysis parameters associated with the
modification of Al–Si alloys. Here, the two selected parame-
ters were the depression in Al–Si eutectic growth temperature
DT as shown in Fig. 2a and the eutectic solidification time
Dt (Dt = ts − tf, where ts is the eutectic nucleation time which
denotes the start of eutectic solidification, and tf is time
denoting the end of the eutectic solidification peak on the
temperature derivative) as shown in Fig. 2b. It is worth
mentioning that the depression in eutectic temperature
DT considered in present investigation is taken as:
Fig. 1 Cooling curves of different Al–Si alloys: a A356 in heated graphite mold, b A319 in heated graphite mold, c A413 in heated graphite
mold, d A356 with 300 ppm Sr in different molds showing how we computed the cooling rates
887
DT ¼ TE; no Sr; heated graphite mold  TE; with Sr; anyother mold
This means that we used the eutectic growth temperature
obtained at no Sr addition from cooling in the heated gra-
phite mold as a reference temperature with respected to
which the depression is computed for any of the investigated
molds at any addition level of Sr. It is also worth mentioning
that the eutectic solidification time Dt was computed for the
data obtained from heated graphite molds (slowest cooling
rates) only because with increasing the cooling rate (as in
unheated graphite and steel molds) the reaction time
becomes very small to differentiate or sometimes obscure.
This can be observed by comparing the heated graphite
curve with the unheated steel curve in Fig. 2a.
Figure 1a shows the cooling curves of the A356 (Al-6Si)
at different addition levels of Sr during cooling in heated
graphite molds kept initially at 700 °C. It can be seen that
eutectic growth temperature for the 0 ppm Sr addition
888
Fig. 2 Procedure used to a compute the depression in eutectic growth temperature (TE), and b compute the eutectic reaction time (Dt = tf − ts).
The figure in (b) is for Al-6Si-3.5Cu (A319) + 150 ppm Sr cooled in a heated graphite mold kept initially at 700 °C
occurred at 576.1 °C. With reference to the rules set forth
above, it can be seen that increasing the addition level of Sr
caused two primary effects. The first effect is the increase in
the depression in the eutectic growth temperature with
increasing Sr addition. The depressions in TE for 50, 150,
and 300 ppm Sr additions were 2.2, 7.8, and 9.6 °C,
respectively. The second effect is the increase in eutectic
solidification time with increasing the level of Sr addition.
The eutectic solidification times were 74.5, 110.6, 114.9, and
140.0 s for 0, 50, 150 and 300 ppm Sr additions,
respectively.
Similar to Fig. 1a, b shows the cooling curves of A319
(Al-6Si-3.5Cu) at different addition levels of Sr addition
captured during cooling in heated graphite molds. At this
point it can be observed that addition of 3.5 wt% Cu to the
Al-6Si (A356) alloy caused the Al–Si eutectic temperature to
decrease from 576.1 to 564.0 °C. Despite the latter fact, the
general trend that the addition of Sr caused a depression in the
eutectic growth temperature and an increase in the eutectic
solidification time, as shown in Figs. 1b and 2a, remained
unaffected. However, the 150 ppm Sr showed a different
behavior. It can be observed that the depression in the eutectic
growth temperature at 150 ppm Sr (7.0 °C) is slightly smaller
than at 50 ppm Sr (8.7 °C). Further, it was also found that the
eutectic solidification time at 150 ppm Sr (50.2 s) was
slightly shorter than at 50 ppm Sr (51.7 s).
As for Al-11Si (A413) alloy, Fig. 1c shows that the
eutectic temperature, captured at no Sr addition in a heated
graphite mold, occurred at 577.7 °C. It is worth noting that
the values of TE measured for A413 and A356 (for 0 ppm Sr
in heated graphite mold) are in complete agreement with the
equilibrium value of eutectic temperature reported in [14].
M.S. Abdelrahman et al.
The depression in eutectic growth temperature and the
increase in eutectic solidification time generally increased
with increasing the Sr addition rate as shown in Fig. 1c.
However, the 300 ppm Sr addition gave a depression in TE of
7.2 °C which is less than that found for 150 ppm Sr (9.8 °C).
Figure 1d shows the cooling curves obtained for A356
after addition of 300 ppm Sr in the three designated molds
(heated graphite, and unheated graphite and steel molds).
The purpose of showing this figure is to show how the
cooling rate was computed for each experiment and to show
the influence of cooling rate on the depression in the Al–Si
eutectic growth temperature. As can be seen in the figure, the
cooling rate was computed from the slope of a straight
segment located between the liquidus arrest point and the
Al–Si eutectic arrest point just above the eutectic nucleation
temperature. It can be seen from the figure that the heated
graphite mold gave a cooling of 0.5°Cs−1 while the unheated
graphite and steel molds gave cooling rates of 2.2 and 6.3°
Cs−1, respectively. The recorded eutectic growth tempera-
tures obtained from the three molds were 566.5, 565.6 and
565.9 °C for the heated graphite, and the unheated graphite
and steel molds, respectively. These numbers indicate that
increasing the cooling rates did not affect the depression in
the eutectic growth temperature in the unmodified Al-6Si
(A356) alloy.
Microstructural Data
The effect of Sr addition and cooling rate on the
microstructure of A413 only is shown here; see Fig. 3.
Similar effects were observed for the other two alloys
Assessment of Eutectic Modification Level in Al–Si Alloys … 889

Heated graphite mold Unheated graphite mold Unheated steel mold

0 ppm Sr
50 ppm Sr
150 ppm Sr
300 ppm Sr

Fig. 3 Influence of Sr addition on the eutectic microstructure of Al-11Si (A413) in the different types of molds employed in the present
investigation

(A356, and A319). It can be seen from Fig. 3 that, for the
same mold type, i.e. approximately the same cooling rate,
increasing the level of Sr improved the modification level
(ML) of the eutectic Si in the A413 alloy which contains
higher fraction of Al–Si eutectic than the other two alloys.
Furthermore, it can be seen that for the same Sr addition
increasing the cooling rate (CR) , i.e. moving from the
heated graphite mold toward the unheated steel mold,
caused a refinement of the Si particles. Addition of
150 ppm Sr to the heated graphite mold gave the same
result as adding only 50 ppm Sr to the unheated steel mold.
This indicates that slower CRs required higher additions of
Sr to produce the same ML obtained from the higher CRs.
It can be seen that the finest Si particles were obtained
from adding 300 ppm Sr to the unheated steel mold. In
fact, the signs of over modification were absent in all the
investigated microstructures at all addition rates of Sr in all
the investigated molds.
890
From the morphological standpoint, the increase in
cooling rate causes refinement in the size of the Si particles
at all addition levels of Sr though it does not cause a change
in the morphology of Si. Only addition of Sr is what is
responsible for the change of the morphology of Si. It can be
seen that for the same mold type further addition of Sr not
only forces the Si particles to be finer, but also forces them to
be more rounded, i.e. the aspect ratio decreases and the
circularity increases. Note that the circularity here is calcu-
lated as 4pA=P2 , where A is the particle area and P is the
particle perimeter. The aspect ratio is obtained from fitting
particle with an ellipse and is equal to the ratio between the
major axis and the minor axis of the fitted ellipse. Qualita-
tively, Fig. 3 shows that the refinement of Si particles was
associated with an increase in the average particle density.
Discussion
In this section, it is attempted to quantitatively correlate the
values of the thermal analysis variables (depression in TE
and increase in Dt) with the microstructural variables (par-
ticle area, perimeter, circularity, and aspect ratio). It should
be noted that used values of microstructural parameters were
based on the central, median values. The reason was the
unacceptable scatter found in the mean values which agrees
with the findings of Djurdjecvic et al. [12]. This considera-
tion also agrees with what Djurdjecvic et al. [12] adopted in
their research on 319 Al–Si alloy. In fact, our analyses
showed that the median occurs very close the highest fre-
quency in the parameter’s value distribution.
Al-6Si (A356) Alloy
The correlations made for the A356 (Al-6Si) alloy are pre-
sented in Fig. 4a–c for heated graphite, and unheated gra-
phite and steel molds, respectively. It can be seen that, on
each plot, the cooling rate, depression in TE, and the eutectic
solidification time were placed on secondary x-axes. It has to
be remembered that eutectic solidification times reported on
all the graphs are those computed from the heated graphite
molds and are used on top of the unheated graphite and steel
molds data for reference to show the possibility of predicting
the modification level (ML) from the data acquired at slow
cooling rates.
A first glance at the three plots at 0 ppm Sr addition
shows the effect of varying the cooling rate on the
microstructural features of the eutectic Si particles in the
absence of Sr. It can be seen that increasing the cooling rate
caused the area and perimeter to slightly decrease, but the
circularity and aspect ratio remained nearly unaffected. This
gives a quantitative proof that the increase of the cooling rate
M.S. Abdelrahman et al.
in the absence of Sr refines the Si particles size without
affecting their polyhedral nature as reported in [7, 15].
For all the types of molds in Fig. 4a–c, it can be seen that
increasing the addition level of Sr progressively decreased
the particle area and perimeter with the perimeter being the
most influenced parameter. The aspect ratio decreased with
Sr addition. The circularity of the particles approached its
ideal value of 1.0 with the addition level of Sr. This indicates
that the modification level improved with increasing the Sr
addition level which agrees with [7, 12]. Associated with the
latter improvement in the microstructural parameters are
both the increase in the depression of the eutectic growth
temperature (TE) and the eutectic solidification time
(Dt) with increasing the Sr addition level. This finding
indicates that the depression in eutectic temperature and the
eutectic solidification time can reflect the successful occur-
rence of modification in the Al-6Si alloy. In fact, the
increased depression in TE with increasing the addition level
of Sr has also been reported by Zamani et al. [7],
Tenekedjiev et al. [8], and Djurdjevic et al. [12]. Similar
effect to the increase in eutectic solidification time with Sr
addition has been reported by Tenekedjiev et al. [8]. The
latter findings and their agreements with the findings
reported in the literature show that the thermal analysis can
be used successfully to predict the extent of the modification
treatment in Al-6Si alloys. In this respect, it has to be rec-
ommended to use the thermal analysis parameters acquired
from slow cooling thermal analyses because some of the
cooling curves features become obscure with more rapid
cooling rates. This has to considered in particular when the
eutectic solidification time is sought as a parameter signi-
fying the success of the modification treatment. As for the
depression in the eutectic growth temperature, the values
shown in Fig. 4a–c indicate that the depression in TE does
not show a significant influence by the cooling rate in Al-6Si
(A356) alloy. For example, at 300 ppm Sr increasing the
cooling rate from 0.5°Cs−1 (Fig. 4a) to 6.3°Cs−1 (Fig. 4c)
increased the depression in TE by 0.6 °C only.
Al-6Si-3.5Cu (A319) Alloy
Similar to Al-6Si (A356), the correlations constructed for the
Al-6Si-3.5Cu (A319) alloy are illustrated in Fig. 5a–c for the
heated graphite mold, and the unheated graphite and steel
molds, respectively. It has to be noted that this alloy is more
complex than the Al-6Si (A356) binary alloy due to the
presence of 3.5 wt%Cu. And, as mentioned earlier the
addition of 3.5 wt% Cu to the Al-6Si (A356) alloy caused
the Al–Si eutectic temperature to be depressed by 12.1 °C in
the near-equilibrium condition. And, despite the higher
complexity of the alloy compared to the A356 and the
depression in TE as a result of the presence of Cu, the
Assessment of Eutectic Modification Level in Al–Si Alloys …
Fig. 4 Correlation of the addition level of Sr with the measured thermal and microstructural variables for Al-6Si (A356) alloy
addition of Sr can still cause a depression in the eutectic
growth temperature and an increase in the eutectic solidifi-
cation time in the samples cooled slowly in heated graphite
molds. However, in all the figures, it is clear that the increase
in the depression in eutectic growth temperature and the
eutectic solidification time did not scale with the addition
level of Sr. The reason is that the values of these parameters
do not reflect the amount of Sr existing in the melt; they
rather reflect the quality of the melt, i.e. the potency of the
added Sr in modifying the size and morphology of the
eutectic Si particles.
At slow cooling rates, it can be seen from Fig. 5a that the
thermal analysis parameters precisely reflected the changes
occurring in the microstructural parameters. With the A319,
the aspect ratio poorly reflected the modification level as was
reported by Djurdjevic et al. [12]. Therefore, the aspect ratio
891
will not be considered to further analyze the microstructure
of A319. However, with increasing the Sr addition, the
microstructural parameters (particle perimeter, area, and
circularity) generally improved. Concomitantly, the depres-
sion in eutectic growth temperature (DT) and the eutectic
solidification time (Dt) increased as reported in the literature
[7, 8, 12]. Even with the odd point appearing at 150 ppm Sr,
the slight coarsening in the Si particles perimeter and area,
and the slight decrease in the circularity were reflected in the
decrease in DT and Dt. These observations agree with what
has been reported by Djurdjevic et al. [12] who found that
the addition of Sr to the 319 Al–Si alloy was accompanied
by an improvement in the modification level as well as the
depression in the eutectic temperature. It has to be noted that
the cooling rate employed by Djurdjevic et al. [12] was very
slow as they immersed a cylindrical graphite cup into the
892
Fig. 5 Correlation of the addition level of Sr with the measured thermal and microstructural variables for Al-6Si-3.5Cu (A319) alloy
melt for 20 s and then recorded their cooling curves during
the subsequent freezing of the melt contained in the cup.
At the rapid cooling rates, Fig. 5b, c, it is obvious that the
depression in eutectic growth temperature and eutectic
solidification time do not really reflect the level of modifi-
cation expressed in terms of perimeter, area, and circularity.
However, it can be observed that the occurrence of modifi-
cation is always associated with a depression in TE and an
increase in Dt compared to the unmodified conditions. This
indicates that the thermal analysis parameters measured from
cooling curves acquired at rapid cooling rates can only
qualitatively indicate the occurrence of the modification
effect, but they fail to precisely predict the exact modifica-
tion level at the high cooling rates which happen here to
correspond to high modification levels of approximately 4.0.
These findings agree with a conclusion drawn by Chen et al.
M.S. Abdelrahman et al.
[11] from their work on the prediction of modification level
in Al-7Si alloy. Chen et al. concluded that DT cannot
quantitatively predict the modification level especially when
the Si modification level is in a high range of 4.0–6.0. It has
to be noted that Chen et al. [11] utilized cylindrical sand
cups, but they did not report any preheating of the sand cups.
The thermal analysis parameters (DT and Dt) obtained at
the slow cooling rates (Fig. 5a) can be seen to agree to a
reasonable extent with the measures of the modification
levels obtained at the fast cooling rates. This indicates that the
thermal analysis parameters measured at the slow cooling
rates can be used to predict the occurrence of modification at
the rapid cooling rates in A319 alloy, but the reverse cannot
be true. It has yet to be noticed that the precise prediction of
the level of modification at the rapid cooling rates cannot be
guaranteed with the aid of the thermal analysis parameters
Assessment of Eutectic Modification Level in Al–Si Alloys …
measured at the slow cooling rate and further work has to be
made to examine this possibility.
The points discussed above can be used to draw some
concluding remarks about the prediction of modification
level in Al-6Si-3.5Cu (A319) alloy. The quantitative pre-
diction of modification level based on thermal analysis is
very successful at the slow cooling rates. At the fast cooling
rates, it can only be used as a qualitative tool to evaluate the
modification effect, i.e. it only shows whether the modifi-
cation occurred or not, but it cannot quantitatively inform
about the extent of modification that occurred in the melt.
Al-11Si (A413) Alloy
Similar to A356 and A319, the quantitative correlations
among the microstructural parameters and the thermal
Fig. 6 Correlation of the addition level of Sr with the measured thermal and microstructural variables for Al-11Si (A413) alloy
893
analysis parameters for Al-11Si (A413) binary alloy are
shown in Fig. 6a–c for the heated graphite, and unheated
graphite and steel molds. It has to be noted that in these
figures the cooling rates are not included because they could
not be calculated using the method adopted earlier in
Section “Thermal Analysis Data”.
The Al-11Si alloy is similar to the Al-6Si alloy in that it is
a binary alloy, but differs considerably in the amount of the
Al–Si eutectic which amounts to 40 wt% in the Al-6Si and
86 wt% in the Al-11Si alloy. As mentioned earlier, the
values of TE measured for A413 and A356 (for 0 ppm Sr in
heated graphite mold) are similar and in complete agreement
with the equilibrium value of eutectic temperature reported
in [14]. The unmodified A413 alloy possesses very coarse
eutectic Si particles at slow cooling rate as seen from Fig. 3.
From Fig. 6a, the values of Si particles perimeter, area,
894
circularity, and aspect ratio are 19.8 lm, 14.0 lm2, 0.47,
and 2.72, respectively, and support the microstructure
observation. Increasing the cooling rate, when using unhe-
ated graphite and steel molds, caused a dramatic refinement
in the eutectic Si particles as seen in Figs. 3 and 6b, c.
Taking the perimeter for instance, it can be seen that the
perimeters were 7.3 and 7.8 lm for the unheated graphite
and steel molds, respectively. This refinement in Si particles
as shown in Fig. 3 did not alter the polyhedral form of the
eutectic Si particles as has been reported by [7, 15]. From the
thermal analysis perspective, it has been found the depres-
sion in the eutectic temperature fell within 1.0 °C below the
eutectic growth temperature of the heated graphite mold.
This value of depression falls within the error of temperature
measurement, so it can be concluded that the refinement in
the Si particles size due to increasing the cooling rate was
not actually accompanied by a true depression in the eutectic
growth temperature.
Addition of 50 ppm Sr to the Al-11 Si melt can be seen
on Fig. 6 to have dramatically modified the Si particles for
all the mold types. For example, the values of the perimeter
reached 4.3, 3.7, and 3.7 lm for the heated graphite and the
unheated graphite and steel molds, respectively, and similar
results were observed for the particle area, aspect ratio, and
circularity. The depression in TE accompanying this refine-
ment was considerable (6.8 °C for the heated steel mold, and
10.7 and 9.6 °C for the unheated steel and graphite molds,
respectively). The eutectic solidification time determined
from the heated graphite mold increased appreciably from
113.6 to 140.3 s. Comparison of the microstructures shown
in Fig. 3 at 50 ppm Sr with the American Foundry Society
(AFS) chart for microstructure control in hypoeutectic Al–Si
alloys [16] showed that the ML of the microstructures is 3–4.
Therefore, at the indicated modification levels, the thermal
analysis parameters could precisely reflect the occurrence of
significant modification by which the ML improved from 1
to 3–4 in the Al-11Si (A413) alloy.
Further addition of Sr caused slight refinement in the
microstructure parameters. The decrease in the particle
perimeter, area, and aspect ratio and the increase in circu-
larity are not as big as those reported for the addition of
50 ppm Sr compared to the unmodified alloy. Comparison
of the microstructures at Sr additions of 150 and 300 ppm
with the AFS chart indicated that the modification level is
definitely above 5. On the thermal analysis side, the
depression in the eutectic growth temperature increased with
increasing the Sr addition from 50 to 150 ppm in the heated
and unheated graphite molds and then decreased with further
addition of Sr (300 ppm). In the unheated steel mold,
additions of Sr above 50 ppm were all accompanied by a
progressive decrease in the depression of the eutectic growth
temperature. The eutectic solidification time decreased with
M.S. Abdelrahman et al.
addition of 150 ppm Sr and then re-increased with the
addition of 300 ppm Sr. These values indicate the thermal
analysis parameters were inconsistent with the extent of
modification even though their values are still considerably
higher than those of the unmodified alloy.
The above findings indicate that the conclusion of Chen
et al. [11] is still valid for Sr additions above 50 ppm. The
thermal analysis can precisely predict the extent of modifi-
cation when the modification rating is below 4 and only
qualitatively indicates the occurrence of modification when
the modification rating is above 4. This statement holds true
for the different cooling rates used here, so it sounds that the
latter conclusion is independent of the cooling rate in the
Al-11Si (A413) alloy.
However, a point of contrast appears to hold here. Chen
et al. [11] mentioned that the depression in the eutectic
growth temperature becomes invariant when the modifica-
tion rating was above 4. Tenekedjiev et al. [8] showed that
addition of 140 ppm Sr to 413.2 Al–Si alloy caused a
depression of 2.0 °C and further addition of Sr (440 ppm)
maintained the depression at the same level (2.0 °C). By
comparison, our results showed that the values of the ther-
mal analysis parameter varied with further increase in Sr
above 50 ppm. The actual reason for this difference is not
clear.
Conclusions
Addition of Sr to Al–Si alloys was found in almost all
conditions to successfully modify the size and polyhedral
geometry of eutectic Si to fine fibrous form. It was found that
slow cooling rates required higher addition of Sr to achieve
the same modification level compared to the rapid cooling
rates. The use of thermal analysis could be successfully used
to predict the modification level in the Al-6Si (A356) alloy.
With the recommendation of using the slow cooling thermal
analysis data, it was found that the depression in the eutectic
growth temperature was independent of the cooling rate in
the A356 alloy.
From the correlation of the thermal analysis and mi-
crostructure data for A319 and A413, it was revealed that
thermal analysis could quantitatively predict the level of
modification if the modification rating is below 4.0. At
higher modification ratings (4.0–6.0), thermal analysis gives
only a qualitative inference about the occurrence of modi-
fication, but it cannot precisely predict the modification
level. Furthermore, the type of predictability of the thermal
analysis to the modification level (whether quantitative or
qualitative) was found to be independent of the cooling
rate.
Assessment of Eutectic Modification Level in Al–Si Alloys …
References
1. A. Kearney, E.L. Rooy, ASM Handbook, vol. 2 (ASM Interna-
tional, Materials Park, OH, 1990), p. 123
2. I.J. Polmear, Light Alloys: Metallurgy of Light Alloys, 3rd ed.,
Chapter 4, (Wiley, New York, 1995), 140
3. L.F. Mondolfo, Aluminum Alloys Structure and Properties (But-
terworth, London, 1976), p. 25
4. M.M. Makhlouf, H.V. Guthy, The aluminum-silicon eutectic
reaction: mechanisms and crystallography. J. Light Met. 1, 199–
218 (2001)
5. M. Dash, M. Makhlouf, Effect of key alloying elements on the
feeding characteristics of aluminum-silicon casting alloys. J. Light
Met. 1, 251–265 (2001)
6. S. Shankar, Y.W. Riddle, M.M. Makhlouf, Nucleation mecha-
nisms of the eutectic phases in aluminum-silicon hypoeutectic
alloys. Acta Mater. 52, 4447–4460 (2004)
7. M. Zamani, S. Siefeddine, “Assessment of modification level in EN
AC-46000 aluminum casting alloys using thermal analysis and
microscopic evaluation”, light metals (Wiley, New York, 2015),
pp. 955–960
8. N. Tenekedjiev, J.E. Gruzleski, Thermal analysis of strontium
treated hypoeutectic and eutectic aluminum-silicon casting alloys.
AFS Trans. 99, 1–6 (1991)
895
9. D. Apelian, G. Sigworth, K. Whaler, Assessment of grain
refinement and modification of Al–Si foundry alloys by thermal
analysis. AFS Trans. 92, 297–307 (1984)
10. G.K. Sigworth, The modification of Al–Si casting alloys: impor-
tant practical and theoretical aspects. Int. J. Metalcast. 2, 19–40
(2008)
11. X. Chen, H. Geng, Y. Li, Study on the eutectic modification
level of Al-7Si alloy by computer aided recognition of thermal
analysis cooling curves. Mater. Sci. Eng. A 419, 283–289
(2006)
12. M. Djurdjevic, H. Jiang, J. Sokolowski, On-line prediction of
aluminum-silicon eutectic modification level using thermal anal-
ysis. Mater. Charact. 46, 31–38 (2001)
13. J.E. Gruzleski, The art and science of modification: 25 years of
progress. AFS Trans. 100, 673–683 (1992)
14. H. Okamoto et al., Metals Handbook, vol. 3 (ASM International,
Materials Park, OH, 2016), p. 79
15. M. Zamani, S. Seifeddine, M. Aziziderouei, “The Role of Sr on
Microstructure Formation and Mechanical Properties of Al–Si–
Cu–Mg Cast Alloy”, Light Metals (Wiley, New York, 2013),
p. 297
16. N. Tenekedjiev, H. Mulazimoglu, B. Closset, J.E. Gruzleski, in
Microstructures and Thermal Analysis of Strontium-Treated
Aluminum-Silicon Alloys, (AFS: American Foundrymen’s Society,
Des Plaines, IL 1995) 40
 Part XXI
Cast Shop Technology:
Melting, Energy, and Dross
 Application and Results of Oxipyr® Diluted
Combustion in Aluminum Furnaces

Michael Potesser and Johannes Rauch

Abstract
Diluted, mild or flameless oxyfuel combustion has shown in the past years huge successes as
an optimization tool for different high temperature applications. This innovative combustion
technology has a lower flame temperature, more uniform temperature distribution and low
concentrations of oxygen as well as nitrogen inside the furnace, leading to low fuel
consumption and very low NOx levels. In this work we analyze the optimization processes of
different types of rotary and reverberatory furnaces (fix, tiltable) with Messer Oxipyr®
burners, which led to impressive savings, dross reduction and ecological improvements for
the customers. A review of the available literature, on this topic, is also given.

Keywords
Oxyfuel Diluted combustion Aluminum furnace Emission reduction Energy reduction

Introduction
Already in the 1930’s F.W. Davis (1) wrote that “All non-
ferrous metallurgy will be benefited by the use of cheap
oxygen … the application of oxygen will revolutionize the
art of smelting and it will probably change the whole
operation and equipment.” Today oxygen is a daily tool for
pyrometallurgy being used in flash smelting and converting
processes. Recent developments for the usage of oxyfuel are
in the secondary production such as TBRC (Top Blown
Rotary Converter) and for different types of holding and slag
furnaces with different types of low calorific fuels. Diluted,
low temperature oxyfuel combustion delivers an additional
tool for further applications such as on aluminum furnaces.
Combustion: Oxyfuel and Diluted, Mild,
Flameless Combustion
The efficiency of industrial combustion processes can be
increased in two ways, either by preheating the fuel and
combustion air or by adding oxygen. In air combustion only
M. Potesser (&)
J. Rauch
Messer Group, Industriestraße 5, 2352 Gumpoldskirchen, Austria
e-mail: michael.potesser@messergroup.com
low flame temperatures can be reached, due to the high 79%
N2 ballast. This results in high heat loss in the exhaust gas,
because of the low combustion efficiency.
In the Fig. 1 the theoretical flame temperature for the
stoichiometric combustion of natural gas is plotted against
oxygen enrichment. Therefore it can be concluded, that even
low enrichment values produce higher flame temperatures
and result in higher combustion efficiency. In addition to the
higher thermal efficiency of oxygen burners compared to air
burners is the second point, which speaks for the use of
oxygen, the much higher energy efficiency due to the heat
transfer. Heat transfer occurs by convection and radiation.
With increasing temperature, the proportion of the radiation
rises compared to convection. In addition, the heat radiation
in an oxygen flame due to the higher content of the three
molecular gases CO2 and H2O as well as the lower NOx
level in the exhaust gas is more intense compared to air
flame.
Thermal NO formation is controlled by the flame tem-
perature, the oxygen concentration in the reaction zone and
the residence time of the products of combustion in the
high-temperature zone of the flame. As fundamental research
shows, thermal NO formation tends to be zero for normal
industrial gas burner residence times as long as the flame

© The Minerals, Metals & Materials Society 2017 899

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_108
900
Fig. 1 a Influence of the
combustion air temperature and
the oxygen concentration on the
combustion efficiency.
b Theoretical flame temperature
for the stoichiometric combustion
of natural gas plotted against the
oxygen concentration of the
combustion air
temperature does not exceed 1600 °C. Therefore, burners
must be designed to avoid peak temperatures above 1600 °C
in high-oxygen zones of the flame. Staged combustion, flue
gas recirculation and flameless/diluted/mild oxidation are
techniques which can reduce NOx emissions substantially.
Diluted Combustion
In the past two decades the diluted combustion has been a
matter of intensive research in order to understand fully the
basic physical parameters in order to introduce this com-
bustion process more into the industry [2, 3]. Mild
(Moderate or intense low oxygen dilution) combustion and
improvement over that known as flameless oxidation is a
newly developed and implemented technique for achieving
low emission of pollutants and improve thermal efficiency of
combustion systems. It is characterized by both an elevated
temperature of reactants and low temperature increase in the
combustion process. It is also called flameless because under
optimized conditions the oxidation proceeds with no visible
or audible flame. The main operation principle for this
technique lies in the concept of exhaust gas and heat recir-
culation. The heat from the exhaust gases is used to raise the
temperature of the oxidant stream and the exhaust gases are
used to dilute the oxidant stream to reduce the oxygen
concentration and maintain low temperature in the com-
bustion zone. The first requirement is, reactant temperature
above the self-ignition temperature, may be achieved by
preheating the fuel, the oxidizer, or additional ignition. The
second requirement, large entrainment of inert species in the
M. Potesser and J. Rauch
reaction region, may be achieved in different ways by either
internal or external recirculation of exhaust gases. Advan-
tage of this combustion technology, is flame stabilization
homogenous temperature, decrease in the temperature gra-
dients, and control of maximum temperatures with beneficial
effects on materials.
Oxyfuel burners using in-furnace flue gas recirculation
were first developed in the late 1970s to provide a
high-momentum, low-temperature flame imitating the tra-
ditional air flame. The concept of in-furnace flue gas recir-
culation was further advanced in the late 1980s to the
conditions approaching those of a “homogeneous reactor” in
which the furnace temperature and species concentrations
are uniform throughout the furnace. The concept of this
combustion process, known as “dilute oxygen combustion”
[4–6]. The basic concept is to react fuel with a hot, dilute
oxidant containing only 2–10% oxygen to produce a low
flame temperature “reaction zone.” The flame temperature
can become as low as 260 °C above the temperature of hot
oxidant. An oxygen or air jet is injected into the furnace,
separated by some distance from the fuel jet, to produce “hot
dilute oxidant” by jet entrainment of furnace gas in a
“mixing zone.” The reaction zone and the mixing zone are
segregated within the furnace to prevent direct mixing and
combustion of the undiluted oxidant and fuel (Fig. 2). One
or more pairs of oxidant and fuel jets are placed on the
furnace walls to create furnace gas recirculation patterns that
promote dilution of oxidant and good mixing of fuel. Further
authors have reported of successful new concepts of flame-
less oxyfuel burners and of implementations in mainly the
steel industry [7–11].
Application and Results of Oxipyr® Diluted Combustion …
Fig. 2 Principle of flameless/
diluted combustion [2]
Types of Oxipyr® Burners for Aluminum
Furnaces
In the past years Messer has developed different Oxipyr®
burners which are able to operate in a flameless mode and
can be used for the optimization of the aluminum Furnace
processes. Oxygen burners use a completely different mixing
between fuel gas and oxidizer and utilize completely dif-
ferent volume flow rates. Therefore the design of oxyfuel
burners differs a lot when compared to air-fuel burners.
Oxipyr®-Flex
If the turn-down ratio of the burner and variable flame length
is needed, the Oxipyr® Flex burner series can be used
(Fig. 3b). A movable cone inside the angled oxygen flow
channel can change the exit velocity of oxygen and the
impulse ratio between fuel gas and oxidizer. With this
movable cone the flame length can be influenced on-the-fly
while the burner is running inside the furnace. A massive
turndown ratio of 20:1 and more can be achieved as well for
minimal ignition loads. This burner type is very common for
rotary furnaces and can be adapted to the needs of the fur-
nace in every possible way.
Oxipyr®-Air
The Oxipyr ® -Air series originates in the Oxipyr ® -Flex
series but uses the moving cone to adjust the burner to
different oxygen enrichment levels of the oxidizer (a
mixture of oxygen and air). This type of burner is mainly
901
used inside reverberatory furnaces in the Aluminum
industry, but can also be used for specialized operation
methods in the copper industry. For example, if the
melting is done with pure oxygen and the phase, where the
furnace is kept warm during weekends, is done with air.
The Oxipyr ® Air can be engineered to fulfill a wide variety
of applications (Fig. 3c).
Oxipyr®-F
The basic and most robust flameless combustion system for
fuel gas and oxygen is formed by the Oxipyr® F series
(Fig. 3a). The pipe-in-pipe design delivers excellent long-
evity and is still used in a lot of furnaces. The flameless
combustion with a low peak temperature and high exit
velocities is responsible for a very good temperature
homogenization inside the furnace (Fig. 4). This minimizes
temperature peaks, dross losses and refractory wear.
Optional exchangeable tips can lower the spare part costs for
extremely harsh environments as well. As with all Messer
burners the exit velocities of the gases are tailor made to the
desired flow rates and stoichiometry.
Development of Oxyfuel in Secondary al
Production
The selection of the most suitable furnace type is determined
by the metal content of the scrap (oxide content), type and
content of impurity (annealing loss), geometry of the scrap,
frequency of change in alloy composition, and operating
conditions (Fig. 5).
902
a b
c
Fig. 3 Different types of Oxipyr® burners for aluminum furnaces a F, b Flex, c Air [10]
Fig. 4 Oxipyr® F tested in the combustion chamber of competence center for metallurgy of the Messer Group at different chamber temperatures
(400/600/900 °C)—changing to flameless mode
The theoretical energy required to heat aluminum from
room temperature to its melting point, melt it, and raise the
molten aluminum to a higher temperature is calculated and
explained in Fig. 6. Pure aluminum melts at 660 °C and
requires 0.30 kWh per kg to melt.
Primary or secondary aluminum is first melted, alloyed
and treated in large fuel-fired furnaces, transferred to holding
furnaces for additional processing and casting into ingots.
Technically, it is possible to melt down scrap with or without
the application of salt. The rotary drum furnace, either static
(Rotary Furnace—RF) or tilting (Tilting Type Rotary Fur-
nace—TTRF), is used for salt fluxing. Hearth/reverb fur-
naces (Closed-well or Side-well) and induction furnaces are
normally used without salt. The most common technology
aimed at removing impurities from the melt is simple flux-
ing. Fluxing is when various compounds (usually inorganic
M. Potesser and J. Rauch
salts), chemicals, and gases are added to: (1) reduce oxida-
tion, (2) encourage certain elements to migrate into the
dross, or top layer of the melt, (3) increase the fluidity or
wettability of the melt which facilitates the separation of
inclusions, (4) remove hydrogen and nitrogen gas, and
(5) remove Ca, Sr, Na, Mg, and Li. Fluxes are useful in
removing calcium, magnesium, sodium, etc. from aluminum
by serving as catalysts for their equilibrium oxidation reac-
tions. The salt mixture covers the aluminum to prevent
further oxidation, strips away the oxide layer from the
molten metal, promotes coalescence of metallic droplets, and
dissolves or suspends other impurities attached to the metal.
How does the energy transfer function in an aluminum
furnace? Radiation and convection transfer heat from the
flame to heat the refractory lining and the surface of the bath.
The refractory then radiates more heat to the bath. If there is
Application and Results of Oxipyr® Diluted Combustion …
Fig. 5 Classification of scrap types and furnace selection criteria by oxide content and annealing loss as well as by ratio of surface area to
intermediate part size [12]
Fig. 6 Aluminum energy requirements for heating and melting [13]
scrap or ingots exposed above the bath level, it also is heated
by the radiation and the convection of hot combustion gases.
When the charged metal is below the level of the liquid bath,
heat is transferred from the liquid by conduction and con-
vection. Aluminum is usually considered a good conductor
of heat, but in fact the amount of heat conducted from the
liquid to the charge is very poor. To effectively transfer heat
from the liquid requires convection—circulation of the liq-
uid metal within the bath—either forced (pump, stirrer,
rotation etc.)
903
In fuel-fired aluminum melting furnaces, O2-enhanced
combustion can provide increased productivity via increased
melt rate, melt energy cost savings, reduced emissions and
reduced melt loss (increased aluminum recovery). In most
cases, an O2 combustion system is selected for retrofit to an
existing melt furnace originally utilizing a 100% combustion
air system to accomplish at least one of the above objectives.
O2 combustion systems can be either 100% oxy/fuel (no
combustion air) or a combination air/oxy/fuel. Factors that
influence the optimum type of O2 combustion system for a
904
particular furnace include type of furnace (well-charged
reverb, direct-charged reverb, rotary), type of charge mate-
rials (clean vs. oily or coated, thick vs. thin-wall), number
and location of burners, level of combustion air preheat (cold
air, recuperator or regenerative burners) and relative cost of
fuel and O2.
Tilting Type Rotary Furnace (TTRF)
Still up till today the rotary drum furnace (RF) is the most
common unit to melt high impurity scraps (contaminated
with hydrocarbons) and dross. The fixed rotary furnace
consists of a cylindrical steel shell, which is horizontally
mounted on wheels and lined with bricks/cement mass. The
newest versions have additional mixing paddles in order to
maintain an improved mixing and the position of the oxyfuel
burner is on the off gas side (double pass RF). Remaining
units are found in countries as Italy and can have a charging
weight of up to 100 tonnes. This type is charged very
quickly using the much larger charge opening. It is operated
under a positive furnace pressure, giving the possibilities to
adjust more exactly the furnace atmosphere. Due to the fact
that it rotates under an adjustable angle the charge is mixed,
improving both the homogeneity and the heat transfer. The
furnace is tilted to pour out the aluminum (Fig. 7). The dry
slag remains in the furnace—no time is wasted for opening
of tap hole. Tilting furnaces are able to pour out the alu-
minum at a quicker rate and with more accuracy, and no time
is lost opening and closing the tap hole. Finally time and
labour required for slag disposal is reduced with TTRFs as
dry slag can be emptied out through a simultaneous tilt and
rotate operation at the end of the cycle. The consumption of
salt is dramatically reduced in comparison to RF (at the salt
factor 1–2)—according to the feeding material resulting in a
Tilting Type Rotary Furnace (TTRF)
Fig. 7 Example for an Oxipyr® fired TTRF in operation >10 years [14]
M. Potesser and J. Rauch
salt factor between 0.3 and 0.5. Much higher thermal effi-
ciencies of 75–80% can be achieved and a productivity
uptime of up to 98%. In comparison to the first reported
TTRF operational data in Europe [10] the efficiency of
operation has improved throughout the years due to high
automatization. Figure 8 compares different rotary furnace
data.
The TTRF has advanced to the standard scrap “omni-
vore”, dealing with all kinds of scrap, even the most polluted
ones. In those furnaces the pure oxyfuel burners are also
widely accepted as the best melting device. Messer is
cooperating with many different furnace builders to provide
new furnaces with out-of-the-box firing systems including
burners and controls. The supplied systems range from very
compact solutions with post-combustion oxygen delivered
through the burner up to top-of-the-shelf solutions with
lances and post combustion chambers with a separate burner.
When using an oxygen lance system, if the charge contains
organics it is possible to exploit this ‘latent’ energy rather
than sending the unconsumed hydrocarbons to the
bag-house filter. In such cases we have recorded energy
returns of less than 200 kWh per ton melted.
Reverberatory Furnace (also Hearth, Shaft,
Multi Chamber, Casting Furnace)
Reverberatory furnaces are used to remelt or recycle alu-
minum, in most cases without flux addition. In order to reach
higher temperatures which are needed for example for liquid
transport of aluminum or to charge bigger scrap parts the
energy demand is higher compared to the TTRF. With Oxi-
pyr® technology, simple chamber furnaces could be changed
in an efficient recycler by using the VOC contaminated flue
gases out of the scrap for post combustion directly in the
Application and Results of Oxipyr® Diluted Combustion … 905

Fig. 8 Basic data TTRF general

TILT TYPE ROTARY FURNACE (TTRF) - OXYFUEL BASIC DATA
and for RF/TTRF oxyfuel
operation and Messer TTRF TTRF gen.
TTRF RF TTRF
examples
Salt factor 0,3 - 0,5 1 0,35
Capacity (t) 5,0 - 30,0 20 14
Cycle time (h) 2,0 - 4,0 5 3,5
Cycles per day 4,0 -7,0 4,8 6,9
Throughput per day (t) 25 - 130 42 55
Energy consumption Scrap clean (kWh/t) 350 - 400
Scrap contaminated (kWh/t) 250 - 350
Dross (kWh/t) 250 - 400 550 380
Yield Scrap clean (%) 90 - 97
Scrap contaminated (%) 85 - 90
Dross (%) 45 - 65
Oxygen demand (Nm³/t) 110 80

Fig. 9 Left temperature

homogeneity of a reverb furnace
with diluted Oxipyr® F burners,
right indication about the
thermographic picture

furnace. According to Messer experience in revamping of System 1: Hot off-Gas Recirculation

furnaces equipped either with cold air, recuperative or even
regenerative burners or building up new ones, two systems
are available for reverb furnaces. Both systems are able to
provide the necessary combination of radiation and convec-
tion according to the actual temperature either by changing
the recirculated flue gas volume (System 1) or changing the
oxygen enrichment mode (System 2). Especially important
and in our focus is “low to no maintenance” hours of the
combustion system (e.g. cleaning of recuperator/regenerator
at conventional burners) because of dusty and aggressive
atmosphere. In order to homogenise the temperatures of the
furnaces and reduce dross building mechanisms, just diluted
combustion is used (Fig. 9). Flameless or diluted combustion
leads to lower NOx values and better temperature uniformity
in furnaces. In some cases such a combustion can contribute
to a reduction of the buildup of corundum (high temperature
dross Al2O3) in case of hotspots by using none flameless
oxyfuel burners (Fig. 10).
(HOR) with Oxipyr®—F an Oxyfuel Burner
System
In order to gain more convection beside radiation (already
available through the oxygen enhanced combustion) a hot
gas fan recirculates the flue gases right from the dumper
either again directly to the Oxipyr®-F burner or to a
certain furnace input area. This leads, besides obtaining
the convection needed for melting of T-bars etc. to a
higher rate of turbulence and a possibility for post com-
bustion of VOC directly in the furnace. With this system a
reduction of energy demand per ton is possible and the
installation of a post combustion chamber, for low to
medium contaminated scrap, is not necessary anymore.
The post combustion is either done over the oxyfuel
burner or in the ceramic fibre lined off-gas channels. The
system is applicable both to single or multiple chamber
furnaces (Fig. 11).
906 M. Potesser and J. Rauch

Original Oxipyr® Original Oxipyr® Original Oxipyr®

Melting+ Melting+ melting 1 melting 1

Furnace type Holding Holding chamber chamber
Furnace size (t) 30 30 50
Combustion system (°C) cold air Air oxyfuel F recuperative F + HOR
Air preheat Temperature (°C) 20 20 400 20
Average melting rate (%) 100% 140% 100% 100% 100% 150%
Energy per t Al output (% or kWh) 100% 50% 100% 95% 900 410 -500
Oxygen enrichment (%) 21% 25 - 70% 100% 100% 21% 100%
Oxygen per t Al output (% or Nm³) 0 50 - 70 100% 95% 0 90 - 100
Natural Gas to Oxygen price ratio (Nm³/ Nm³) 2,5 2,5 2,3

Fig. 10 Examples of Oxipyr® burners and system applications on aluminum reverb furnaces

Fig. 11 Oxipyr® F + HOR applied to single (upper row) or multiple chamber (lower row) reverb furnaces

System 2: Oxipyr®-Air Oxyfuel Burner Systems
The most frequently applied burner in reverb furnaces
which were optimized by Messer is the Oxipyr®-Air burner
which has a movable cone and can use a wide range of
oxygen enrichment in combustion—between 25 and 100%.
Generally we use oxygen enrichment between 30 and 70%
in order to achieve total costs close to regenerative fired
furnaces including maintenance and electric power costs 8
(Fig. 12).
Application and Results of Oxipyr® Diluted Combustion …
Fig. 12 Application of Oxipyr® air burners on a reverb furnace
Conclusions
Aluminum is developing faster than any other main material
due to economic growth and substitution of steel. Recycling
is going to contribute continuously more to the production
demand and open additional possibilities for oxygen
enhanced combustion also due to melting furnaces which are
optimized for oxyfuel. Messer Oxipyr® applications both on
TTRF and reverb furnaces show the high economic and
ecological optimization potential in this segment.
References
1. F.W. Davis, Report of Investigations no. 2502 (Bureau of Mines,
Washington, D.C., 1923)
2. J.W. Wünning, in Thermprocess Symposium 2003
3. J.A. Wünning, J.W. Wünning, Prog. Energy Combust. Sci. 23, 81–
94 (1997)
4. J.E. Anderson, Symposium of Industrial Combustion Technologies
(1986), pp. 329–334
907
5. H.M. Ryan et al., Dilute Oxygen Combustion—Phase I Report,
Report No. DOE/ID/1331-T1 (U.S. Department of Energy,
Washington, D.C., 1997)
6. M.F. Riley, H. Kobayashi, A.C. Deneys, JOM, 21–24 (2001)
7. D. Spoljaric, M. Potesser, B. Holleis, M. Demuth, J. Rauch, in
Proceedings of the 3rd Euroasia Mena Steel Summit, 22–23
January 2013
8. M. Potesser, B. Holleis, M. Demuth, D. Spoljaric, J. Zauner,
Cu 2010, vol. 2, Pyrometallurgy I (GDMB, 2010), pp. 1051–
1060
9. M. Potesser, B. Holleis, D. Spoljaric, H. Antrekowitsch, Stahl und
Eisen (2008), pp. 59–63
10. M. Potesser, B. Holleis, D. Spoljaric, BHM, 153. Jg. Heft 3 (2008),
pp. 121–125
11. W. Blasiak, W.H. Yang, K. Narayanan, Sche´ele J. J. Energy Inst.
80(1), 3–11 (2007)
12. U. Boin, T. Linsmeyer, F. Neubacher, B. Winter, Stand der
Technik in der Sekundäraluminiumerzeugung, Band 120, M-120,
(Wien, 2000)
13. U.S. Energy Requirements for Aluminum Production, Historical
Perspective, Theoretical Limits and Current Practices, February
2007
14. D. Spoljaric, D. Wieck, Recycling aluminium with oxygen
combustion technology, in Aluminium International Today,
July/August 2003, pp. 26–28
 Case Study of Magnetically-Stirred Casting
Furnaces at New Zealand Aluminium Smelters
Limited

Ray Cook, Marcos Varayud, Steve Iijima, and Eishin Takahashi

Abstract
New Zealand Aluminium Smelters Limited (NZAS) manufactures the highest purity
primary aluminium ingot, high quality extrusion billet and rolling slab products. In 2011,
NZAS installed Zmag’s MagStir™ into a 50T casting furnace. MagStir utilises Zmag
Permanent Magnetic Circuit, the world’s first, proprietary permanent magnet-based
technology for contactless stirring in the bath. Agitation of casting furnaces during alloying
to achieve elemental dissolution and temperature control is the key part of furnace
preparation and when performed in an efficient manner, it can give significant savings in
fuel and alloying costs and increased throughput. In 2016, NZAS added MagStir to two
more casting furnaces and achieved significant improvements in temperature control during
all phases of furnace preparation. This paper is a case study on the benefits of stirring in
general, specific benefits observed using Zmag’s MagStir at NZAS as well as lessons
learned in the operation of the systems over 5 years.

Keywords
NZAS Zmag Stirring Aluminium Magnets

Introduction electromagnetism and mechanical pumps are also discussed

Zmag was started in 1990 and over the past 26 years has
pioneered the field of magnetic circuit design. One of the
many technologies the company has industrialised is the
Eddy Current Separation technique [1], now widely used in
the recycling and scrap sorting industry. Technologies based
on magnetic circuit design are now being introduced to
molten metal processing. The Zmag Permanent Magnetic
Circuit (zPMC™) technology has been developed for
moving molten metal. The technology discussed in this
paper is MagStir™, a product line for stirring aluminium in a
furnace, however stirring using other methods such as
R. Cook (&)
M. Varayud
NZAS (New Zealand Aluminium Smelters Limited), Tiwai Road,
Tiwai Point, Invercargill, 9877, New Zealand
e-mail: RAYMOND.COOK@pacificaluminium.com.au
S. Iijima
E. Takahashi
Zmag, Ltd, 235-5 Ne, Shiroi, Chiba, 270-1431, Japan
in this paper.
The NZAS smelter is a joint venture between Pacific
Aluminium and Sumitomo Chemical Company and was
commissioned at Tiwai Point, New Zealand in 1971. The
primary focus of the plant is the production of Value Add
Product (VAP). These include foundry ingot, extrusion bil-
let, rolling slab, high purity (>99.90% Al) and ultra-high
purity (>99.97% Al) ingot [2].
In the first half of 2016, NZAS cast 33 different alloys in
61 different diameters and cast length configurations. Each
day, several routine alloy changes must be managed effi-
ciently to achieve the required throughput. An efficient fur-
nace preparation procedure is the key to maintaining
throughput in this challenging climate.
In the current economic climate for the industry, and for
the NZAS smelter, increased volume of high quality extru-
sion billet is a key input in the drive to maintain profitability.
The addition of the MagStir system to the billet casting
furnaces is one initiative in NZAS’ aim to produce the

© The Minerals, Metals & Materials Society 2017 909

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_109
910
highest quality extrusion billet. Other recent work on opti-
mising grain refiner additions has led to a significant
reduction in TiB2 contents in cast products. Improvements
have also been made on final inspection with the introduc-
tion of an automatic multichannel ultrasonic inspection
system (Fig. 1) to replace hand held inspection. This offers
benefits of full scans of the surface, volume and centreline of
all billets to detect surface defects and internal inclusions,
cracks, oxide films and coarse grains [3].
These initiatives, together with MagStir reduce variation
in melt quality. Boride inclusion levels are reduced and by
using the multichannel inspection system NZAS is able to
provide the highest quality extrusion billet for the most
demanding applications.
Why Stir?
The aluminium used in everyday products and industries (for
example, automotive, aerospace and beverage cans) is
almost never pure aluminium. Instead it is a complex recipe
of elements, the composition of which varies by application.
Whatever the application, the elements need to be added,
melted and/or dissolved uniformly in the melt to produce a
homogenous material suitable for casting. Furthermore,
particularly in today’s challenging and competitive global
economy, it is critical that maximum value be extracted from
the manufacturing process. Stirring provides the plant
operator with a tool which can lower direct costs, increase
productivity and therefore increase profits. In an industry
which has maximised efficiencies in most other areas, stir-
ring is one of the remaining areas where opportunities for
improved productivity are still available.
Fig. 1 Multichannel ultrasonic
inspection station
R. Cook et al.
Stirring Benefits
An efficient stirring process contributes in multiple ways
to furnace preparation that will be further discussed in
this paper. While the benefits vary among the types of
furnace (e.g., tilting, stationary, side-well) and operations
(e.g., dry hearth, continuous), broadly speaking, the fol-
lowing benefits are observed with efficient and continu-
ous stirring:-
• Temperature homogenisation between top and bottom of
molten aluminium.
• Increase in melting speed.
• Shorter cycle time and thus an increase in productivity.
• Improved chemical homogenisation resulting in a com-
position which is uniform throughout the molten
aluminium.
• Continuous stirring reduces dross by minimising
molten aluminium overheat and necessity of manual
stirring.
• Melt loss reduction and recovery increase. Less manual
stirring translates to a smaller chance of breaking the
surface and oxidising molten aluminium.
• Heat loss through opening the furnace door is minimised,
and less energy is required to bring a furnace up to
temperature.
Stirring Techniques
There are many methods of stirring. Several of the most
common are as follows:
Case Study of Magnetically-Stirred Casting Furnaces …
Manual
Traditionally, stirring was limited to raking; literally
attaching a long steel rake to a forklift and rapidly agitating
the melt at various points in the cycle (such as introduction
of ingots and scrap, alloying, adding molten aluminium from
a pot line). Today, raking is still the dominant form of
stirring due to its simplicity, cost, and basic inertia against
process change. However, raking has significant disadvan-
tages, including:
• Non-continuous. Raking is done infrequently;
non-continuous stirring leads to uneven elements distri-
bution, poor temperature homogenisation and longer
furnace cycle time.
• Loss of heat. Opening the furnace door for raking leads
to significant loss of energy, especially with burners
turned off as well.
• Introduction of Oxygen. Opening the furnace door also
introduces an unwanted chemical element into the bath—
oxygen. Oxygen contributes to dross which contributes
to product loss.
• Safety. Manual stirring by its very nature requires oper-
ator involvement. A process which minimises operator
involvement around the furnace reduces risk factors.
Mechanical Pump
A mechanical pump uses an impeller typically made of
graphite which spins rapidly, agitating and stirring the melt.
While better than manual stirring, maintenance is a signifi-
cant issue. The graphite impeller will break at unpredictable
and inopportune times. Resulting maintenance, repair, run-
ning cost, and downtime negatively and cumulatively affect
the furnace and casthouse productivity.
Fig. 2 MagStir under furnace
application
911
Electromagnetic
Electromagnetic stirrers (EMS) have been around for
roughly 40 years and are the system most widely considered
in casthouses for indirect (contactless) stirring. EMS offers
continuous stirring and reliable service and is a good solu-
tion for casthouses that can support its requirements. How-
ever, one of the limitations is the significant power
requirements necessary to generate the magnetic fields.
Adequate power infrastructure needs to be secured and in
place at the time of installation. Furthermore, the additional
running cost from electrical consumption can detract from
the productivity benefits inherent in stirring. EMS also
requires a large, complicated control panel, transformer,
frequency converter, and most cases water cooling system
(or large air blower system).
Zmag’s MagStir
MagStir is a line of products (Fig. 2) which uses a propri-
etary permanent magnetic circuit. A full description of the
technology is beyond the scope of this paper. However,
simply put, the rotating permanent magnetic circuit shifts
magnetic fields in molten aluminium. This generates an eddy
current, moving molten aluminium in the general direction
of the permanent magnetic circuit rotation. Since the per-
manent magnetic circuit is a magnetic circuit that is con-
figured with permanent magnets, electricity is not required to
generate the magnetic fields.
The benefits of the stirrer are as follows:
• It can be used continuously and with minimal operator
interaction.
• Energy Efficient. Electricity is not required to generate
the magnetic fields. Electricity use is limited to turning
912
Fig. 3 Canal/full depth trough
design
the permanent magnetic circuit and running a small
cooling air blower. Typical consumption varies by
application and version but is generally between 5 and
22 kW (6.75–30HP) in total.
• Powerful. While stirring performance varies greatly by
application, the stirrer can move a significant volume of
molten aluminium. Flow rates up to 90 tonnes per minute
have been measured in the field. Actual results depend on
a variety of factors.
• Simple Operation, Simple Maintenance. Controls for the
stirrer are On/Off and rotational speed/direction. Main-
tenance is limited to application of bearing grease and
change of motor oil on a regular schedule.
Installation Types
Permanent magnetic systems can be designed to be posi-
tioned under a furnace, on the sidewall, or utilizing a
canal/full depth trough going around the stirrer in order to
maximise flow into the furnace (Fig. 3). The best design
depends on space, customer requirements and other factors.
Magstir at NZAS
Slab Casting Furnace
The first installation at NZAS in 2011 was a floor mounted
unit located under a 50 tonne casting furnace used for rolling
slab production. The installation was made as part of a
package of improvements. In this stirrer, the permanent
magnetic circuit rotates in a vertical plane and thus the
R. Cook et al.
magnetic fields interact with the melt intermittently pushing
it gently towards the side wall causing a circular motion as it
then ascends to the surface, thus giving mixing from bottom
to top (Fig. 4).
Following installation of this unit significant benefits
were achieved [4] including:
• Reduction in dross generation of 25%.
• 50% reduction in stirring and skimming time and thus
also savings in tool and equipment wear.
• Improved refractory life due to reduction in manual
stirring damage to furnace walls and hearth.
• Reduced personnel safety risks due to reduced interac-
tions with hot aluminium.
• 7% reduction in fuel oil usage and thus equivalent CO2
emissions.
• Reduced variation in alloying efficiencies and especially
improved recoveries in hard alloy (Ti) and a reduction in
magnesium burning on the melt surface.
Fig. 4 Flow pattern from floor Mount—vertical plane
Case Study of Magnetically-Stirred Casting Furnaces …
• Improved temperature homogeneity in the furnace lead-
ing to reduction in temperature related defects in cast
products.
• Improved product quality due to increased control of
furnace preparation (temperature, inclusions, oxides and
spinels).
• Increased throughput (16.7%) due to reduced furnace
preparation times by achieving alloy and temperature
targets more reliably.
Billet Casting Furnaces
Following the success of the slab casting installation, further
permanent magnetic units have recently been installed under
50 and 65 tonne billet casting furnaces.
Due to space limitations under these furnaces, a different
version of the floor mounted units were installed. These units
rotate in a horizontal plane producing a circular motion in
the hearth (Fig. 5). The continuous rather than intermittent
interaction of the magnetic fields with the furnace charge can
give a more aggressive mixing pattern forming a vortex at
higher speeds. Initial installation showed significant visible
liquid motion in the furnace and temperature homogenisa-
tion from surface to bulk was rapid as expected. Excessive
dross formation was noticed at the higher speeds, so the
speed was limited to a point where no additional dross was
formed; however, temperature homogenisation was still
excellent.
Reduction in Alloying Stir Requirements
Alloying additives at NZAS are generally added first to the
liquid heel remaining from the end of a cast. Although this
gives the maximum time available for dissolution of these
additives, it is generally to a cold hearth at casting
Fig. 5 Flow pattern from floor Mount—horizontal plane
913
temperature and thus is not optimal. An efficient manual stir
is imperative to achieve maximum dispersion before addi-
tion of scrap, re-melt billet and finally potroom metal as it
becomes available. Further manual stir is not possible whilst
scrap melting is occurring, so possible segregation of addi-
tives can occur leading to reduced or inaccurate recoveries.
One of the features of the MagStir system is the ability to
vary the stirring speed. A high speed stir is seen as being
beneficial for alloying and offers the possibility of replacing
the requirement for the initial manual stir of alloying addi-
tives or at least a significant reduction in duration.
Trials with the stirrer in slab casting found that there were
issues with high iron alloys when using flux free additives.
The less aggressive stir meant it was necessary to spread the
iron additives around the furnace and follow this up with a
manual stir to gain minimum variance in iron content on
sampling. Although there was melt homogenisation, some
areas were quicker to reach this point than other areas.
Addition of the iron additive above the magnetic stirrer in
large quantities was not recommended. A different rotation
(horizontal plane) with higher and continuous mass flows is
seen as a possible solution to this issue.
Improved Scrap Melting
Because NZAS does not operate a dry hearth charging
strategy, scrap charging occurs after alloying additions are
made to a liquid hearth. This results in less than optimal heat
transfer from the burners to the scrap resulting in super-
heating of the liquid surface and high dross formation. The
continuous stir offered by permanent magnetic stirring gives
a more uniform temperature distribution and allows the
colder metal to be moved away from the scrap to facilitate
faster and more efficient melting. The continuous stir will
also aid in dissolution of any remaining alloying additives.
The high speed vortex is not seen as necessary in this situ-
ation due to the higher levels of dross formation.
Casting Temperature Control
In a reverberatory furnace, heat transfer occurs from the
walls to the charge by radiation through the surface layer of
the charge. Without stirring, there is temperature stratifica-
tion with low temperatures at the bottom of the furnace and
superheating of the surface. This leads to dross formation
and in the worst case allows thermiting.
Previously, manual stirring using a rake attachment on a
forklift or furnace tender vehicle was the only way to
achieve a uniform temperature distribution in the charge.
Prior to casting, the furnaces must reach a pre-defined
temperature which is achieved whilst cooling from a higher
914
Fig. 6 Temperature control with/without permanent magnetic stirring
setpoint. If there is any casting delay, the temperature target
may be missed and the furnace would then need to be
reheated. Without mixing this again results in a superheated
surface and reliance on the experience of the furnace oper-
ator in deciding when sufficient superheat has been added to
heat the furnace. In the past, manual stirring was used to
rehomogenise the furnace to get the correct temperature.
This manual stirring can result in further delays as well as
higher energy costs. With permanent magnetic stirring,
temperature stratification is virtually eliminated, so the fur-
nace operator can heat the whole charge to the required
temperature in a controlled manner, saving energy and time
in furnace preparation.
The benefits on temperature control can clearly be seen in
Fig. 6 on reheating a 47 tonne furnace charge. Without
permanent magnetic stirring and with the burners firing,
there is rapid and significant variation between the surface
and bulk temperatures. When the permanent magnetic stir-
ring is started, temperature equalisation occurs rapidly and
further temperature increase is controlled. Deviation from
surface to hearth is usually ±2 °C or better when the per-
manent magnetic stirring system is operating. This results in
efficient fuel usage and minimisation of the time taken to
reach temperature setpoints.
Increased Throughput
As a result of the improved temperature control prior to cast
start, there can be productivity gains. With a single casting
station being serviced by two casting furnaces, maximum
throughput can be achieved if the time from ending one cast
to starting the next is minimised. After the routine tasks of
stripping the pit, servicing the moulds and preparing the
launder/filter systems are completed, the most common
delay at NZAS has been waiting for the furnace to be ready
R. Cook et al.
Fig. 7 Productivity improvements with magnetic stirring
to cast. This is a combination of reaching temperature and
chemical targets. Delays are costly in any casthouse and at
NZAS more so due to the daily requirement to consume over
900 tonnes of potroom metal in the most profitable manner.
If not used for high quality extrusion billet, then this metal
may have to be cast as lower value products.
To manage the daily requirements for production of a
range of ingot, slab and billet products, NZAS has developed
a Casting Visualisation system that balances potroom tap-
ping to furnace preparation requirements. One of the mea-
sures of daily efficiency is casting to this plan. Since the
introduction of the new permanent magnetic stirring systems
at NZAS, efficiency in casting to plan has increased by 13%.
This is as a result of reduced variation and shorter furnace
preparation times. The Cycle Time between casts have been
reduced by 9% (Fig. 7). This is before any further work on
optimising scrap melting and reduction in manual stirring
times has taken place.
Inclusion Level Control
One of the concerns with continuous stirring is inclusion
control. Continuous mixing keeps any inclusions and oxide
films suspended in the melt. Although flux injection and
filtering systems can be used to reduce these levels, they
can never be completely eliminated and can result in
quality concerns downstream with customers when pro-
cessing extrusion billet or rolling slab. Earlier work at
NZAS looking at inclusion contents in billet alloys has
demonstrated that settling time in the furnace can have
significant impacts in reducing inclusion contents in the
melt even after filtration (Fig. 8). Thus controls are
required to ensure that minimum times are enforced
between turning off the permanent magnetic stirring system
and starting to cast. Continuous monitoring of the
Case Study of Magnetically-Stirred Casting Furnaces …
Fig. 8 Effect of settling time on inclusion contents
permanent magnetic stirrer status has been implemented in
all installations at NZAS which does not allow casting to
start until the required settling time has elapsed. This also
has to include other methods of furnace agitation such as
rotary flux injection, manual stirring or additional solid or
liquid charging. This is achieved by monitoring all doors
and access ports of furnaces and if any are triggered during
a settling period the timer is reset. A balance is required
between settling times and throughput with consideration
given to customer quality requirements.
915
Conclusions
Zmag MagStir technology has been installed in three casting
furnaces at NZAS. The continuous stirring functionality of
these systems has resulted in significant cost savings as well
as increased efficiency, throughput and quality of final cast
extrusion billet and rolling slab products. Further savings are
anticipated as the systems are further integrated into the
alloying and scrap melting processes.
Acknowledgements The authors would like to thank Zmag and the
members of the NZAS Metal Products Departments Project Engineer-
ing and Operations Teams and Automation Engineering for their sup-
port in making these installations a success and Pacific Aluminium for
permission to present this publication.
References
1. K. Takahashi, Inside/out light metals: the origin of the eddy current
separator. Light Metal Age 62 (2015)
2. S. Hamilton, R. Cook, Impact on smelter operations of operating
high purity reduction cells, in Light Metals 2013, ed. By B.A. Sadler
(Wiley, Hoboken, NJ, 2013)
3. “NZAS Multichannel Ultrasonic Inspection Station for Billet”, to be
published
4. Secat Newsletter 4(2), (2016)
 Energy Efficiency Status-Quo at UK Foundries:
The “Small-Is-Beautiful” Project

Mark R. Jolly, Konstantinos Salonitis, Fiona Charnley, Peter Ball,

Hamid Mehrabi, and Emanuele Pagone

Abstract
Energy efficiency is a critical issue for all manufacturing sectors. In the present paper the
energy efficiency of UK foundries was assessed. In the context of this research 80 foundries
were studied, 60 were contacted and 10 were visited. General energy data were collected
using structured questionnaires, interviewing energy managers and process operators.
A number of foundries are operating to a good standard, by employing energy managers
and regularly auditing; they are in control of their process and working rigorously to
improve their efficiency. Simultaneously though, smaller foundries have not adjusted to the
new market demands and are not operating in the most energy efficient manner. Important
barriers to energy efficiency in these foundries include lack of knowledge on auditing
methods, poor knowledge in managing energy consumption, the inefficiency of individual
process steps, production disruptions, aging equipment, personnel behavior, inadequate
maintenance and lack of investment, automation and research.

Keywords
Energy efficiency Sustainability UK foundries

Introduction on improving the quality of the process (for example through

Manufacturing sector accounts for one third of the total
energy consumption in the United Kingdom [1]. Casting
processes are among the most energy intensive manufac-
turing processes. Although, casting sector has a very long
history, as being among the first manufacturing processes
that humans mastered, the focus and thus research has been
M.R. Jolly
K. Salonitis (&)
H. Mehrabi
E. Pagone
Manufacturing Department, Cranfield University, Cranfield,
MK43 0AL, UK
e-mail: k.salonitis@cranfield.ac.uk
M.R. Jolly
e-mail: m.r.jolly@cranfield.ac.uk
F. Charnley
Cranfield Centre for Competitive Creative Design, Cranfield
University, Cranfield, MK43 0AL, UK
P. Ball
The York Management School, University of York, York, YO10
5GD, UK
the famous “10 rules of castings” [2]), and obviously not on
the energy efficiency. However, energy efficiency has
become important for a number of reasons; to name a few is
the energy cost, the green movements, and the improved
environmental consciousness. Foundries thus, will have to
control and eventually decrease their energy consumption, in
order to follow this trend. Further to just following the
trends, legislation is also becoming stricter, posing specific
requirements to foundries around the world. Indicatively, the
Climate Change Agreement published by the U.K.
Government [3] required that the foundries have to attain an
energy burden target of 25.7 GJ/tonne by 2020. However,
the average energy burden for the UK foundry sector in 2013
was 55 GJ/tonne.
In the UK, there are more than 400 foundries [4], with
most of them being small and medium enterprises, and as
such face great challenges when trying to implement energy
efficiency initiatives [5]. Furthermore, no study has been
undertaken, to reveal the current status of the UK foundries

© The Minerals, Metals & Materials Society 2017 917

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_110
918
with regards to energy efficiency. Under this environment,
The Engineering and Physical Sciences Research Council
(EPSRC), who is the UK’s main agency for funding research
in engineering and the physical sciences, has funded a
research grant to Cranfield University for addressing this
research gap. The funded project, under the title “Small is
Beautiful” launched on March 2015 and will end on
December 2016. The principal objective of the study is to
“develop a new philosophy/methodology and a software tool
incorporating metrics for the handling of materials and
energy throughout the process in foundries using computer
numerical process simulation to support the decision mak-
ing”. The project can be considered of composed of two
phases, with phase one being the assessment of the energy
efficiency status-quo at the UK foundries, and phase two the
development of a software tool that will allow the foundries
to implement energy efficiency initiatives.
In the present study, the results of phase one of the “small
is beautiful” project will be presented that will lead to the
research currently undertaken for completing phase two. In
the context of this research 80 foundries were studied, 60
were contacted and 10 were visited. General energy data
were collected using structured questionnaires, interviewing
energy managers and process operators. The outcome of
these communications with the foundries will be presented
and discussed. Important barriers to energy efficiency in the
foundries are identified and will be discussed.
Research Methodology
In order to capture the current practices in the foundries in
the UK, a survey was undertaken. As a starting point,
working closely with Cast Metals Federation (CMF) allowed
for identifying foundries to be contacted and interviewed. In
Fig. 1, the foundry sector business in the UK is outlined.
There are 426 foundries in the UK producing 523,000 tonnes
of casting with a turnover of £2.2 Bn [6]. In 2014, global
production of casting increased to more than 105 million
metric tonnes, an increase of 2.3% to the previous year [7].
Fig. 1 Foundry sector in UK
M.R. Jolly et al.
In total 60 foundries (across a number of casting pro-
cesses and cast alloys) were contacted over 6 months. The
foundries were asked for access to their facilities, and a
questionnaire was sent for collecting information. Ten
foundries (17% response rate) provided information on the
energy consumption profile, materials handling and waste
streams. The ten foundries included two investment, four
sand and four die casting foundries. These foundries repre-
sent a diverse cross-section of the sector in terms of alloys
cast, type of products, annual tonnage of casting produced,
types of melting and furnaces and the degree of automation.
Furthermore, a total of 100 papers, reports, articles and
books have been reviewed as well as attending GIFFA 2015
at Dusseldorf, Germany for five days interviewing various
foundries and suppliers to the foundries.
Key Findings
Energy Consumption Monitoring
The visits at foundries and interviews with production and
foundry managers revealed that foundries do not monitor the
energy consumption in detail, but rather focus in energy
bills. One of the key reasons for such practice, as identified
by these interviews, is that foundries do not know how to
measure the energy consumption of their installed systems.
Typical data recorded by foundries are shown in the form of
a graph in Figs. 2 and 3, where the energy consumption and
the production are shown for two different foundries. Such a
graphical representation can help foundries focus in periods
of time that the performance was better and investigate if
practices were different as to establish a cause and effect
relationship. However, this level of information (energy
consumption on factory level) cannot provide detailed
information on the performance for example of various
assets in the factory. For example questions such as: “which
process step is the most energy demanding so for the
foundries to focus in controlling it?”, “how can improve-
ments be assessed if the measured data are on a monthly
Energy Efficiency Status-Quo at UK Foundries … 919

Fig. 2 Example of energy data

information captured by a gravity Gravity and Sand casƟng 2014
and sand casting foundry in the
UK Electric
70 900.00
Thermal (gas)
Shipped 800.00
60

Energy consumpƟon (MWh)

Melted
700.00
50

ProducƟon (ton)
600.00
40 500.00
30 400.00
300.00
20
200.00
10 100.00
0 0.00
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

Fig. 3 Example of energy data

information captured by a high High Pressure Die CasƟng 2014
pressure die casting foundry in
the UK Electric
30 Thermal (gas) 180.00
Shipped 160.00

Energy consumpƟon (MWh)

25 Melted
140.00
ProducƟon (ton)

20 120.00
100.00
15
80.00
10 60.00
40.00
5
20.00
0 0.00
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

basis?”, etc. cannot be answered. This is not a problem
though of only foundries; most manufacturing companies
face similar challenges.
Frameworks have been developed for addressing this
challenge. Indicatively, Dave et al. [8] developed a frame-
work based on the concept of data granularity and validated
it in a furniture manufacturing company. Using such a
framework, can allow for the more efficient use of simulation
models. Based on the realization that no energy measure-
ment framework exist that is tailored to foundries, Salonitis
et al. [9] developed one that will be described in detail in a
following section.
Key Decision Making Factors
As a follow up of the preceding finding, the interviews were
focused in identifying the key decision making factors that
foundries rely upon. Previous studies [1, 10] highlighted the
need for updating the classical manufacturing decisions
attributes (Cost, Quality, Flexibility and Time) by adding
another one being the “sustainability” (Fig. 4). Within the
“sustainability” decision attribute, the energy efficiency and
the emissions can be considered as key performance indi-
cators (KPIs). The interviews with the foundries, confirmed
that UK foundries do not consider energy efficiency and
emissions as key decision making factors, but there is a
growing understanding of the need to control them.
Different Practices with Regards Energy
Efficiency
The review of scientific papers and discussions with repre-
sentatives from international foundries in GIFFA 2015 indi-
cated that major differences on practices between the
foundries might exist. As a result, an agreement with four
international foundries was set up for benchmarking their
practices. The foundries were visited and additionally more
than 100 companies and industry experts (including other
foundries, suppliers, raw material suppliers etc.) were
contacted.
920
Fig. 4 Manufacturing decision making attributes evolution [1, 10]
A key difference identified was that the foundries visited
closely monitor the energy consumption of a number of
phases during casting (not all though) focusing mostly on the
consumption of the melting and the holding phases. Con-
sidering that these two phases can account for up to 60% of
the total consumption [11], this obviously is a good practice.
Furthermore, the awareness of the importance of sustain-
ability and energy efficiency was found to be higher, espe-
cially with the four big foundries interviewed.
Energy Audit Framework
Energy and resource measurement aids foundries to under-
stand the quality and quantity of materials and energy used
in each step of the process and deal with any inefficiencies
and variations during the casting operation. Materials weight
can be measured simply after each step of the process, so
overall yield can be quantified by adding them up. However,
energy consumption of each step of the process needs to be
measured regularly on daily, monthly and annual basis. The
information required for this stage can be estimated indi-
rectly by calculation using nominal data specified by the
manufacturer, operating hours and work load factors or
directly by measuring data using meters or data logger
Fig. 5 Proposed energy
measurement framework
M.R. Jolly et al.
systems to monitor the energy consumptions [12]. Energy
and materials consumption patterns are the main part of the
audit process. These patterns are used to understand the
materials and energy flow in a foundry and help to control
their cost by identifying areas where waste can occur and
where scope for improvement may be possible [13]. This
will help management make prompt and on time decisions to
avoid losses due to inefficient operations by personnel or
equipment.
To address the lack of knowledge on how to measure
energy, a simplified framework has been developed that is
composed of three major phases: the preparation, the mea-
surement and the analysis phase [9]. Figure 5 shows the
framework and the intermediate stages.
The first phase is about setting up the energy audit. Ini-
tially manufacturing process chain is analyzed and decom-
posed into specific processes such as melting, holding,
casting etc. Each one of these phases is analyzed as per the
specific needs that it might have in energy, source of energy
(electricity, gas, etc.), the recycling streams etc. Based on
this information, the measuring strategy can be decided, in
terms of type of sensors to be used, resolution of data (data
granularity), measuring period etc. These data can be rep-
resented in various forms, IDEF0 being one of this was
found to be very practical. In Fig. 6, the IDEF0 modelling of
an aluminum gravity die casting process in one of the visited
foundries is shown.
Within the second phase (measurement phase) all the
measurements are taking place (including energy usage and
materials flows—yields, scrap, machining quantities etc.)
Such measurements can be graphically represented in the
form of Sankey diagrams. The final phase deals with the
analysis of the results. The energy consumed from each
phase can be estimated after direct measurement. Using a
Pareto style analysis, the various subsystems are ranked with
Energy Efficiency Status-Quo at UK Foundries …
Fig. 6 IDEF0 modelling of
aluminum gravity die casting
(left) and melting sub-process
detailed IDEF0 diagram (right)
Fig. 7 Energy consumption and
losses for an aluminum gravity
die casting foundry
regard to the energy consumption, establishing in this way
which subsystems are best to focus improvement efforts.
Figure 7 shows as an example the outcome of such analysis
for an aluminum gravity die casting process, highlighting
where the analysis is consumed.
Next Steps
As a result of the survey, the need for a software that will be
able to easily visualise the energy and material flows in a
foundry plant was confirmed. A detailed analysis of the
entire production chain from charge to waste will be enabled
by the use of the computer program. This analysis will help
921
decision makers to experiment with scenarios where differ-
ent improvements are implemented and the software will
allow to quickly evaluate their impact in a visual manner
(e.g. by means of process flow or Sankey diagrams). In
particular, the identification of neglected or difficult to
identify waste can uncover potential synergies. Another
useful application of the computer program would be
training the behavior of foundry personnel in showing
clearly the impact of their actions on the overall perfor-
mance. Finally, the thorough analysis previously described
may benchmark the performance of the plant against similar
ones. The first step to this approach was the development of
a simple to use Excel tool (Fig. 8). This excel tool was
validated during the benchmarking exercise with the four
922
Fig. 8 Outline of the software core idea
international foundries. The next version of the tool will be a
stand-alone software to be used for the collection of energy
and material flow, the comparison of these with the bench-
marking data and the identification of areas of “quick-wins”
for the foundries. This tool will be able to provide insight to
the process chain to be selected, will cover the supply chain
(for example the mould/die making suppliers, the manufac-
turers of the inserts, etc.) and be linked to the product design
software.
The work-flow of the program is designed to start from an
input file describing the plant that is parsed and stored in the
form of an internal data structure. A modular architecture
interfaces the tool with other packages (e.g. graphviz) for the
final graphical representation using the information con-
tained in the mentioned internal data structure. The tool
produces automatically Process Flow Diagrams (PFDs)—
e.g. Fig. 9—with a user-specified set of colours and shapes
to represent components and material or energy flows. The
user can select the specific categories of flow to be repre-
sented (material or energy, although this could be extended)
or all of them. In this last case, it is possible to specify that
the flows describing the same physical process in two dif-
ferent categories will be hidden in the PFD to avoid double
accounting. For example, in a melting furnace fossil fuels
and air (material flows) describe the same physical process
M.R. Jolly et al.
of thermal energy input and it is possible to request the
visualisation of only one of them. Thus, besides a default
behaviour, the program is designed to be largely customis-
able on a case to case basis. Another envisaged output
module is a Sankey diagram generator. Particular attention
has been devoted during the design of the computer program
to make it easily extensible to introduce future additional
flows (e.g. embedded energy) and new graphical output
modules [14].
Conclusions
In the present study the outcome of the first phase of “Small
is Beautiful” EPSRC funded project is presented. The pro-
ject was based on an intensive survey of the current practices
the UK foundries are employing with regards the energy and
resource efficiency.
The key findings from this survey can be summarized
into: foundries do not monitor the energy consumption in
detail, but rather focus in energy bills, foundries do not know
how to measure the energy consumption of their installed
systems, subsequently energy consumption and emissions
are not considered to be among the key decision making
Energy Efficiency Status-Quo at UK Foundries …
Fig. 9 Example showing the
overall material and energy flows
in a foundry melting aluminium
alloys with a low pressure sand
casting process [14]
criteria, and finally there are indications of major differences
on practices between the foundries.
The authors, for addressing these findings have developed
a new energy measurement framework for the needs of the
foundries. Furthermore, they are in the process of developing
a software that will be able to effectively represent material
and energy flows involved in the process and will be able to
integrate with legacy systems.
Acknowledgements The authors would like to acknowledge the
UK EPSRC Small is Beautiful (EP/M013863/1) project for the support
of this work. All data are provided in full in this paper.
References
1. K. Salonitis, P. Ball, Energy efficient manufacturing from machine
tools to manufacturing systems. Procedia CIRP 7, 634–639 (2013)
2. J. Campbell, Castings Practice—The Ten Rules of Castings
(Knovel, 2004)
3. Department of Energy & Climate Change (2011)
4. Cast Metal Federation (2016), Website: http://www.castmetal
sfederation.com/. Accessed 31 Aug 2016
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5. A. Trianni, E. Cagno, Dealing with barriers to energy efficiency and
SMEs: some empirical evidences. Energy 37(1), 494–504 (2012)
6. UKcastings.org (2015), http://www.ukcastings.org/page.asp?node
=79&sec=Facts___Figures. Accessed 02 Sept 2016
7. Modern casting (2005–2015), http://www.afsinc.org/multimedia/
modernCasting.cfm. Accessed 02 0Sept 2016
8. A. Davé, K. Salonitis, P. Ball, M. Adams, D. Morgan, Factory
eco-efficiency modelling: framework application and analysis.
Procedia CIRP 40, 214–219 (2016)
9. K. Salonitis, M.R. Jolly, B. Zeng, H. Mehrabi, Improvements in
energy consumption and environmental impact by novel single
shot melting process for casting. J. Clean. Prod. 137, 532–1542
(2016)
10. K. Salonitis, P. Stavropoulos, On the integration of the CAx
systems towards sustainable production. Procedia CIRP 9, 115–
120 (2013)
11. K. Salonitis, B. Zeng, H.A. Mehrabi, M. Jolly, The challenges for
energy efficient casting processes. Procedia CIRP 40, 24–29
(2016)
12. R.M. Lazzarin, M. Noro, Energy efficiency opportunities in the
production process of cast iron foundries: an experience in Italy.
Appl. Therm. Eng. 90(5), 509–520 (2015)
13. M. Arasu, R.L. Jeffrey, Energy consumption studies in cast iron
foundries. in Transaction of 57th IFC (2009)
14. E. Pagone, M.R. Jolly, K. Salonitis, The development of a tool to
promote sustainability in casting processes. Procedia CIRP 55,
53–58 (2016)
 Optimization of Recovery Efficiency
for Briquetted Aluminum Chips
up to Briquetting Parameters

Ali Ulus, Hamdi Ekici, and Erdem Güler

Abstract
Nowadays, the most important problem is the high cost of casted products. Foundries are
increasing the use of secondary sources to reduce their raw material costs. Continuous
caster edge milled swarf has a large potential as a possible new secondary source. Usually
this swarf has a high amount of oil ingredient and low density. These properties lead this
material as a low quality and low recovery rate source. To solve this problem some of the
companies try to reduce oil usage, some of them changing the oil type. However especially
for reverberatory melting furnaces the density must be higher than molten aluminum
density. We will evaluate the chip briquetting solutions to improve melting efficiency for
chips. Also we will be conducting the density and oil amount results together with edge
miller oil usage, swarf oil amount, cyclone filter parameters, pressing parameters, oil
reduction methods and melting efficiency of briquetting.

Keywords
Briquetting machine Melting efficiency Secondary aluminum Chips

Introduction • Preventing of solid wastes which occurs in primary

production
Recycling in Aluminum Manufacturing Industry • Economic gain

Eight percent of earth’s surface contains aluminum [1].
Aluminum production began in 1886 after the invention of
electrolysis [2]. Extracting aluminum from bauxite ores is
called primary production of aluminum and it’s very
expensive and it pollutes environment. Secondary produc-
tion of aluminum is recycling of scrap aluminum and this
method is inexpensive and more ecological than the first
method. Secondary production can occur with only 5% of
first method’s energy.
As follows advantages of secondary production:
• Raw material savings
• Energy savings and exhaust emission
A. Ulus (&)
H. Ekici
E. Güler
Teknik Alüminyum A.Ş., 59880 Çorlu, Tekirdağ, Turkey
e-mail: ali.ulus@teknikaluminyum.com.tr
Table 1 exhibits required energy amounts and emission
amounts of primary and secondary productions of aluminum.
Both environmental problems and energy costs make
secondary production of aluminum more important every
day. Regarding this, in secondary aluminum production
process; new designs and enhancements are continuously
occurring [4]. The process scheme of secondary production
of aluminum is given below:
• Scrap collection
• Separating scrap, pretreatment of scraps
• Melting
• Alloying
• Refining
• Casting

© The Minerals, Metals & Materials Society 2017 925

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_111
926 A. Ulus et al.

Table 1 Required energy Energy consumption For 1 tonne primary For 1 tonne secondary
amounts and emission amounts aluminum aluminum
of primary and secondary
productions for 1 tonne Total (MJ) 193,702.0 10,321.0
aluminum [3] Renewable energy (MJ) 57,352.0 452.0
Provided energy from fossil 13,635.0 9869.0
fuels (MJ)
Coal (MJ) 50,807.0 937.0
Petrol (MJ) 21,268.0 1319.0
Natural gas (MJ) 36,335.0 7151.0
Nuclear energy (MJ) 8282.0 419.0
Other energy (MJ) – 44.0
Bauxite mining and alumina 19,657.0 –
production
Emission of greenhouse gasses – –
CO2 (kg) 1047.0 620.0
Perfluorocarbon (kg) 0.3 –
PFC, CO2 equivalent 2227.0 –

Figure 1 exhibits the amount of primary and secondary
production of aluminum in World.
In secondary production, casting methods are constantly
being optimized [5, 6]. Especially in scrap preparation and
melting process; recycling engineers focus on the new
capabilities of the recycling equipment. Additionally; on the
low density raw materials; together with new technological
improvements, the usability of these scraps increase properly.
Edge Milling and Result Scraps in Twin Roll
Casting
In the twin roll casting method, casting and rolling processes are
done simultaneously and thus thin aluminum sheets can be
produced directly from molten aluminum. In this process molten
metal is fed through twin rolls with ceramic tips and the molten
aluminum solidifies. Roll temperatures are controlled by cooling
channels inside them. Rolls apply pressure on the solidified
aluminum sheet and adjust the final product thickness (Fig. 2).
In the final product there are many edge segregations due to
barrel type roll shape. Due to the roll’s geometry and the force
application point; edge pressure is more than other locations on
the rolls. These points result in faster solidification of molten
metal. This edge segregation cause edge cracks (Fig. 3).
Casted sheet product is edge milled before making a coil
because if casted sheet contains edge mill cracks this will
inhibit the following cold rolling processes. Edge milling is a
process which cuts sheet’s edges with high period rotating
blades. While cutting sheets cutting oil is used to lower fric-
tions between blades and sheet. You can see these mechanisms
of Fata Hunter Super Speed Caster Lines (Fig. 4).

Fig. 1 World’s primary and

secondary aluminum production
between 1950 and 2010 [4]
Optimization of Recovery Efficiency for Briquetted Aluminum … 927

Fig. 2 Twin roll casting

production line [7]

Fig. 3 a Casting edge cracks,

b extrusion edge cracks

Fig. 4 a Edge milling blades,

b edge milling machine

Briquetting Separating scraps according to their sizes like swarf,

Aluminum is prepared to recycle in 3 steps:
• Separating and classification of aluminum
• Breaking and/or pressing
• Cleaning and preheat treatment
burrs, cast, and piece is one of the most important point of
scrap aluminum classification. The scrap comes from edge
milling can’t be separated because they are one kind. To
increase scrap swarf’s melting efficiency and decrease sur-
face area briquetting is used. In briquetting, swarfs are bound
together under pressure. If the surface area of swarf is not
928
decreased, there will be a high amount of oxidation when
melting [8]. Melting efficiency will decrease and there will
be metal loss. You can see swarf and briquetted swarf with
GÖKMASAN briquetting machine in Fig. 5a, b.
In briquetting process milling oil, briquetting period, final
briquette measurements, pressure and mold oil are main
elements.
Preheat Treatment and Melting
In the aluminum melting process melting efficiency can be
increased by preheating materials. Preheating advantages are:
– Increasing dissolution speed of molten metal and material
feed
– Cleaning material feed from oil, dirt, etc.
– Increasing thermal efficiency of melting [9].
Köksal and his friends determined there will be 34%
energy saving with heat treatment at 400 °C [10]. Rever-
beratory furnace can be used while melting aluminum. This
furnaces’ ceilings and surfaces built with refractory which
provides the required mechanical and thermal endurance.
Fig. 5 a Swarf, b briquetted
swarf
Fig. 6 Lateral section of melting
furnace
A. Ulus et al.
Natural gas is used as the fuel inside them and heating
efficiency is increased with regenerative air burners [11].
Flame is sent inside the furnace by burners. The oxidation
reaction is given below:
CH4 þ O2 ! CO2 þ H2 O
Flame released from oxidation is sent angular to material
feed. Flame and material are in direct contact. This situation
increases heat efficiency but also increases oxidation rate
(Fig. 6).
Preheat treatment in furnace occurs at the furnace
ramp. With this heat, scrap heat efficiency increases and the
swarf oil vaporizes.
Refining
Refining steps at twin roll cast process are given below:
– To remove hydrogen inside melted aluminum inert gas-
ses are used and to remove inclusions flux is added inside
the melting furnace
– To remove hydrogen inside melted aluminum inert gas is
used in the holding furnace
Optimization of Recovery Efficiency for Briquetted Aluminum … 929

– After the holding furnace melted aluminum is sent to the
degasser to remove the remaining hydrogen
– Molten metal goes through two filters to clean inclusions
(Fig. 7)
Refining with Flux
Aluminum alloys are easily oxidized during melting. The
density of the resulting metal oxide is very close to the
molten aluminum. Metal oxides which remain suspended in
liquid aluminum, impairs the casting quality.
In aluminum casting, the rate of oxidation is reduced,
inclusions are removed and recovery of aluminum is pro-
vided with the flux process. Fluxes are used for protection,
degassing, refining and skimming according to the type of
application [12].
Al2O3 is one of the oxides at slug layer. This oxide adheres
to the surface of slag due to surface tension in the molten
aluminum. Cover flux is used to minimize this situation [13].
This flux prevents the oxidation of the metal further by
reducing contact between atmosphere and molten metal. In
addition, flux is added to metallic aluminum droplets which
combine and coalesce into a molten pool [14].
This flow is shown schematically in Fig. 8.
Experimental Procedure
Measuring of Different Oils’ Volatilities
Starting specimens are sampled from 20 briquettes which are
briquetted under 150 bar pressure and two different milling

Fig. 7 Schematic representation

of twin roll casting method

Fig. 8 Fluoride contained flux

effect on merging droplets on
molten dross [15]

Fig. 9 Classified samples

930 A. Ulus et al.

This sample groups are fed into a melting furnace. Refi-

nation, skimming, and cleaning steps are done before feeding
samples. After waiting 10-min, fluoride based flux is added
into the furnace. After 5 more minutes the bath is skimmed.
Metal/dross rates are calculated after skimming. For enable to
compare the efficiency results, total amount of the molten
metal in the furnace was kept similar in each charge.

Results

Results of Different Oils’ Volatilities

Fig. 10 Heater inside fume cupboard
Measurements

oils (X and Y). After measuring height, diameter, and weight
of samples, the volume and densities of them are calculated.
Samples dried in fume cupboard at 350 °C for 0.5–1 to 1.5–
2 and 2.5 h by pairs. After this step samples are weighed
again and densities noted (Figs. 9 and 10).
Experiments show that in briquettes oil Y is more volatile and
lightweight than X oil. Experiments are given in Table 3.
Graphic 1 shows density changes on briquettes after
vaporizing oil.

Results of Preparing Briquettes, Casting,

Preparing Briquettes, Casting, Refining
and Deslagging
At briquette preparation, swarf is taken from AA1050,
AA5005, AA3005 alloys, used different oils while milling
and chosen different briquette measurements. This briquette
samples are dried at 750–780 °C for 50 min.
Sample groups are given in Table 2.
Refination and Deslagging
In casting experiments first of all AA1050 swarfs which
milled with X oil are fed into the furnace and skimmed. The
observed loss was 28.19% and after this same experiment
repeated with briquettes. With changing briquette oil and
size the observed loss was lower. All parameters and results
given at Table 4.

Table 2 Casting experiment Alloy Briquetting pressure (bar) Briquette diameter (mm) Briquette height (mm) Milling oil
sample groups
AA 1050 – – – X
AA 1050 150 62 60 X
AA 1050 150 62 40 X
AA 1050 150 62 60 Y
AA 1050 150 62 40 Y
AA 3005 150 62 60 X
AA 3005 150 62 40 X
AA 3005 150 62 60 Y
AA 3005 150 62 40 Y
AA 5005 150 62 60 X
AA 5005 150 62 40 X
AA 5005 150 62 60 Y
AA 5005 150 62 40 Y
Optimization of Recovery Efficiency for Briquetted Aluminum … 931

Table 3 Oil volatility experiment results

Measurement X1 X2 X3 X4 X5 X6 X7 X8 X9 X10
Briquette diameter (mm) 61.9 61.98 61.9 61.4 61.8 61.9 61.9 61.9 61.8 62
Briquette height (mm) 55.4 50.4 50.9 52.02 46.8 51.3 48.9 51.7 53.8 49.24
Weight before drying (g) 408 372 375 375 347 381 359 378 396 365
Weight after drying (g) 406 370 373 373 344 378 355 374 391 360
Density before drying (g/cm3) 2.448 2.447 2.449 2.435 2.473 2.469 2.44 2.429 2.455 2.456
3
Density after drying (g/cm ) 2.436 2.433 2.435 2.422 2.451 2.449 2.412 2.403 2.424 2.422
Density difference 0.012 0.014 0.014 0.013 0.022 0.02 0.028 0.026 0.031 0.034
3
% density difference (g/cm ) 0.492 0.575 0.574 0.536 0.897 0.816 1.16 1.081 1.278 1.403
Measurement Y1 Y2 Y3 Y4 Y5 Y6 Y7 Y8 Y9 Y10
Briquette diameter (mm) 61.8 62.3 62.4 61.1 62.2 61.98 62.1 62.2 62 61.78
Briquette height (mm) 53.4 49.5 50.9 46.3 47.9 50 46.9 49.5 49.7 49.6
Weight before drying (g) 379 356 363 333 343 357 331 357 353 356
Weight after drying (g) 379 356 363 333 342 356 329 355 351 354
3
Density before drying (g/cm ) 2.367 2.36 2.333 2.454 2.357 2.367 2.331 2.374 2.353 2.395
Density after drying (g/cm3) 2.367 2.36 2.333 2.454 2.35 2.36 2.316 2.36 2.339 2.381
Density difference 0 0 0 0 0.007 0.007 0.015 0.014 0.014 0.014
% density difference (g/cm3) 0 0 0 0 0.297 0.296 0.647 0.593 0.598 0.587

Graphic 1 Density change—

sample no graphic for samples of
a Group X b Group Y

Table 4 Casting experiment results

5005 briquette 5005 slag 1050 briquette 1050 slag 3005 briquette 3005 slag 5005 1050 3005
weight (kg) weight (kg) weight (kg) weight (kg) weight (kg) weight (kg) loss (%) loss (%) loss (%)
X oil
Swarf 305 86 28.19
Briquette 352 25 900 50 512 36 7.10 5.55 6.94
40 mm
Briquette 804 51 860 45 812 54 6.34 5.23 6.65
60 mm
Y oil
Briquette 664 21 620 13 374 9 3.16 2.09 2.40
40 mm
Briquette 530 11 710 8 556 11 2.07 1.12 1.97
60 mm
932
Conclusions
In this study it is shown in twin cast rolling that changing
parameters like briquette size and milling oil brand to opti-
mum values gives better results. This changes lowered
alloying element losses in the process and also with lowering
oil volatility and briquette surface area/volume provides
advantages on recycling step.
Results achieved in this study:
1. In the oil vaporizing experiment with constant temperature
and increased time, it was observed oil Y evaporated faster
than X in all samples. Besides that, density change on
briquettes which has oil Y was lower than X. In this case,
the preheat treatment duration on oil Y containing bri-
quettes was shorter than X and the oxidation rate was low.
2. While melting AA1050 swarfs, observed recovery effi-
ciency was 71.81%.
3. With constant oil brand and briquetting measurements,
changing swarf alloy resulted in different metal loss rate.
The most loss was on AA5005 and the least was on
AA1050. This situation occurred because AA5005 alloy
contains Mg which has a high oxidation rate. AA3005
contains less Mg than AA5005. AA1050 contains the
lowest level of Mg.
4. It is observed if briquette height changes while other
parameters are constant, the higher surface area/volume
ratio causes higher oxidation rate.
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technological challenges and opportunities, in Light Metals 1990,
ed. by C.M. Bickert (TMS-AIME, Warrendale, PA, 1990), p. 675
 The Evaluation of Hot Dross Processing
Systems

David J. Roth

Abstract
On site Hot Dross Processing systems (HDP) can offer a method for significant
environmental savings with on site aluminum recovery. HDP often can eliminate the
remelting of the recovered sows or at worst take advantage of the retained heat in the
poured off sow. The most advantageous systems offer productive end use of the dross
oxides and aluminum fines left in the residual materials after the aluminum is recovered. All
of these systems offer significant environmental advantages over pan cooling or dross
pressing of materials that simply change the form of the aluminum and require further off
site rotary salt furnace processing. There are four HDP systems that will be reviewed in this
paper.

– Hot dross stirrers

– Hot dross stirrers plus dross coolers/size separators
– Hot dross rotary furnace operations
– TAHA hot dross mixer, cooling and sizing

Keywords
∎∎∎

Introduction re-melting of scrap aluminum produces dross that presents

Worldwide production of aluminum continues to grow. At
present it is annually at approximately 60 million metric
tons. This production level produces over 600,000 tons of
dross containing an estimated 300,000 tons of aluminum still
in the usable form of Al2. The production of aluminum has
contributed to about 1% of global green house gases and all
industry is under pressure to reduce these emissions. The
percentage of aluminum recycled, (currently about one third
of primary production), continues to increase and may be
looked upon as a cornerstone for the reduction of green
house gases. Recycled aluminum needs just 5% of the
energy and emits only 5% of green house gases but the
D.J. Roth (&)
GPS Global Solutions, Downingtown, PA, USA
e-mail: david.roth@global-solutions.us.com
its own environmental problems. The dross generation from
this recycled material is about 5% of the scrap melted or
almost 1,000,000 tons of dross annually. Today rotary salt
recycling furnaces are the most common method of recy-
cling dross. Processing 1,600,000 tons of dross by this
method generates nearly that much salt cake that has to be
recycled in costly processes or landfilled [1].
Hot Dross Stirring 1965—Present
Stirring was the first physically active process on dross to be
introduced to the aluminum industry getting wide commer-
cial acceptance. The first records show it being used in the
1960s. This process disappeared in the late 80s with the use
of dross presses. We have now however seen a resurgence of
this technology in China, Asia and in Mexico.

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A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_112
934
The reason for this resurgence is the positive approach
from many aluminum melters to maximize the in house
recovery of their metal units.
This process provides a low cost system for small dross
generators to retain aluminum units inside their facility while
disposing of the small oxide quantities that are generated.
The basic principle is that the hot dross is skimmed
directly from the furnace into a refractory lined cylindrical
dross pot or cast dross pot. This pot is then transferred to a
fabricated frame, which contains a rotating paddle or blade
device. The pot could be raised into the paddle or the paddle
lowered into the pot and then stirred.
The processing time averages about 5–10 min. After this
period of stirring, the hole in the bottom is “tapped” into a
sow mold. If the material is hot going into the process and
not a “dry” thermited dross, high Al sow recoveries are
possible. The recoverable aluminum typically ranges from
35 to 65%. The stirring action of the paddle causes the
coalescence of the droplets in the dross/metal matrix,
enhancing the drain recovery. The stirring action however
also can cause increased oxidation of the remaining dross
and produces a material with really no secondary aluminum
recovery.
The stirrer’s negative mechanical features revolved
around the stirring mechanism itself. The thermiting reaction
caused by the stirrer can cause by elevated temperatures a
dissolving away of the stirring blades in the aluminum.
Large amounts of fumes and smoke can be generated in the
process that can be difficult to deal with. The remaining
oxide material in most cases after stirring can be hot and
hard to handle, causing uncomfortable conditions in the
casting facility. Cold dross materials will not stir and are left
unprocessed. Sometimes fluxes were added to colder mate-
rial to get the thermite reaction to occur, losing aluminum
units and generating more fumes. The cold oxides that are
left in this process typically have to be disposed of because
of the relatively small quantity and non-uniform sizes
(Fig. 1).
Hot Dross Stirrers Plus Dross Coolers/Size
Separators 1970—Present
Dross stirrers were added originally to rotary coolers that
replaced the water cooled table systems utilized in the 1970s.
In this period more emphasis was given to preserving all
metal units possible and not just the drain from stirring.
Although you do not see this technology often in the US or
Europe it is widely used in China and Japan.
This system consists of a stirrer in the front end of a drum
section, which is typically externally water cooled. There is a
tilting charging device that dumps the hot oxides into the
drum for the cooling process, with a trammel screener on the
D.J. Roth
discharge end of the system for oxide and retained metal
sizing. A pollution control system is connected to the units
for dust control. Other items that set the various systems
apart were vibratory chargers, ball and autogenous milling
sections.
The process starts by skimming the dross into skim
pot/sow mold combinations. Some designs utilize draining
pans where there is no longer the need to “tap” the pots
because holes in the skim pots allowed draining as soon as
the skimming procedure. Others require the tap hole opening
method (Fig. 2).
The skim pots are placed into the charging device the
stirring blades move down into the dross draining the alu-
minum. After this stirring process the oxide and generally
aluminum free material is tilted into the water cooled,
rotating drum. Several methods are used to cool the drum
shell ranging from submergence, spray nozzles or lifting
flights. The cooling system is good at handling a range of
material from cold dross to very hot thermiting dross.
The drain recovery is typically in the range of the 35–
65%, as in the stand-alone stirrer. The cooling action pro-
vided by the physical contact with the drum allows for
secondary recovery of any finer metal units that are not
recovered by the stirring action alone. The mixing action of
the drum keeps the recovered aluminum in a finer size range
than other processes.
The oxide and finer aluminum particles are graded by size
in the combined screening section for secondary recovery,
use or disposal. The disposition of these products is up to the
customer. The cold processed dross will also pass thru the
system but then is a product for secondary recycling.
The cost for these systems is significantly higher than the
stand-alone stirrer. They require larger pollution controls
units, taking up much more floor space in the melting facility
with a higher level of sophistication and operator controls.
The safety record of the rotary cooler systems in North
America was not good. Poor maintenance or operating
procedures left the process open for the possibility of molten
aluminum being poured on top of water or of having contact
with oxidized steel. Both of these scenarios opened up the
potential for significant explosions. Several units failed in
the field during the early 80s with catastrophic results.
Maintenance of the systems is relatively high.
Hot Dross Rotary Furnace Operations 1960s—
Present
Asia has been using small rotary furnaces in their operations
for many years to separate the molten aluminum from the
oxides in the dross. I first saw this technology in the 80s in
Taiwan. I am sure it was being employed many years before
that thru out the region. Hot freshly skimmed dross in
The Evaluation of Hot Dross Processing Systems
Fig. 1 Dross stirrer [2]
Fig. 2 Stirrers/rotary coolers [3, 4]
refractory lined containers was brought from the melting
furnaces to small rotaries. The heat of the material was
typically all that was needed combined with the rotating
action of the furnace to cause the separation of the aluminum
from the oxides in the dross. The reported recoveries were
good. Alloyed molten metal could be returned to the melting
furnaces and the remaining oxides were provided to small
local companies for various uses. In Asia this was a rela-
tively inexpensive technology with apparently no waste
generation.
This technology was brought into Europe and North
America in the late 90s. Its use in this market however is not
wide spread. The level of controls, safety features, pollution
935
controls and oxide cooling techniques made it considerably
more expensive than the units used in Asia. Operator skills
are important to making the system work with good recov-
eries. There are a few major companies operating single
sites. Success is as variable as the operators controlling the
process (Fig. 3).
There are two key points to understand with this tech-
nology. First there is the recovery of aluminum in its molten
and alloyed state for direct return to the melting furnace.
This is worth significant dollars if the logistics work.
Additionally, with magnesium alloys you do not get the
typical “mag burnout” from secondary recycling. This can
be a significant savings. The logistics however are difficult
936
Fig. 3 ALTEK—hot dross
rotary furnace process [5]
and require multiples furnaces. The hot freshly skimmed
dross must be brought quickly to a waiting rotary for the
most efficient processing. If the dross is cold or too hot
recoveries will suffer. In some cases salt fluxes are used to
control the thermite reactions in the rotary, contaminating
the oxide materials for further use [6].
Second, the oxides generated in the process are typically
very hot and needs to be cooled in an environmentally
controlled process. This is an expensive addition to the
overall cost of the system. In some cases salt fluxes are used
here also to quench the thermite reaction. The final dispo-
sition of the oxide products, are the responsibility of the
dross generator. Direct landfilling has been the most used
final course of operation.
TAHA Hot Dross Mixer, Cooling and Sizing
2005—Present
The TAHA process is a unique patented system that is rel-
atively new on the market. It uses a semi-rotational/mixing
action and pour technology that removes the metal from the
dross right after skimming on site at the melt shop. The dross
is skimmed into a specially designed steel pan moved by
fork truck to the mixing unit. A lid is put on the pan and it is
rotated from side to side with an alternating arm in a fume
control chamber. The vigorous movement of the hot dross in
the closed container coalesces the aluminum and provides a
clean separation from the oxides. At the end of the mixing
cycle, the liquid metal is poured separating it from the oxide
matrix. Thermiting and metal loss are typically limited to a
bare minimum. The hot alloyed sows are then returned to the
furnaces that the dross was removed from.
D.J. Roth
TAHA has reported that in a process comparison with an
on site rotary furnace over several months that the recovery
of the TAHA process was superior due to more control over
thermiting and less aluminum retained in the oxide fractions.
The TAHA process is most likely very similar in aluminum
recoveries to the stand-alone stirrer process. The major dif-
ference comes in handling of the oxide fractions.
The process operates without the addition of chloride
base fluxes, which make a high quality down stream oxide
applications possible as they are not contaminated with the
chlorides.
The final separation of the fine aluminum granules from
the oxides is easily achieved with a DIDION machine.
The DIDION Metal/Dross Separator, cools and breaks the
depleted dross and allows the remaining fine metal to be
separated as an aluminum concentrate from the oxides.
The oxides now very low in metal content are cold, dry,
not contaminated with chloride salts and contain about an
80% aluminum oxide equivalent. This represents a product
grade that can be used for high quality byproducts (Figs. 4
and 5).
TAHA does not sell the processing equipment but rather
provides the dross removal services on a long term contract
basis to the aluminum melting operation. Supplying back to
the melting furnaces an alloyed metal in sow or molten form
and providing a managed, zero waste solution for the fine
aluminum and oxide components of the dross. The handling
of the fine aluminum and the oxide products sets their pro-
cess apart from all the others [7].
TAHA collects the data about the dross skimmed, the
metal recovered and the remaining oxides. This information
is made available to the melt shop management as an
enabling tool for process improvements.
The Evaluation of Hot Dross Processing Systems
Fig. 4 TAHA SARAH unit
Fig. 5 DIDION mechanical processing unit
Summary: Benefits and Drawbacks of HDP
The disadvantage of any HDP system is its ability to handle
cold dross, which generally comes in two forms. First,
typically dross from holders that was skimmed hot but
because of logistics or special pans was not transported to
the HDP process. This material can be processed in either
the rotary cooling system or DIDION system described
937
above for metal/oxide separation. The second type of cold
dross is material that has been cold skimmed and looks like
silver “ice cream”. The oxides and aluminum are intimately
bonded and reheating with some type of flux processing is
required to separate the aluminum form the oxides.
The most significant advantage of all these HDP pro-
cesses is the ability to watch the cause and effect reaction to
process changes in the melting furnace and understanding
the effects these process changes have on dross generation
and metal recovery. The ability to adjust practices based on
observations of the melt loss and dross generation saves a
facility many thousands of dollars by improving practices,
keeping the metal in the furnace and not carrying it out as
dross that must be processed.
The next major advantage of any HDP process is that the
metal is recovered without cross contamination between
different alloys. The HDP process is a batch process treating
the dross from each individual skimming operation. That
means that the recovered aluminum can be returned directly
into the same furnace hot, conserving energy and providing
the same alloy that generated the dross. This is a very
valuable aspect of this type of in house dross treatment.
Other benefits would include reducing or eliminating the
costs of shipping and toll conversion costs. Also eliminating
any potential losses that can also occur during shipping and
storage in the aluminum content.
References
1. D.J. Roth, The History and Future of Dross Processing (GPS
Global Solutions, TMS 2014)
2. M.G. Amdur et al., US Patent 3,198,505, 3 Aug 1965
3. Figure 2 Photo, Remetal SA, Bilbao Spain
4. Figure 2 Photo, Runsan Metallurgical Equipment Company,
Quzhou City, China
5. D.J. Roth, Some Like It Hot (Altek International LLC, 2001)
6. D.J. Roth, New Hot Dross Processing Technology at Hydro
Holmestrand Rolling Mill (Niels Erik Hald, Hydro Aluminum,
ALETK TMS, 2002)
7. R. Vesper, Aluminum Dross Processing (TAHA International,
Manama, Kingdom of Bahrain, Aluminum Times Sept/Oct 2016)
 Part XXII
Cast Shop Technology: DC Casting
and Macrosegregation
 A Study on DC Casting Trough/Launder Design
and Material Selection

Bin Zhang

Abstract
For successful and consistent casting on ingot DC casting systems, metal heat loss has to be
reduced. Metal heat loss is directly influenced by casting trough/launder design and
material selection. To assist in developing solutions to reduce metal heat loss from furnace
to casting table, a CFD modeling program was developed for heat loss analysis from
furnace spout to casting station. The influence of the degasser, CFF units, and automated
metal level controls are all included in the program to improve accuracy. Case studies are
reported to reveal the influence of refractory geometry and material selection on metal heat
loss. It is shown that when the main launder refractory material is changed from REF-1 to
REF-2, heat loss is *15.0 °C less at start and *3.5 °C less at run cast at a *136 kg/min
flow rate. A trough/launder with a V-Shape cross section has less heat loss than a
trough/launder with a U-Shape cross section as a result of increased metal flow due to
reduced cross section area and the reduced metal contact surface area. The reasonable
agreement between our modeling results and field measurements show that the developed
casting process modeling program can be used to analyze refractory/insulation materials
and trough/launder geometry designs.

Keywords
Aluminum alloy Ingot DC casting Trough Launder Heat loss

Introduction body of work was especially relevant to Wagstaff® Inc.

Heat loss reduction is an ongoing challenge during DC
casting startup process control. If metal heat loss is exces-
sive, pre-solidified grains in ingots, frozen pins, spouts, or
combo-bags and ingot cracks might occur at cast start. Work
has been continued to reduce heat loss through proper
material selection and trough/launder geometry design for
DC casting equipment. Previously, practical analytical
models were used to analyze heat loss in molten metal dis-
tribution systems for steady state [1–3]. Computational
modeling of fluid flow and heat transfer were also conducted
on billet DC casting metal distribution systems [4–6]. This
B. Zhang (&)
Wagstaff Inc., 3901 N. Flora Rd, Spokane Valley, WA 99216,
USA
e-mail: bin.zhang@wagstaff.com
when building a 30 ton DC ingot casting line (DC #6) for
their R&D needs and redesigning the main launder for their
10 ton DC ingot casting line (DC #1) to reduce the metal
heat loss. Thus, a casting process modeling program was
developed to examine the thermal and fluid flow field at
transient and near steady state conditions to optimize the
trough/launder design to obtain consistent start-up process
temperature control.
Model Description
3-D heat transfer and fluid flow models were developed
using the commercial CFD (Computational Fluid Dynamics)
package, Flow-3D®. This package solves the transport
phenomena equations including heat transfer, momentum

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A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_113
942
and continuity. TruVOF® technique was utilized for free
surface flow. The GMRES (General Minimum Residual)
pressure-velocity solver was used for pressure iteration
convergence. Turbulent fluid flow was included in the model
using similar equations as in the k-e model. In the model, the
latent heat release follows a non-linear function of fraction of
solid during solidification. Forchheimer porous-media satu-
rated drag flow was included for the CFF.
Geometry of the Metal Distribution Systems Two ingot
DC casting lines were investigated in this study. Models
were constructed in 3-D of the metal distribution systems for
DC #1 and DC #6 and are presented in Fig. 1a, b. DC #1 is an
older casting line mainly dedicated for ingot casting. It has a
total trough length of *11.8 m (the main laun-
der = *8.9 m and the table trough = *2.9 m; furnace
capacity = 10 tons). DC #6 is the newer casting line and it
has a total trough length of *11.7 m (the main laun-
der = *6.2 m and table trough = *5.5 m; furnace capa-
bility = 30 tons). The older DC #1 has a U-Shaped
refractory (cavity cross sections are *203 cm2 for the
main launder and *457 cm2 for the table trough). The
newer DC #6 has a V-Shape refractory (cavity cross sections
are *153 cm2 for the main launder and *207 cm2 for the
table trough).
Initial and Boundary Conditions The incoming metal
in the model was 6061 alloy unless otherwise specified. Its
thermo-physical properties were from JMat-Pro®. Metal at
furnace spout was assumed to be at a temperature of 700 °C
when the CFF and degasser were not considered or at a
temperature of 727 °C when they were considered. Metal
(a)
Main Launder
Table Trough
Fig. 1 3-D models of main launder (prior to CFF) and table trough (after CFF), rotary degasser and CFF units: a DC #1 and b DC #6
Table 1 Thermophysical properties and calculated properties of the materials in the model
Materials Thermal conductivity Specific heat
(W/mK) (kJ/kgK)
REF-1 0.577 0.8
REF-2 0.12 − 0.22 1.256
INS-1 0.025 − 0.045 1.25
INS-2 0.1 − 0.2 0.8
Note Maximum values of the thermophysical properties were used for the calculated properties
B. Zhang
level at the furnace spout was 122 mm when the CFF and
degasser were not considered or 133 mm when they were
considered. It is noted that the degasser and CFF units were
not considered in models for refractory and geometry com-
parison to save computation time. This will bring some
inaccuracy to the predicted metal temperatures but it will not
change the result in comparison. Initial temperature for the
refractory/insulation was assumed to be at ambient temper-
ature of 27 °C. Metal exits the computation domain below
the downspout with a specified flow rate of *54 kg/min
(*2.0 lbs/s) or of *136 kg/min (*5.0 lbs/s) unless
otherwise specified. For case studies with CFF and degasser
considered, the CFF of 30 ppi was assumed to be at 700 °C
and the preheated CFF bowl was at 377 °C. The degasser
was preheated to 720 °C. It is important to note that the
degasser rotor speed was assumed to be 10 RPM (much
lower than that in practice) to reduce the computation time.
This is not believed to affect the thermal profile significantly.
Heat transfer coefficient between metal and refractory
was assumed to be 4000 and 200 W/m2/K, respectively for
liquid metal and solid metal; it was linearly temperature
dependent during solidification with 4000 W/m2/K at liq-
uidus temperature and 200 W/m2/K at solidus temperature.
The heat transfer coefficients at the environment-type
boundaries of the refractory and steel shell from environ-
ment were 25 W/m2/K. The emissivity of aluminum alloy to
the air was 0.15. The assumptions of these boundary con-
ditions were from previous models with the best match
between modeling result and field measurement on
temperatures.
(b)
Main Launder
Table Trough
Density Heat diffusivity Thermal diffusivity
(kg/m3) (W2s/m4K2) (m2/s)
1842.3 8.504e5 3.92e−7
1041.3 2.877e5 1.68e−7
256.3 0.144e5 1.41e−7
480 0.768e5 5.21e−7
A Study on DC Casting Trough/Launder Design … 943

Thermophysical Properties and Calculated Properties
for Refractory and Insulation The thermophysical prop-
erties, calculated heat diffusivity (thermal conductivity times
density and heat capacity) and thermal diffusivity (thermal
conductivity divided by density and heat capacity) for
refractory (REF-1 and REF-2) and insulation (INS-1 and
INS-2) materials are summarized in Table 1.
Result and Discussion
Refractory and Insulation Material V-Shape refractory for
the main launder and trough are modeled for DC #6. Fig-
ure 2a–c presents metal temperature contours for three dif-
ferent refractory and insulation materials at 240 s. It is noted
that time is counted from when metal is tapped out of the
furnace spout. When the main launder refractory is REF-1
and insulation is INS-2 (Fig. 2a), the metal temperature at
the end of table trough is *678 °C. When the main launder
refractory is REF-2 and the insulation is INS-2 (table trough
is REF-2 refractory and INS-1 insulation) (Fig. 2b), the
metal temperature at the end of table trough is hotter,
*688 °C. When the main launder refractory is REF-2 and
all insulation is INS-2 (Fig. 2c), the metal temperature at the
end of the table trough is the same as in Fig. 2b, *688 °C.
The metal temperature histories at the entry and end of
the main launder, and at the end of the table trough are
presented in Fig. 3 along with a sketch showing the probe
positions. At *100 s, the metal is *662 °C at the end of
launder when the launder refractory is REF-1. When the
launder refractory is REF-2, the metal is hotter at the end of
the launder, *684 °C. At *2000 s, when the launder
refractory is REF-1, the metal is *691 °C at the end of the
launder; when the launder refractory is REF-2, the metal is
hotter at the end of launder, *696 °C. At cast start, heat loss
reduction from *38 °C for REF-1 refractory to *16 °C for
REF-2 refractory is directly associated with the *66%
lower heat diffusivity of REF-2. At run cast, heat loss
reduction from *9.0 °C for REF-1 refractory to *4.0 °C
for REF-2 refractory is related to the *57% lower thermal

Fig. 2 Metal temperature contours at 240 s when the main launder and table trough are: a REF-1 + INS-2 and REF-2 + INS-1; b REF-2 + INS-2
and REF-2 + INS-1; and c REF-2 + INS-2 and REF-2 + INS-2. Metal flow rate = *136 kg/min (*5.0 lbs/s)

Fig. 3 Metal temperature histories for main launders with REF-1 and REF-2 refractories. Metal flow rate = *136 kg/min (*5.0 lbs/s)
944
diffusivity for REF-2. Indeed, the model probed average
peak heat flux from metal to refractory at cast start reduced
from *78 kW/m2 for REF-1 to *24 kW/m2 for RFM-2;
average heat flux at run cast reduced from *8.4 kW/m2 for
RFM-1 to *4.4 kW/m2 for RFM-2. It is noted that metal
heat loss is defined as the metal temperature difference
between the furnace spout (700 °C) and the probed
location.
The metal temperature histories in the table trough when
REF-2 + INS-2 were used for the table trough (Fig. 2c)
were also examined (not shown here). When INS-2 was used
instead of INS-1 for table trough insulation, no metal tem-
perature difference between the two was seen. INS-2 has
greater thermal conductivity than the INS-1 insulation, but at
2000 s, both the model and the analytical calculation show
Fig. 4 Metal temperature contours at 240 s when the model has a a V-Shape refractory (DC #6), and b U-Shape refractory (DC #1); Metal flow
rate = 136 kg/min (*5.0 lbs/s)
Fig. 5 Metal temperature histories for models with V-Shape and U-Shape refractories. Metal flow rate = 136 kg/min (*5.0 lbs/s)
B. Zhang
that the thermal penetration depth for the refractory (REF-2)
is *6.0 cm, thinner than the refractory average thickness, of
*8.0 cm. This explains why there is no difference in metal
heat loss seen when INS-1 was used or INS-2 was used for
the table trough insulation.
Trough/Launder Refractory Geometry The older DC
#
1 has a U-Shape refractory with a larger cavity cross section
and the newer DC #6 has V-Shape refractory with a smaller
cavity cross section. Metal temperature contours at 240 s are
presented in Fig. 4a, b. It is noted that the main launder is
REF-1 + INS-2 and the table trough is REF-2 + INS-1 here
in the models. The metal temperature at the cold end is
*678 °C for the V-Shape refractory (Fig. 4a) and *656 °C
for the U-Shape refractory (Fig. 4b). It is *22 °C hotter
when V-Shape refractory is used.
A Study on DC Casting Trough/Launder Design …
Fig. 6 Metal temperature contours at *1000 s: a U-Shape REF-1 main launder and b V-Shape REF-2 main launder. Metal flow
rate = 54 kg/min (*2.0 lbs/s)
Fig. 7 Metal temperature histories for main launder with U-Shape REF-1 refractory (fine line) and V-Shape REF-2 refractory (coarse line). Metal
flow rate = 54 kg/min (*2.0 lbs/s)
The metal temperature histories at the furnace spout, the
end of the main launder, and at the end of the table trough
are presented in Fig. 5. At cast start, the coldest metal at the
table trough end is *662 °C (at *100 s) when the V-Shape
refractory is used. It is *653 °C (at *240 s) when the
U-Shape refractory is used. At run cast (at *2000 s), the
metal at the end of the table trough is *691 °C when the
V-Shape refractory is used and it is *688 °C when the
U-Shape refractory is used.
At cast start, the lowest metal temperature is *7 °C
colder in the U-Shape table trough than that in the V-Shape
table trough and the cold metal takes much longer to cast
away. At run cast, metal is *4 °C colder in the U-Shape
table trough than in the V-Shape trough. Model results
showed that the average cross section metal flow speed is
*2 faster in the V-Shape launder than in the U-Shape
945
launder, and *5 faster in the V-Shape trough than in the
larger U-Shape trough. The model probed average peak heat
flux from metal to the REF-1 refractory at cast start
increased from *78 kW/m2 for the V-Shape launder to
*92 kW/m2 for the U-Shape launder; heat flux from metal
to the REF-1 refractory at run cast increased from
*8.4 kW/m2 for the V-Shape launder to *9.4 kW/m2 for
the U-Shape launder. The model probed average peak heat
flux from metal to the REF-2 refractory at cast start
increased from *22 kW/m2 for the V-Shape trough to
*24.8 kW/m2 for the U-Shape trough. Heat flux from metal
to the REF-2 refractory at run cast for the V-Shape and
U-Shape troughs tended to be the same, *4.4 kW/m2. The
lower heat flux from metal to the refractory for the V-shape
launder/trough is a result of less metal contact surface area
than for the U-Shape launder/trough. The combination of
946
decreased metal residence time and reduced metal contact
surface area associated with the V-Shape refractory result in
less metal heat loss than the U-Shape refractory.
The maximum local metal flow speed at surface was also
investigated to make sure surface turbulence will not occur
and metal damage is reduced; model results showed that the
maximum local metal flow speed is *0.25 m/sec in the
V-Shape launder and trough, greater than that in the
U-Shape launder and trough, respectively, *0.12 and
*0.04 m/sec. All velocities are still lower than
Fig. 8 Metal temperature contours at: a 145 s, b 400 s and c 2000 s at DC #6. 7075 aluminum alloy; metal flow rate = *116 kg/min
(*4.3 lbs/s)
B. Zhang
*0.50 m/sec, a critical metal speed accepted for aluminum
alloys beyond which surface turbulence will occur.
Case 1: DC #1 Main Launder In order to improve the
heat loss at DC #1, it was proposed to rebuild the DC #1
main launder with V-Shape REF-2 refractory. The metal
temperature contours at 1000 s are presented in Fig. 6a, b,
respectively, for the U-Shape REF-1 launder and the
V-Shape REF-2 launder. It is noted that the degasser and
CFF units were both included in the models. Metal tem-
perature at the end of the table trough is *698 °C for the
A Study on DC Casting Trough/Launder Design …
Fig. 9 Metal temperature histories from model at inlet (HE) and cold end (CE) along with that measured in the field at the end of table trough at
DC #6. 7075 aluminum alloy; metal flow rate = *116 kg/min (*4.3 lbs/s)
V-Shape REF-2 main launder, *18 °C hotter than that of
the U-Shape REF-1 main launder (*680 °C).
The metal temperature history at the end of the table trough
is presented in Fig. 7. At cast start (*500 s), the coldest metal
at the end of the table trough is *678 °C when the refractory
is U-Shape REF-1. It is *691 °C when the refractory is
V-Shape REF-2. At run cast (*2000 s), the metal at the end of
the table trough is *694 °C when the refractory is U-Shape
REF-1. It is *705 °C for when the refractory is V-Shape
REF-2. Heat loss was also calculated; when the main launder
refractory was V-Shape REF-2, the heat loss is *35 and
*21 °C, respectively, at start cast and run cast, significantly
lower than those obtained when the main launder refractory is
U-Shape REF-1, *49 and *32 °C.
The models were probed for the average heat flux from
metal to the refractory; the peak average heat flux at cast
start decreased from *76 kW/m2 for the U-Shape REF-1
launder to *23.4 kW/m2 for the V-Shape REF-2 launder;
heat flux from metal to the refractory at run cast decreased
from *8.8 kW/m2 for the U-Shape REF-1 launder to
*4.9 kW/m2 for the V-Shape REF-2 launder. The heat
fluxes from metal to the REF-2 from the table trough were
very close to each other for DC #1 before and after the main
launder was rebuilt. At start cast, they were *25.4 and
*24.2 kW/m2, respectively, for DC #1. At run cast, they
were *4.6 and *4.9 kW/m2, respectively, for DC #1.
The heat loss reduction associated with the V-Shape
REF-2 refractory for the main launder is the result of the
combination of the faster metal flow velocity (*2 faster,
50% reduction on metal residence time), less metal contact
947
surface area and smaller thermal conductivity of REF-2
(*0.5 smaller). DC #1 has been renovated and casting
temperature profiles show that the run cast heat loss is
indeed better than before.
Case 2: DC #6 Main Launder and Table Trough DC
#
6 was constructed and commissioned with V-Shape REF-2
refractory and INS-2 insulation. The degasser and CFF units
and automated dams were all considered in the models.
Metal temperatures and metal level at furnace spout were
collected at DC #6. It is noted that the measured 7075 alloy
metal temperature and metal level at the furnace spout were
used as boundary conditions in the model. Metal temperature
contours at 145, 400 and 2000 s are presented in Fig. 8a–c.
At 145 and 400 s (Fig. 8a, b), a significant amount of heat
loss occurs at the CFF and the metal temperature at the end
of the table trough is *692 and *672 °C, respectively;
After *400 s, cold metal begins to cast away and the metal
at the end of the table trough gets hotter, *698 °C at 2000 s
(Fig. 8c).
The metal temperature history at the end of the table
trough is presented in Fig. 9 along with that measured at DC
#
6. At start cast from *140 to *400 s, metal temperature at
the end of the table trough decreases from *692 to *673 °C
and metal heat loss is *60 °C at *400 s. From *400 s,
cold metal begins to cast away and the metal temperature at
the end of the table trough increases to *690 °C. At *800 s
metal heat loss is *45 °C. From *800 to *2000 s, the
metal temperature slowly increases from *690 to 698 °C
and the metal heat loss is *35 °C at 2000 s. The predicted
metal temperature at the end of the trough end agrees well
948
with that measured in general, but it tends to be lower at time
less than *700 s. Some factors considered contributing to
the under-prediction on temperature are: (1) constant initial
temperatures assumption for the CFF and degasser refracto-
ries; (2) thermocouple location error between DC #6 and that
in the model; (3) uncertainty associated with the empirical
determination of interfacial and radiation heat transfer coef-
ficients in the model; (4) metal wasn’t held to build up head in
front of CFF unit in reality where the model did.
Summary
A DC casting process modeling program was developed for
trough/launder design and metal heat loss analysis. Two DC
casting lines at Wagstaff® R&D facility were investigated.
Degassers, CFF units, and automated metal level controls
were all included in the CFD modeling program for heat loss
analysis.
When the main launder refractory is changed from REF-1
to REF-2 (DC #6, metal flow rate = *136 kg/min), it was
found that the heat loss is *15 °C less at cast start and
*3.5 °C less at cast run as a result of lower heat diffusivity
and thermal diffusivity; when the table trough insulation is
changed from INS-1 to INS-2, no significant difference is
seen on the heat loss. It was also found that the V-Shape
launder/trough (DC#6, metal flow rate = *136 kg/min) has
less heat loss (*7.0 °C less at start cast and *3.7 °C less at
run cast) than the U-Shape launder/trough (DC #1, metal
flow rate = *136 kg/min) as a result of increased metal
flow speed and reduced metal contact area. When the main
launder is changed from U-Shape REF-1 refractory to
V-Shape REF-2 refractory at DC #1 (Case 1, DC #1, metal
flow rate = *54 kg/min), the combined heat loss is
*11.5 °C less at cast start and *12.0 °C less at cast run as
a result of lower refractory heat diffusivity and thermal dif-
fusivity, increased metal flow speed and less metal contact
B. Zhang
surface area. Heat loss at the newly constructed DC #6 (Case
2, DC #1, metal flow rate = *116 kg/min) was measured
and shows reasonable heat loss agreement between the
model and field measurement. It is believed that the devel-
oped casting process modeling program can be used to
analyze materials and geometry during DC casting trough/
launder design.
Acknowledgements The author is very grateful to K. Bodeau and K.
Becker at Wagstaff® Inc. for their assistance in solid modeling, and also
to C. Shaber for his support and many helpful discussions.
References
1. J.M. Ekenes, A practical model for determining heat loss in a
molten metal distribution system, in Proceedings of the TMS Annual
Meeting and Exhibition: Light Metals 1996, Anaheim, USA (1996),
pp. 949–953
2. J.O. Marthinusen, S.F. Ray, Computer modeling and practical
experiences of temperature loss in launder systems and casting
tables, in Proceedings of the TMS Annual Meeting and Exhibition:
Light Metals 1998, San Antonio, USA (1998), pp. 1183–1189
3. J. Kastebo, T. Carlberg, Temperature measurements and modeling
of heat loss in molten metal distribution systems, in Proceedings of
the TMS Annual Meeting and Exhibition: Light Metals 2004, San
Diego, USA (2004), pp. 649–654
4. G.U. Grun, W. Schneider, Numerical modeling of fluid flow
phenomena in the launder—integrated tool within casting unit
development, in Proceedings of the TMS Annual Meeting and
Exhibition: Light Metals 1998, San Antonio, USA (1998),
pp. 1175–1182
5. S. Blais, J. Alexander, JV. Opbergen, Fluid flow and heat transfer in
a billet hot top casting distribution pan, in Proceedings of the TMS
Annual Meeting and Exhibition: Light Metals 1998, San Antonio,
USA (1998), pp. 1037–1044
6. B. Zhang, Metal flow and heat transfer in Wagstaff® RapidFillTM
metal distribution systems for billet DC casting, in Jim Evans
Honorary Symposium: Proceedings of the Symposium Sponsored by
the Light Metals Division of The Minerals, Metals and Materials
Society(TMS), 2010, Seattle, USA (2010), pp. 11–18
 Critical Role of Thermal Management During
Cast Start-Up of the DC Casting Process

Sabrina Guy, André Larouche, and Josée Colbert

Abstract
In the past, numerical modeling and measurements in the field have provided insight into
direct chill casting of sheet ingots and helped identify critical parameters to achieve
successful cast start-ups. The control of these critical parameters is of key importance to
maximise performance and throughput of the cast house as well as to meet stringent client
requirements. Among these key parameters, management of liquid metal temperature, at
start of cast, is critical in regard to casting performance. This paper presents several process
variables influencing direct chill casting performance such as ingot recovery, false start and
ingot quality.

Keywords
Direct chill casting Thermal management Sheet ingot

Introduction To further progress and continue reducing defects and

Productivity and cost control are essential to the overall
performance of modern cast houses. Over the last decades,
significant progress has been done in improving the casting
technologies and understanding the critical parameters of the
DC casting process. Numerical modeling and experimental
studies have been extensively used especially for direct
chilled casting of sheet ingots. The main objective of these
studies was to increase the understanding of the effect of
direct chilled casting parameters such as casting speed and
water flow rate on hot tear generation, ingot geometry and
cast ability limits [1–6]. Casting trials at the plant along with
this understanding of thermo-mechanical and microstructural
phenomena allowed to validate the fundamental phenomena
and to develop robust casting practices adapted to alloy
specifications and to the casting technology used. This
consequently contributed to a major reduction of rejects and
cast abort occurrence.
S. Guy
A. Larouche (&)
J. Colbert
Rio Tinto, Aluminum divsion, Arvida Research and Development
Centre, P.O. Box 1250, Saguenay, QC G7S 4K8, Canada
e-mail: andre.larouche-crda@riotinto.com
cast abort occurrence, cast house metallurgists must tightly
control the critical process variables and reduce their varia-
tions during a cast and from cast to cast. One of the key
parameters at the start of a cast is the temperature of the
molten metal. Inadequate management of incoming metal
temperature at the starting phase of a cast can lead to
excessive curl, hot tears, run-out, undesired microstructure
or to cast aborts.
This paper highlights the influence of cast house operat-
ing conditions on the thermal behavior at cast start-up and
the positive influence of a tight control on cast abort rate.
Start of Cast: Molten Metal Thermal History
from the Furnace to the Mold
Every casting center has its particular layout and specific
characteristics and equipment. Characteristics such as the
casting pit capacity, drop rate, trough dimension and mate-
rials, furnace dimension and tilting rate and in-line metal
treatment equipment influence the thermal history of molten
metal.

© The Minerals, Metals & Materials Society 2017 949

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_114
950 S. Guy et al.

Fig. 1 Typical cast house layout

for DC casting of sheet ingots

A schematic of a typical cast house layout for DC casting of

sheet ingots is shown in Fig. 1. Two tilting furnaces are
alternatively used to feed one DC unit. The number of ingots
varies with the size of the furnace and DC pit, specific
dimensions of ingots and cast length. An in-line treatment unit
and a filtration system may be used to reach the final quality
required for the application. In the layout illustrated, two dams
are used to guide the metal flow (at the exit of the other furnace
and at the filtration unit). Gates are also used to ensure suffi-
cient metal flow rate and adequate operation of filtration unit at
start of cast. Thermocouples are used to control the tempera-
ture at the beginning of the cast and during the steady-state
phase. Typically, thermocouples are located near the furnace
spout (inside and/or outside the furnace) and near the casting
table. Various types of molten metal level sensors (laser or Fig. 2 Temperature at 25 mm from the bottom of the trough at start of
capacitive sensors) are used to measure and control the molten cast
metal level during filling and casting. The signal from those
metal level sensors is used to control the tilting rate of the
furnace to ensure an appropriate metal head for the filtration the trough length. Depending on the cast house layout and
and degassing unit and filling of the molds. thermal conductivity of the refractory, this temperature dif-
The sequence of operation begins with the titling of the ference can reach, for a short period of time, 10–15% of the
furnace. When the molten metal has reached the desired molten metal temperature in the furnace. This means that the
level at the first gate, this latter is opened and the molten temperature of the metal entering the pin and spout assembly
metal flows to the next gate. This process is repeated up to is much lower than the casting temperature set-point. This
the last gate. Finally, metal reaches the casting trough and temperature drop and duration are mainly due to the molten
the filling of the mold begins. The metal flow rate and metal metal superheat transferred to the trough and metal treatment
head in the mold are then controlled for each ingot using a refractory lining. This heat loss reduces gradually during the
pin and spout assembly that acts has a needle valve. transient part of the cast. After this transition, the metal tem-
Figure 2 shows the molten metal temperature at different perature reaches the target temperature.
locations inside the trough during filling until the start of a This phenomenon has several drawbacks. Firstly, there is
cast. Note that the temperature has been divided by the molten a possibility of metal freezing in the pin/spout assembly that
metal temperature in the furnace. The temperatures shown in can lead to a cast abort. Secondly, lower metal temperature
Fig. 2 were measured at 25 mm from the bottom of the trough, also decreases the fluidity of the molten metal while filling
which represents the temperature of the first metal filling the the mold/bottom block assembly. This lack of fluidity can
mold. One can see the important temperature decrease along lead to slower or temporary stalling of molten metal
Critical Role of Thermal Management During Cast Start-Up … 951

Table 1 Description of variables Variable name Description Unit

in the heat balance
m_ Molten metal flow rate during filling kg/s
cp Molten metal specific heat J/kg °C
Tf Molten metal temperature in the furnace °C
Tm Molten metal temperature at pin/spout °C
h Heat transfer coefficient between metal and trough refractory W/m2 °C
Ar Trough refractory wetted area m2
Tavg Average molten metal temperature in the trough °C
Tr Initial trough refractory temperature °C
r Stefan-Boltzmann radiative constant W/m2K4
e Molten metal emissivity –
Am Molten metal area exposed to atmosphere m2
Ta Casthouse ambient temperature °C

meniscus movement, which can affect the detection of the

metal level in the mold. At worst, the cast must be stopped
due the signal loss.
Another drawback for microstructure critical products is
the time it takes for the metal temperature to reach the
minimum cast temperature requirements in the trough.
During this period of time (or ingot length), the colder
temperature influences the microstructure. For some critical
alloys, this affected zone has to be removed before shipping
to the customer, thus leading to a decrease in the overall
recovery performance at the plant.

Influence of Operating Conditions

on the Casting Temperature at Start of Cast
A simplified and averaged equation to calculate the heat
balance during the filling of the trough is presented below.
The left end side of the equation represents the molten metal
temperature drop along the trough while the right end side
represents the convective/conductive losses to the trough
refractory as well as the radiative losses to the atmosphere.
Table 1 describe each variable of this equation.
_ p ðTf  Tm Þ ¼ hAr ðTavg  Tr Þ þ reAm ðTm4  Ta4 Þ
mc
The analysis of each term of this heat balance will
highlight the process and design parameters that influence
the metal temperature at the start of a cast.
Fig. 3 Calculated temperature at 25 mm from the bottom of a trough
for different filling times
that variation in filling time can lead to a 10–15 °C differ-
ence in the metal temperature drop. This is important and
must be considered in the design phase of the trough layout
in order to achieve the desired temperature targets. Varia-
tions in the filling time, from cast to cast, may also occur.
These variations are due to different sources such as poor
cleaning of the furnace spout (reduced section area),
hydraulic piston malfunction and delay in gate opening in
case of manual operation. Figure 3 shows that a small delay
of 20 s in gate opening can lead to a 3–5 °C difference in the
metal temperature drop.

_
Metal Mass Flow Rate (m)
Furnace Temperature and Control (Tf)
Figure 3 shows the calculated temperature of the molten
metal at the bottom of a 4-m long trough section with dif- The molten metal temperature set-point in the furnace as well
ferent filling times. In this figure, the furnace is on the left, as the burner control shortly before and after the start of the
and a gate is located at the right end side. This figure shows cast have an effect on ingot quality and performance.
952 S. Guy et al.

Fig. 4 Molten metal temperature

at casting pit and in the furnace
before and during the start of cast
for two casts (same product and
dimension)

Inadequate control of those two parameters can increase the

probability of either molten metal freezing in the distributor
pin/spout assembly or ingot hot tearing [7]. It can also
increase the time duration of the transition from cast start-up
to steady-state. For some critical products requiring a specific
casting temperature to meet the desired microstructure and
ingot quality, a longer transition time to steady-state can lead
to an increase in internal scrap at the cast house due to a
longer butt cut. Figure 4 shows the casting temperature in the
trough above the ingot being cast for two identical casts
(same alloy and ingot dimension). This figure also shows the
molten metal temperature in the furnace. As it can be seen,
the molten metal temperature in the furnace, at start of cast, is
the same for both casts. However, for Cast No. 2 the casting Fig. 5 Measured temperature decrease of a typical trough after a cast
temperature in the furnace is in a descending phase, while it is start with and without an insulation blanket
stable for Cast No. 1. In Cast No. 2, the temperature con-
tinues to decrease in the furnace for a certain time leading to a
lower temperature at the casting pit compared with Cast trough. These measurements show that a possible increase of
No. 1. For Cast No. 2 and for this particular critical product, 100 °C can be expected in refractory temperature with an
the ingot butt length to be cut will be longer. insulating blanket. A potential increase of molten metal at
pin/spout of 6 °C per 100 °C of initial trough refractor was
calculated for a typical trough layout.
Trough Refractory Temperature Tr The time duration between two consecutive casts (inter-
cast time) can affect the variation of thermal history of
The typical layout shown in Fig. 1 implies that the furnaces molten metal at start of cast. The intercast time may,
are alternately used for casting. For example, when Furnace amongst other things, vary from cast to cast depending on
1 is used to cast, Furnace 2 is prepared for the next cast the product being prepared in the furnace. This implies that
(metal charging, alloying and fluxing). With this layout, the the trough refractory thermal state, hence the molten metal
small trough section, close to the furnace, is used every two extracted heat may be different from cast to cast. This phe-
cast and hence has more time to cool between casts and nomenon created by the cast house layout and product mix
absorbs more heat from the molten metal. Figure 5 shows have an influence on metal freezing as well as on the time
the measured temperature decrease of a typical trough after a required to reach minimum cast temperature requirement in
cast with and without blanket insulation onto the top of the trough, as shown in Table 2.
Critical Role of Thermal Management During Cast Start-Up … 953

Table 2 Effect of intercast duration on calculated time to reach

minimum cast temperature
Initial trough refractory surface Time to reach minimum cast
temperature (°C) temperature (min)
25 20
125 15
225 11
325 9

Fig. 7 Typical curve with the heating and cooling zone for the pin

pins and spouts, the temperature loss can be several hundred

degrees before cast start, as shown in Fig. 7. The table
within Fig. 7 shows the calculated initial molten metal
temperature drops as a function of the pin and spout average
temperature. In order to avoid freezing of molten metal in
the pin/spout, the time between pin installation and start of
cast must be minimized and controlled to reduce variations.

Conclusions

It is well know that the molten metal temperature is

Fig. 6 Typical pin/spout assembly
Pin/Spout Heating
Figure 6 shows a typical pin/spout assembly. The pin and
spout assembly acts as a needle valve to regulate the molten
metal flow rate during the cast. The preheating of the pins
and spouts typically uses two types of equipment. The pins
are heated in an electric furnace during intercast time. The
spouts are preheated with an electric element that is located
inside the spout. Few minutes before start of the cast, the
spout heaters are removed, and the pins are installed on the
actuator that controls the pins’ opening. During this time, the
temperature of the pins and spouts decreases due to a
chimney effect. Because of the relatively small mass of the
responsible for different ingot defects (hot tearing, inade-
quate microstructure). The temperature of molten metal can
also affect cast abort occurrence. This paper has identified
cast house operating conditions that affect the thermal his-
tory of the molten metal at the start of the cast. The most
important parameters are the trough filling time, pre-heating
of the equipment (trough, pins and spouts) and adequate
control of the molten metal temperature in the furnace before
and during the early stage of cast. Variations of those
parameters from cast to cast may lead to an important
variation of molten metal temperature drop and hence
influence cast house performance. To reduce variation with
low investment and to optimize cast house assets, tight and
automated thermal data management and proper operating
practice must be set up first. New equipment can eventually
(lid, heaters, and gate) contribute to further improve the
process. This philosophy was applied in a plant with mini-
mal cash investment at Rio Tinto leading to a 50% percent
reduction of casts aborted.
Acknowledgements The authors wish to thank Rio Tinto for per-
mission to publish the present paper. Special thanks are given to
Messrs. Martin Fortier, Claude Dupuis, as well as to the other
researchers and technicians involved, for their active contributions.
954
References
1. T.S. El-Raghy, M.F. El-Dmerdash, H.A. Ahmed, A.M. El-Sheik,
Modelling of the transient and steady-state periods during aluminum
DC casting, in TMS Annual Meeting (1995)
2. Y. Wang, M.J.M. Krane, K.P. Trumble, Thermal stress prediction in
AA5182 rectangular ingots, in TMS Annual Meeting (2015)
3. M. M’Hamdi, A. Mo, Microporosity and other mushy zone
phenomena associated with hot tearing, in TMS Annual Meeting
(2002)
S. Guy et al.
4. J.-M. Drezet, M. Plata, Thermomechanical effects during direct chill
and electromagnetic casting of aluminum alloys part I: experimental
investigation, in TMS Annual Meeting (1995)
5. G.P. Grealy, J.L. Davis, E.K. Jensen, P. Aé Tondel, J. Moritz,
Advances for DC ingot casting: part 2—heat transfer and casting
results, in TMS Annual Meeting (2001)
6. G.-U. Grun, W. Schneider, 3-D modeling of the start-up phase of
DC casting of sheet ingots, in Annual TMS Meeting (1996)
7. Y. Caron, A. Larouche, Importance of understanding ingot butt
cooling conditions at cast start-up: a case study, in Annual TMS
Meeting (1996)
 Modelling and Analysis of a Horizontal Direct
Chill Casting Process

Gardar Gardarsson, Throstur Gudmundsson, Magnus Th Jonsson,

and Halldor Palsson

Abstract
The objective of this study is to analyze bleed-outs in Horizontal Direct Chill (HDC) casting
process by using a finite element model (FEM). HDC casting machines for aluminium are
made for continuous casting with typical duration from 3 to 20 days according to the
equipment manufacturer. Reduced duration due to technical difficulties affects capacity,
productivity and cost. In order to improve understanding of the operation and the effect of
alternative casting parameters an FEM model was developed for a 36 bar HDC machine
installed in the Alcoa Fjardaal casthouse. Simulations were done for alternative inlet metal
temperatures, cooling water temperatures, cooling water flow rate and casting speed with
the focus on extracting information about potential bleed out conditions of a cast bar.
Physical measurements were done on the HDC under real casting conditions and compared
with the results of the numerical simulation showing good agreement with the measured
results.

Keywords
HDC casting Bleed-out FEM simulation

Introduction
This paper is based on a M.Sc. work [1] on a Horizontal DC
(HDC) casting machine at the Alcoa Fjardaal casthouse.
The HDC was analyzed and a finite volume model was devel-
oped in the software Ansys Fluent computational fluid dynamics
(CFD). This model was used to improve the understanding of
the casting conditions and relationship between the casting
parameters and known casting defects such as bleed out.
A HDC machine from Hertwich Engineering is installed in the
casthouse. The machine is fed with liquid metal with two 100 ton
tiltable holding/casting furnaces as demonstrated in Fig. 1.
G. Gardarsson (&)
Alcoa Fjardaal, Hrauni 1, 730, Reydarfjordur, Iceland
e-mail: gardar.gardarsson@alcoa.com
T. Gudmundsson
Reykjavik University, Menntavegur 1, 101, Reykjavik, Iceland
M.Th. Jonsson
H. Palsson
University of Iceland, Saemundargotu 2, 101, Reykjavík, Iceland
The two furnaces allow the cast to continue for days by
working in tandem such that while one furnace is casting,
the other is charged with liquid metal and prepared to take
over as the first furnace gets empty. The casting machine is
connected to the furnaces through metal launder system and
two separate tundishes (A and B). The two tundishes are
considerably deeper than the launders to ensure adequate
metal pressure and efficient flow of liquid aluminium into the
casting molds. The cast product (cast bar in the case of the
study) is then pulled away from the casting mold by a
conveyor belt at a set transfer rate. The transfer rate defines
the casting speed of the machine in mm/min of cast product
or ton/h. The arrangement is demonstrated in Fig. 2.
Each tundish feeds two molds, each set up to cast nine
bars as demonstrated in Fig. 1. The molds are copper based
DC molds as shown in Fig. 3 with primary cooling inside
the mold and secondary cooling caused by water jet from the
holes at the edge of the mold. The primary cooling can be
further divided into zone 1 and zone 2 due to different heat
transfer rates as presented in Fig. 4.

© The Minerals, Metals & Materials Society 2017 955

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_115
956 G. Gardarsson et al.

Fig. 1 Schematic overview of the equipment arrangement at Alcoa Fjardaal casthouse. The figure is not in the right proportions

Fig. 2 Schematic overview of tundish and DC casting molds

Fig. 3 HDC casting molds

Modelling and Analysis of a Horizontal Direct …
Fig. 4 Different cooling zones for an alloyed bar [4]. Zones 1 and 2 belong to the primary cooling inside the mold and the secondary cooling is
the water injection at bar’s surface
Fig. 5 Sankey diagram—relative distribution of heat transferred in
alloyed bar
Cooling Conditions
The heat transfer varies by different cooling zones. The
greatest heat transfer occurs in the secondary cooling where
the water is in direct contact to the bar. At first contact the
cooling water boils and the heat transfer reaches its maximum
[2, 3]. After the first contact, in the secondary cooling, the
heat transfer decreases rapidly when getting further from the
molds and the water stops boiling. The second largest heat
transfer occurs in zone 1 where the alloyed bar is in direct
contact to the mold. The least heat transfer occurs in zone 2
where an air gap acts as an insulation between the alloyed bar
and the mold [4]. Downstream of the secondary cooling the
remaining residual heat dissipates slowly into the air but as it
is of no interest it will not be discussed further. A Sankey
diagram of the heat transfer is presented in Fig. 5. The dia-
gram shows heat extraction distribution in a simplified way
957
Fig. 6 Location of measurement points in the tundishes. The arrows
show the flow direction of the aluminium alloy. The figure is not in the
right proportions
for the different cooling zones of the HDC process, showing
that relatively more heat is transferred in the secondary
cooling. The Sankey diagram is based on measurements.
Measurements were performed to examine the tempera-
ture distribution of the aluminium alloy in the tundishes.
Figure 6 shows graphically the location of the measuring
points. The red circles (points 1 and 6) denote points where
thermometers are constantly collecting data to a database.
The blue squares (points 2, 3, 4 and 5) denote new mea-
suring points for comparison with points 1 and 6. The
thermometers were submerged into the aluminium alloy at
the same level as the outlet from the tundish, Fig. 2 shows
the location of the thermometers in the tundish. Measure-
ments were performed during three different days and the
temperature distribution was even in all cases, the results is
shown in Table 1. The flicker in the measurement device
showed ±0.5 °C for each measurement, which is within the
confidence limits.
From this it can be concluded that it is sufficient to have
one thermometer in each tundish located at the ends, such as
points 1 and 6 in Fig. 6. It can be assumed that the temper-
ature is the same for the entire tundish and that all the alloyed
bars at the same tundish have the same initial temperature.
958 G. Gardarsson et al.

Table 1 Results from the temperature measurements in tundishes, shown in °C

Date 1 2 3 4 5 6
23.Jan.12 671–672 671–672 671–672 670–671 670–671 670–671
15.Feb.12 672–673 672–673 672–673 672–673 672–673 672–673
16.Feb.12 670–671 670–671 670–671 669–670 669–670 669–670

Fig. 7 Location of outlets measured, marked with blue squares. The arrow denotes casting direction. The figure is not in the right proportions

Table 2 Results from Date Intake 1 2 3 4 dT

measurements at water outlets,
showing temperatures in °C 23.Jan.12 15.7 17.9 17.8 17.9 17.7 2.1
15.Feb.12 16.1 18.1 18.0 18.2 18.1 2.0
16.Feb.12 15.6 17.7 17.8 17.9 17.8 2.2

Table 3 Conditions for cooling Condition Inlet water temperature (°C) Flow rate (m3/h) Other variables
water
A 15 130 Constant
B 15 135 Constant
C 15 140 Constant
D 20 130 Constant

Fig. 8 Surface temperature of the cast bar—cooling condition A. Water temperature 15 °C and cooling water rate 130 m3/h

Measurements were performed to examine the tempera-
ture difference in the cooling water inside the molds. To get
as accurate results as possible only outlets close to the
intakes were measured. Four such outlets were examined,
see locations in Fig. 7. A failure analysis shows all bars are
equally likely to bleed.
The results show that the temperature change of the
cooling water in the molds is in the range 2.0–2.2 °C, see
Table 2. From this results it can be estimated that the
average temperature change is 2.1 °C.
To understand what effect the cooling water has on the
temperature distribution in the alloyed bars, measurements
were performed for four different cooling water conditions,
as can be seen in Table 3.
Surface temperature of the alloyed bars were measured
when it came out of the mold and until it was 110 mm
outside from the mold. An average curve showing surface
temperature distribution and range was calculated for each
condition, see Fig. 8. The curve shows the average value of
the measurements at each point. The range is shown with
Modelling and Analysis of a Horizontal Direct …
maximum and minimum curves, representing the maximum
and minimum values at each point. The three curves follow
each other quite nicely up to 20 mm from the mold when
they start to deviate for a short distance (approximately
10 mm) until they start following each other again. The
average surface temperature of the cast bar 10 mm from the
mold is 112.4 and 61.9 °C at 106 mm from the mold.
The range (between min. and max. temperatures) goes from
5.1 up to 10.3 °C. The reason for the change in heat
extraction 20 mm from the mold may be due to water
boiling and evaporation on the surface of the cast bar while
the surface temperature is above the boiling point of the
water and water flow rate is not too aggressive to destroy the
thin water film boiling conditions. Based on the quantity of
required makeup water for the HDC machine cooling system
it can be estimated that 0.012% of the cooling water evap-
orates during the casting process.
Similar measurements were performed for all the condi-
tions presented in Table 3 and can be seen in the original
M.Sc. work [1]. Figure 9 shows the comparison for all
conditions. Condition D has the highest temperature and
therefore lowest cooling capacity, which makes sense since
the water has the highest temperature and low flow rate.
Comparing conditions A, B and C shows clearly that by
keeping the temperature still and just increasing flow rate
results in a higher cooling capacity. Comparing A and D
shows that the temperature of the cooling water does not
affect the cooling condition inside the molds, resulting in the
same surface temperature at first, but it just seems to start
having influence around 17 mm outside of the molds.
These measurements show that the amount of cooling
water has greater impact on the heat extraction than the
initial temperature of the cooling water. This can also be
demonstrated with the following equation for convection
heat transfer.
_ p DT
Q ¼ mC ð1Þ
Fig. 9 Surface temperature of the cast bar, compared with different
cooling water conditions
959
The heat transfer changes in proportion to the change in
the amount of cooling water (m) _ while a change in initial
temperature of the cooling water affects only the specific
heat capacity Cp and the temperature change of the cooling
water (DT) remains practically constant. Lowering the initial
temperature of cooling water from 20 to 15 °C increases the
specific heat capacity only by 0.07% [5].
Numerical Model—2D
A 2D numerical model of a solidification process was con-
structed in Ansys Fluent to verify the functionality of the
model against a known case from previous study by Krane
and Vusanovic [4]. Figure 10 shows a schematic presenta-
tion of the physical model, which is designed to be similar to
HDC casting of Mg alloys found in the model [6].
It represents a 300 mm long and 80 mm thick alloyed bar
with the first 45 mm inside a casting mold (top and bottom
surface). The left side is a plate with no slip conditions and a
10 mm center inlet. There is heat flux into the bar through
the inlet but the end plate is otherwise considered to be
perfect insulation with no heat flux. The cooling is divided
into three zones: mold cooling zone h1, air gap zone h2 and
secondary cooling with water impingement. The secondary
cooling has two values, htop and hbottom and the ratio
htop/hbottom has been defined as 1.7, similar to Krane and
Vusanovic study. It is estimated that the heat transfer in the
secondary cooling is uniform and does not decrease when
getting further from the molds. The inlet speed is defined as
eight times the casting speed [4]. The case was tested for two
different casting speeds. Values for the casting parameters
can be seen in Table 4.
Krane and Vusanovic used the alloy Al-4.5 wt% Cu,
which is comparable to cast aluminium alloy A201.0.
Thermophysical properties of the cast aluminium alloy
A201.0 can be seen in Table 5.
Fig. 10 Schematic figure of the known case that was tested [4]
960 G. Gardarsson et al.

Table 4 Values for the casting Variable Value Reference

parameters in the 2D simulation
h1 1500 W m−2 °C−1 Grandfield and Dahle [6]
−2 −1
h2 150 W m °C Grandfield and Dahle [6]
htop 10,000 W m−2 °C−1 Hamed and Akmal [7]
Tinlet 730 °C Krane and Vusanovic [4]
Vcasting − 1 300 mm/min Krane and Vusanovic [4]
Vcasting − 2 210 mm/min Krane and Vusanovic [4]

Table 5 Thermophysical Property Value

properties of cast aluminium alloy
A201.0 [8] Density 2800 kg/m3
Specific heat capacity 963 J/kg °C
Thermal conductivity 121 W/m °C
Viscosity 0.0013 kg/m-s
Heat of fusion 389,000 J/kg
Liquidus temperature 649 °C
Solidus temperature 571 °C

Fig. 11 Casting speed 1 (300 mm/min)—results from Ansys Fluent,

showing solidification

Fig. 13 Model representation of simulated casting arrangements

Numerical Model—3D

A 3D model of 150 mm long alloyed bar with inflow pipe

Fig. 12 Casting speed 2 (210 mm/min)—results from Ansys Fluent,
showing solidification
Figures 11 and 12 show the results from Ansys Fluent.
They are comparable to the results presented by Krane and
Vusanovic. The depth of the mushy zone decreases with
decreasing casting speed, causing faster solidification. Inside
the molds, thin shell is formed next to the walls. When leaving
the mold, faster cooling begins, and the bar freezes all the way
to the core. In the comparison, the solidus and the liquidus
lines have similar locations and the depth of the mushy zone is
the same as in Krane and Vusanovic publication.
was created, see Fig. 13. Symmetry was assumed and
required calculation power reduced by limiting the simula-
tion to half a bar.
After stepwise iteration a 50,000 cell model was deemed
adequate for the simulation work of several physical con-
ditions. A center section of the mesh is shown in Fig. 14.
The length of the bar (150 mm) was also based on iteration
process based on altering the length of the bar. Boundary
conditions for the calculations are shown in Fig. 15.
Figure 16 shows how the cooling zones were defined in
the model. These cooling condition were applied to all
cooling surfaces; bottom, top and sides of the bar. Heat
transfer coefficients h1 and h2 belong to the primary cooling
and are located inside the molds.
Modelling and Analysis of a Horizontal Direct … 961

Fig. 14 Mesh of 3D model

Fig. 15 CFD boundary

conditions. Arrows show casting
direction

Fig. 16 Cooling distribution in

the numerical model. These
conditions were applied to all
cooling surfaces of the bar;
bottom, top and sides

To simulate the heat transfer in the secondary cooling and

how the heat transfer decreases, the cooling was divided into
six zones and it was estimated that the heat transfer is uniform
within each zone. Heat transfer coefficients h3, h4, h5, h6, h7
and h8 belongs to the secondary cooling and are all located
outside the molds. This is just an approach and does not fully
reflect the complexity of a jet impingement heat transfer.
The heat transfer coefficients for the model were calcu-
lated from the physical measurements described previously
and by using the numerical model. By knowing temperature
difference of the cooling water inside the molds and the
water flow rate, the heat transfer in the primary cooling can
be calculated with Eq. 1. Knowing the heat transfer in the Fig. 17 Simulation of the temperature curve presented in Fig. 8
primary cooling and the surface temperature distribution of
the cast bar outside of the molds, then the numerical model results of the simulation, along with the upper and lower
was used to simulate and optimize all the heat transfer limit for the temperature curves (min/max). The target for
coefficient until the simulation gave the same surface tem- the simulation was to be within the min/max limits, obtained
perature distribution in the model. Figure 17 shows the from case shown in Fig. 8.
962 G. Gardarsson et al.

Table 6 Conditions used for Parameter Value

simulation and results for heat
transfer coefficients Temperature of aluminium alloy 675 °C
Casting speed 360 mm/min
Cooling water rate 130 m3/h
Cooling water temperature 15 °C
Heat transfer coefficient—h1 3000 W/m2-°C
Heat transfer coefficient—h2 600 W/m2-°C
Heat transfer coefficient—h3 90,000 W/m2-°C
Heat transfer coefficient—h4 60,000 W/m2-°C
Heat transfer coefficient—h5 39,000 W/m2-°C
Heat transfer coefficient—h6 26,000 W/m2-°C
Heat transfer coefficient—h7 19,000 W/m2-°C
Heat transfer coefficient—h8 19,000 W/m2-°C

Fig. 18 Heat transfer coefficient

in the secondary cooling. Blue
lines denote simulation values
and black curve denote a 3rd
order polynomial fitting through
the points

Table 7 Simulation parameters Parameter Case 1 Case 2 Case 3

for evaluation of bleed-out
conditions Temperature of aluminium alloy (°C) 675 725 625
Casting speed mm/min 360 360 360
Cooling water rate m3/h 130 130 130
Cooling water temperature (°C) 15 15 15

Table 6 shows the conditions used for this simulation
along with the results for the heat transfer coefficients.
These results show how the significance of the secondary
cooling compared to the primary cooling. In cooling zone h3
where the water spray hits the cast bar the cooling rate
reaches its maximum, 90,000 W/m2 °C due to boiling of the
water. This is quite consistent with studies from others [2, 3].
Approximately 60 mm from the molds, the heat transfer
coefficient has decreased by 79%. Figure 18 shows a 3rd
order polynomial fitting of the heat transfer coefficients as a
function of the distance from the casting mold.
The model and the extracted heat transfer coefficients
were then used to simulate alternative casting conditions at
the Fjardaal casthouse.
Simulations
The model was used to simulate bleed-out potential for
alternative casting conditions. Three cases will be presented
in this paper. The cases are listed up in Table 7.
Modelling and Analysis of a Horizontal Direct …
Case 1 represents actual casting conditions while Case 2
is calculated to see the effect of excessive increase in casting
temperature (50 °C increase) of the liquid metal and Case 3
similar drop in casting temperature.
Case 1—Actual casting conditions
The temperature distribution of the cast is shown in Fig. 19.
The figure shows the constant temperature in the infeed
pipe and a liquid sump directly behind the pipe. The effect
of the rapid primary cooling in cooling zone h1 is visible at
the upstream end of the bar and an increase in surface
temperature in zone h2 is also visible. The extreme heat
Fig. 19 Isometric view of temperature distribution in a bar—normal state (case 1)
Fig. 20 2D views of
solidification in a bar—normal
state. In the symmetry view and
the side view, location of molds is
shown
963
extraction at zone h3 shows rapid decrease in bar tempera-
ture and formation of the mushy zone inside the liquid
sump. The effect can also be viewed as liquid fraction dis-
played in Fig. 20.
As expected the highest potential bleed-out areas are at the
center of the bottom surface and directly behind the infeed
pipe on the side vertical side. The potential risk of bleed-out
increases with increased liquid fraction and microstructural
solidification effects such as macro-segregation can alter the
local condition resulting in bleed-out. Figure 21 shows
location of six points that were used for plotting liquid
fraction curves along the length of the cast bar.
964 G. Gardarsson et al.

Fig. 21 Locations of curves

plotted along the length of the bar

The liquid fraction decreases rapidly for the first 10 mm as

expected while the bar is inside cooling zone h1 as seen on
Fig. 22. The formation of the air gap and hence reduced cooling
rate at zone h2 can be seen on the figure as increase in liquid
fraction inside the bar. This effect has the strongest visualization
at locations C1 and C6 (surface points) due to the reduced
cooling rate and effect of the large heat sump inside the bar.
Another important feature to notice is the impact of the
secondary cooling on the solidification conditions inside
the casting mold. Due to the rapid heat extraction caused by
the water spray the liquid fraction at all locations starts to fall
(and hence the percentage of solid metal to increase) some
5–20 mm inside the mold.

Case 2—Effect in excessive increase in casting

temperature
As can be expected all the curves for the liquid fraction are
higher due to the increased heat flow into the bar with the
hotter metal. The surface at locations C1 and C6 is no longer
completely solid as seen with the liquid fractions not being
zero and the case represents a bleed-out condition. The liq-
uid fraction at locations C2 and C5 have also increasing
from approximately 0.02 and 0.10–0.30 and 0.50 respec-
tively as can be seen on Fig. 23.
Case 3—Effect in excessive decrease in casting
temperature
The shift in the liquid fraction curves in Fig. 24 is opposite
to the shift presented in Fig. 23 as expected. The liquid
fraction at location C5 at the end of the mold is almost zero.
Discussions
The changes to the solidification process with altering
casting temperature has been displayed in Figs. 22, 23 and
24. As expected, an increased casting temperature results in
Fig. 22 Case 1—liquid fractions in normal casting a on side of the bar
at locations C1, C2 and C3 and b at the bottom of the bar at locations
C4, C5 and C6
an increase in heat needed to be extracted from the liquid
metal sump and hence increased fraction of semi liquid
metal closer to the surface of the cast product.
Figure 25 displays in a clear way the difference in liquid
fractions and hence state of solidification for the three cal-
culated cases. The thin shell of solidified metal near the edge
displayed in Fig. 23b gives an indication that the casting
conditions are becoming critical and the likelihood of
bleed-out due to localized melting of the thin shell is high.
Due to the nature of the simulation it is possible to alter only
one parameter at a time like the presented simulation has
done with altering the temperature of the cast metal when it
enters the casting mold. In real life casting environment, the
operators do not have the luxury of altering only one
parameter at the time due to fluctuations and time dependent
changes in multiple outside and uncontrollable conditions
and parameters that affect the casting conditions. Changes in
Modelling and Analysis of a Horizontal Direct …
Fig. 23 Case 2—liquid fractions in casting with increased casting
temperature a on side of the bar at locations C1, C2 and C3 and b at the
bottom of the bar at locations C4, C5 and C6
chemical composition, impurities in the metal, addition of
grain refining agents, conditions of casting molds such as
surface quality facing the liquid metal and cleanliness of the
internal waterways and water holes for secondary cooling
will all have impact on the microstructural solidification in
the cast product and can individually or jointly lead to dis-
turbance in the solidification process and hence cause the
thin shell to break and bleed of liquid metal to occur.
Another important conclusion that can be indirectly
drawn from the present study is the importance of the time
that the cast bar stays within cooling zone 1. The liquid
fraction curves shifts upward and hence also to the right with
increased liquid temperature in Figs. 22, 23 and 24. One can
visualize that a possible decrease in casting speed and hence
longer residence time within cooling zone 1 would bring the
liquid fraction curves in case 2 outside the mold with the
result of metal bleed-out.
965
Fig. 24 Case 3—liquid fractions in casting with decreased casting
temperature a on side of the bar at locations C1, C2 and C3 and b at the
bottom of the bar at locations C4, C5 and C6
Conclusions
A numerical model was established in the software Ansys
Fluent CFD, to simulate the casting process of a HDC
casting machine at the Alcoa Fjardaal casthouse. Heat
transfer coefficients were calculated for the primary and
secondary cooling zones based on physical measurements.
The low heat transfer at h2 is the primary reason for
bleed-out of liquid metal from within the cast bar as the
excessive heat inside the bar starts to re-melt the solidified
shell formed at zone h1. It is interesting to see the rapid
changes in heat transfer in the secondary cooling.
Simulations were done for normal casting conditions at
the Fjardaal casthouse as well as extreme increase and
decrease in inlet metal temperature. Correlation between
bleed-out sensitivity and changes in casting temperature has
been established and possible impact of casting speed discussed.
966 G. Gardarsson et al.

Fig. 25 Liquid fractions in

casting at the end of cooling zone
h2 for alternate casting
temperatures, a case 1, b case 2,
c case 3

Cooling water temperature and flow rate has shown to have
smaller impact on bleed-out likelihood than the casting
temperature. Conclusions can be drawn from the work that
bleed out frequency can be strongly affected by unstable
casting conditions.
References
1. G. Gardarsson, Modeling and analysis of a horizontal direct chill
casting process. M.Sc. thesis, University of Iceland, 2012
2. J. Grandfield, P. McGlade, DC casting of aluminium: process
behaviour and technology. in Materials Forum-Rushcutters Bay,
vol. 20 (1996), pp. 29–51
3. J. Zuidema et al., Secondary cooling in DC casting: modeling and
experimental results. Light Metals TMS, 873–878
4. M.J. Krane, I. Vusanovic, Macrosegregation in horizontal direct
chill casting of aluminium slabs. Mater. Sci. Technol. 25, 102–107
(2009)
5. Engineering ToolBox, Retrieved Apr 2012, from http://www.
engineeringtoolbox.com/water-thermal-properties-d_162.html
6. J.F. Grandfield, A. Dahle, Modeling of Casting and Solidification
Processes 1999, ed. by C.P. Hong, J.K. Choi, D.H. Kim (Seoul)
(2000)
7. M.S. Hamed, M. Akmal, Determination of heat transfer rates in
industry-like spray quench system with multiple impinging water
jets. Int. J. Mater. Prod. Technol. (IJMPT) 24, 184–198 (2005)
8. Subs Tech, Retrieved Apr 2012, from http://www.substech.com/
dokuwiki/doku.php?id=cast_aluminum_alloys&DokuWiki=d404e75
606031f9bf1386610391719ad (2012)
 Circulation of Grains During Ingot Casting

Carolyn Joseph, Samuel R. Wagstaff, and Antoine Allanore

Abstract
A novel method based on the use of a turbulent jet has recently been proposed to minimize
the degree of centerline segregation in Direct-Chill (DC) casting of aluminum ingots. The
functionality of this method relies on the ability of the jet to re-suspend solute poor grains
which have settled to the bottom of the molten pool. To date, the presence of these grains
has mostly been acknowledged by theory and post-mortem observations. Herein are
reported results of a series of experiments designed to allow the sampling of grains in DC
cast ingots with and without the use of a turbulent jet. Analysis of the shape and chemical
composition of the samples are reported.

Keywords
DC casting Macrosegregation Floating grains

Introduction and Theory
Macrosegregation is a metallurgical defect in DC cast
aluminum alloys. It has been studied extensively, and most
commonly leads to negative centerline segregation in
hypoeutectic aluminum alloys [1–3]. Macrosegregation is
caused by the relative motion of the liquid and solid phases
during solidification [2, 4]. Several factors contribute to this
relative movement, including sedimentation of free-moving
“floating” grains, shrinkage-induced flow, thermal and
solutal convection, and deformation due to thermal or
mechanical stress.
In a previous study, experiments were conducted with a
turbulent jet designed to suspend and circulate floating
grains from the ingot sump and minimize macrosegregation
[5]. These findings support the free-floating grain theory as
the dominant contributor to negative centerline segregation
in DC casting of large-scale aluminum ingots. The present
study investigates the floating grain theory with direct grain
sampling.
C. Joseph (&)
S.R. Wagstaff
A. Allanore
Massachusetts Institute of Technology, 77 Massachusetts Ave.,
Cambridge, MA, USA
e-mail: cmjoseph@mit.edu
The existence and motion of floating grains was previ-
ously postulated based on the observation of a duplex
microstructure at the center of DC cast ingots [6]. The
presence of fine- and coarse-cell dendrites suggests that
some of the grains present in the center of the ingot originate
elsewhere and are transported to the center. Due to
non-equilibrium effects, grains are initially solute poor, and
their motion to the center of the ingot contributes to negative
centerline segregation. Further evidence comes from the
positive centerline segregation of grain refining elements
like Ti, which exhibits a peritectic reaction with Al and is
expected to be transported with floating grains [7].
There has been discussion as to whether the coarse- or
fine-cell dendrites observed in the duplex ingot microstruc-
ture are the floating grains responsible for macrosegregation
[3, 6]. Compositional analysis by Eskin et al. shows that the
coarse-cell dendrites are solute-lean relative to the fine-cell
dendrites, indicating that their accumulation could lead to
negative centerline segregation [8]. Recent work by Wagstaff
and Allanore supports this idea by showing that the static
angle of repose for the coarse-cell dendritic morphology
matches the critical sump angle of inclination after which
negative centerline segregation occurs [9].

© The Minerals, Metals & Materials Society 2017 967

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_116
968
Various postulates have been made regarding the nature
of floating grains. These are based on theory and
post-solidification measurements made on the coarse- and
fine-cell dendrites observed in the center of ingot
cross-sections.
Eskin et al. [8] noted that in grain refined casts,
coarse-cell grains tend to cluster together in the final cross
section. Line scan data was presented by Eskin et al. and
Nadella et al. to compare the compositional variation across
fine- and coarse-cell dendrites [8, 10]. In general, line scan
measurements showed that the coarse-cell grains exhibit a
plateau of minimum solute composition with steep solute
buildup towards the grain edges. The line scan average and
the minimum (plateau) solute concentrations in the
coarse-cell grains were reported.
The effect of stirring with a turbulent jet on floating grain
characteristics has not yet been studied, but it has been
observed that the stirring decreases the average final grain
size in the center of the ingot by over 30% [11].
Knowledge of floating grain properties is of particular
importance for casting models. If floating grains are to be
incorporated into computational macrosegregation models, it
is critical to know the size, shape, and composition of grains,
which indicate their microstructural development and
behavior in two-phase flow [12–15].
To date, grains have rarely been observed in or sampled
directly from the melt. Anticipating that the in situ obser-
vation of free-floating grains is an important step in proving
their existence and studying their motion, this study aims to
measure grain properties in a standard DC cast as well as in a
cast that has been stirred with a turbulent jet.
Fig. 1 Diagrams of molds used
for grain sampling. a Surface
quenching (SQ) mold. b Deep
quenching (DQ) mold
C. Joseph et al.
Experimental Method
Free-floating grains were captured from the melt with copper
quenching molds. The surface quenching (SQ) mold design
was based on the design of Martinez and Flemings [16].
Samples were obtained from the ingot head, several mil-
limeters below the surface of the metal. The mold was made of
two copper plates separated by 1 mm graphite spacers, which
created an opening with dimensions of 25 mm  1 mm. The
bottom of the mold was sealed with plastic wrap and the top
was connected to a vacuum generator. Samples were obtained
by touching the bottom of the mold to the liquid metal surface.
The plastic wrap melted and a thin sample of metal was pulled
into the mold’s opening. The deep quenching (DQ) mold
captured samples from the ingot sump (up to 0.6 m below the
surface.) The DQ mold consisted of a copper mold fitted into
the end of an alumina-silica composite tube with rope seals.
The mold opening was sealed with a refractory plug attached
to a wire. To take a sample, the mold was lowered into the
metal to the desired depth and the plug was removed to allow
metal to pass into the mold’s opening. Figure 1 shows the
mold dimensions. The metal cooling rates were *300
and *500 °C/s for the SQ and DQ molds, respectively. The
rates were determined by measurement of the secondary
dendrite arm spacing of the quenched microstructure [17].
The microstructure of the samples obtained with these
molds exhibited large grains (presumably those present in
the semi-solid region) that were surrounded by fine crystals
(formed during quenching). Figure 2 shows an example of a
quenched sample and a representative image of sample
microstructure.
Circulation of Grains During Ingot Casting
Fig. 2 a Sample obtained with DQ mold. b Representative SEM image of quenched microstructure
Two Al4.5%Cu ingots were cast using a 600 mm 
1750 mm Wagstaff LHCTM mold. The metal was grain
refined with 10 ppm of B grain refiner in the form of 3:1 TiB
rod. In one ingot, the melt was distributed with a standard
fiberglass combo (or distribution) bag (hereafter called
standard), while in the other, metal was introduced with a
turbulent jet (hereafter called stirred) as used by Wagstaff
and Allanore [5]. Once the steady state sump had developed,
the surface and deep quenching molds were used to obtain
samples from the locations shown in Fig. 3.
The quenched samples were sectioned and prepared for
optical and scanning electron microscopy. Optical micro-
graphs were taken for grain sizing and shape measurements.
Grains areas and perimeters were measured from optical
Fig. 3 Sampling locations in DC cast ingot sump
969
micrographs with an image processing software. The mea-
surements were used to determine a 2D shape factor pro-
posed by Saltykov, which is the ratio of the perimeter of a
circle of equal area as the grain to the measured grain
perimeter [18]. Solute composition was measured by
energy-dispersive x-ray spectroscopy. Line scans of com-
position were measured across grain diameters.
Results
No large grains were observed in samples quenched from the
surface of the standard DC cast. Grains were obtained with
the deep quenching mold in the sump of the standard DC
cast ingot. Grains were also obtained from the surface and
sump of the ingot stirred with a turbulent jet. Figure 4 shows
representative SEM images of the captured grains. In gen-
eral, the standard DC cast ingot contained both globular and
dendritic grains, while grains in the stirred casts were more
globular.
Grain areas were used to determine an average grain
diameter, which is reported in Table 1 with corresponding
error. Table 1 also reports the average Saltykov 2D form
factor for the entire grain populations from each cast and for
the subset of grains with diameters >40 µm.
Line scan measurements across grains were used to
determine the average and minimum grain compositions for
each cast. These results are reported in Table 2. The average
solute concentration in each grain was determined by inte-
grating the composition across each line scan and dividing
by line length to normalize to grain diameter. Since line
scans exhibited a plateau of minimum solute concentration,
the average of these plateau points is reported as the mini-
mum composition.
970 C. Joseph et al.

Fig. 4 Representative SEM images of quenched samples. a Standard surface quench. b Standard deep quench. c Stirred surface quench. d Stirred
deep quench. Floating grains are present in all samples except those from the surface of the standard cast

Table 1 Floating grain Cast Average grain Saltykov 2D form Saltykov 2D form factor (grain
diameters and form factors diameter (µm) factor (all grains) diameter >40 µm)
Standard cast 39 ± 22 0.67 ± 0.18 0.50 ± 0.13
deep quench
Stirred cast deep 47 ± 22 0.74 ± 0.13 0.70 ± 0.14
quench
Stirred cast 52 ± 19 0.73 ± 0.13 0.70 ± 0.13
surface quench
Reported error represents the standard deviation from the mean

Table 2 Average and minimum Cast Average composition (wt% Cu) Minimum composition (wt% Cu)
solute compositions of grains in
the Al4.5%Cu standard and Standard cast deep quench 1.40 ± 0.20 1.16 ± 0.09
stirred ingots Stirred cast deep quench 1.40 ± 0.37 1.04 ± 0.12
Stirred cast surface quench 1.21 ± 0.13 1.09 ± 0.05
Reported error is the standard deviation from the mean
Circulation of Grains During Ingot Casting
Discussion
The observation of grains in quenched samples confirms the
existence of free-floating grains. They are present in the
sump (*0.5 m below the surface) of standard DC cast
ingots as well as in the sump and at the surface of ingots
stirred by a turbulent jet. Grains were not observed at the
surface of the standard DC cast because the distribution
method did not circulate grains to the surface.
As was observed by Eskin et al. in the coarse-cell grains
in post-solidified microstructures, floating grains tend to
cluster together in quenched samples (Fig. 4b–d). It seems
that grains move as agglomerates or as a connected network
(dendrites or welded mass) in the melt.
Grains obtained in the standard cast ranged in size
from *20 to 60 µm. The standard DC cast contained
floating grains that were dendritic in shape as well as those
that were globular (Fig. 4b). The average form factor for
these grains was 0.67, though it decreased to 0.50 in grains
with diameters >40 µm, indicating that larger grains tend to
be less globular than smaller grains. It was not expected that
globular grains would be present in the cast without stirring
from the turbulent jet. Their presence indicates that fluid
motion in a standard ingot can create conditions under which
globular grains form or that dendritic features form at some
time after grain sampling occurred.
Line scans from grains captured from the sump of the
standard cast ingot show a similar profile to the one reported
by Eskin et al. for coarse-cell dendrites [8]. They exhibit a
plateau of minimum solute composition as opposed to the
more irregular variation in composition that was observed in
the fine-cell dendrites.
The minimum Cu content in the floating grains in the
standard DC cast ingot was 1.07–1.25 wt% Cu, which rep-
resents 72–76% depletion from the alloy composition. Eskin
et al. observed minimum compositions that corresponded to
75–83% depletion from the alloy composition in the
coarse-cell dendrites. The average floating grain composition
for the standard DC cast ingot was found to be 1.20–1.60 wt%
Cu, which corresponds to a depletion from the alloy furnace
composition of 64–73%. Eskin et al. reported average com-
positions of 27–58% depletion from the alloy in the coarse-cell
dendrites. The minimum Cu content is therefore the same for
grains captured from the melt and coarse-cell dendrites
observed in the final microstructure. The average Cu content
of the floating grains suggests however a larger depletion than
in the coarse-cell dendrites. This can be considered indicative
of a buildup of solute at the outer edges of coarse-cell grains.
The buildup would occur between the time the grains were
captured in the melt and their final state in the ingot
microstructure.
Turbulent jet stirring had little effect on the average or
minimum composition of the floating grains as compared to
971
the standard cast. Grains from the stirred cast do not show a
greater buildup of solute at their edges, which could indicate
diffusion of solute into the grains during circulation. This
lack of solute buildup could indicate that the grains circulate
for a short time in the melt relative to the timescale of solute
diffusion or that stirring washes away solute rich liquid that
surrounds the grains. The buildup of solute that is present in
grains in the final cast microstructure likely occurs after the
grains have welded to the solidification interface at the
bottom of the sump.
Grain shape analysis indicates that, in general, grains
from the casts stirred with a turbulent jet tend to be more
spherical, while a higher number of grains from the
standard DC cast are more dendritic. Variation in shape
after stirring is more pronounced for larger grains. Grains
that have diameters greater than 40 µm represent 35% of
the grains in the standard cast, 56% of grains in the sump
of and 67% of grains at the surface of the stirred cast.
They have 2D form factors of 0.50 ± 0.13, 0.70 ± 0.14,
and 0.70 ± 0.13, respectively. Despite these general
trends, a significant number of globular grains were pre-
sent in the standard cast, as were dendritic grains in the
stirred cast.
It has been shown that stirring with a turbulent jet causes
grain refinement [11], but measurement of grain size
(Table 1) does not indicate that stirred floating grains are
smaller than grains in the standard DC cast at the time they
were captured from the sump. This indicates that the
mechanism by which stirring with a turbulent jet refines the
grains does not affect the average size of floating grains in
the melt.
Conclusion
It has been shown by direct observation that free-floating
grains are present in the sump of a standard DC cast Al 4.5%
Cu ingot and have an average size of *20–60 µm. Den-
dritic as well as globular grains have been observed. These
grains are depleted in solute and have an average composi-
tion of 1.2–1.6 wt%Cu. The floating grains are on average
more depleted in solute than the coarse-cell grains observed
in final cast microstructures.
Floating grains have also been observed in ingots stirred
with a turbulent jet. These grains do not vary significantly in
size or composition from the grains in the standard cast.
They do not show evidence of increased solute buildup at
grain edges with circulation. In general, the grains in the
stirred cast are more spherical, though dendritic grains were
observed as well. Since no obvious refinement in the size of
floating grains is observed in casts stirred with a turbulent
jet, further work is needed to help understand the mechanism
by which stirring refines grains.
972
Acknowledgements The authors would like to thank Novelis Solatens
Technology Center for their support and invaluable assistance in
completing this work.
References
1. S.R. Wagstaff, A. Allanore, Experimental observations of
macrosegregation in DC casting of rolling slab ingots, Light
Metals, 877–882 (2016)
2. D.G. Eskin, Physical Metallurgy of Direct-Chill Casting of
Aluminum Alloys (CRC Press, Boca Raton, 2008)
3. M.G. Chu, J.E. Jacoby, Macrosegregation characteristics of
commercial size aluminum alloy ingot cast by the direct chill
method, Light Metals, 925–930 (1990)
4. M.C. Flemings, Solidification Processing (McGraw-Hill, New
York, 1974)
5. S.R. Wagstaff, A. Allanore, Minimization of macrosegregation in DC
cast ingots through jet processing, Metall. Mater. Trans. B (2016)
6. H. Yu, D.A. Granger, Macrosegregation in aluminum alloy ingot
cast by the semicontinuous direct chill (DC) method, in Interna-
tional Conference on Aluminum Alloys—their Physical and
Mechanical Properties (1986), 17–29
7. B. Gariepy, Y. Caron. Effects of casting parameters on the extent
of centerline macrosegregation in DC cast sheet ingots, Light
Metals, 961–971 (1991)
8. D.G. Eskin, R. Nadella, L. Katgerman, Effect of different grain
structures on centerline macrosegregation during direct-chill
casting. Acta Mater. 56, 1358–1365 (2008)
C. Joseph et al.
9. S.R. Wagstaff, A. Allanore, Centerline depletion in direct-chill cast
aluminum alloys: the avalanche effect and its consequence for
turbulent jet casting, Metall. Mater. Trans. B (2016)
10. R. Nadella, D.G. Eskin, L. Katgerman, Effect of grain refinement
on structure evolution, Floating grains, and centerline macroseg-
regation in direct-chill cast AA2024 alloy billets. Metall. Mater.
Trans. A 39A, 450–461 (2008)
11. S.R. Wagstaff. A. Allanore, Modification of macrosegregation
patterns in rolling slab ingots by bulk grain migration, Light
Metals, 715–719 (2016)
12. C. Beckerman, Modelling of macrosegregation: applications and
future needs. Int. Mater. Rev. 47(5), 243–261 (2002)
13. C.J. Vreeman, M.J.M. Krane, F.P. Incropera, The effect of
free-floating dendrites and convection on macrosegregation in
direct chill cast aluminum alloys part 1: model development. Int.
J. Heat Mass Transf. 43, 677–686 (2000)
14. C.J. Vreeman, F.P. Incropera, The effect of free-floating dendrites
and convection on macrosegregation in direct chill cast aluminum
alloys part II: predictions for Al-Cu and Al-Mg alloys. Int. J. Heat
Mass Transf. 43, 687–704 (2000)
15. M.J.M. Krane, Macrosegregation development during solidifica-
tion of a multicomponent alloy with free-floating solid particles.
Appl. Math. Model. 28, 95–107 (2004)
16. R. Martinez, M. Flemings, Evolution of particle morphology in
semisolid processing. Metall. Mater. Trans. A 36, 2205–2210
(2005)
17. R. Martinez, Formation and Processing of rheocast microstruc-
tures, Ph.D. thesis, MIT, (2004)
18. S.A. Saltykov, Stereometric Metallography, 2nd edn. (Moscow,
Metallurgizdat, 1958)
 Minimization of Macrosegregation Through
Jet Erosion of a Continuously Cast Ingot

Samuel R. Wagstaff and Antoine Allanore

Abstract
Recent investigations have suggested important benefits in using a turbulent mixing jet
impinging into the molten pool of a continuously cast Al4.5Cu ingot [1]. It was for example
demonstrated that such jet can significantly modify the macrosegregation patterns found in
large castings. One possible reason put forth for this modification is the ability of the jet to
suspend sedimented grains from the ingot centerline. In this study, we propose a model to
optimize the re-suspension of grains through the use of an engineered jet. We have recently
completed series of full scale experiments using a variety of jet powers for Al4.5Cu ingots.
In this study we completed a blind study of a new alloy (AA3104) cast under different
conditions in order to validate the robustness of our model. Results confirm the potential of
a turbulent jet to mitigate the degree of centerline segregation in DC cast products for a
relatively broad range of alloys.

Keywords
DC casting Macrosegregation Turbulent jet Stirring

Introduction and Theory
The technology behind Direct-Chill (DC) casting is well
developed with a lengthy history stretching back to the
1940s. However, research into the theories, hypotheses, and
available factual data illustrate that even after 70 years of
extensive research and practice, structure and defect forma-
tion in DC cast products are still not completely understood,
let alone controlled. Perhaps one of the most pernicious of
these defects is macrosegregation, i.e. large scale composi-
tional inhomogeneity throughout the dimensions of the
casting. While the average composition may match the target
product, local compositional variances can fluctuate up to
20% from nominal. Such variances can cause drastic chan-
ges in physical properties throughout the ingot [2].
S.R. Wagstaff (&)
A. Allanore
Massachusetts Institute of Technology, 77 Massachusetts Ave,
Cambridge, MA 02139, USA
e-mail: swagstaff@gmail.com
While research into the causes of macrosegregation has
been steady since before the development of DC casting,
there has been very little progress in treating its fundamental
causes. Instead, research and development efforts have been
focused on minimizing the effects of macrosegregation while
maintaining productivity. The present research has been
undertaken in an effort to leverage the knowledge gained
over the past 70 years in order to eliminate macrosegrega-
tion from DC cast rolling slab ingots without sacrificing
production.
The degree of macrosegregation of a given alloy is
dependent on the ingot dimensions, composition, and the
casting process utilized. Continuous, or semi-continuous
casting routes are frequently used to produce ingots of
wrought-alloy compositions, destined for subsequent pro-
cessing [3–8]. Moreover, the semi-continuous DC casting
technique is the most efficient technology for the produc-
tion of large ingots destined for rolling or forging. The
presence of macrosegregation in these products sets limi-
tations on the sizes and compositions that can be cast in
productive and efficient manners. Thus, the importance of

© The Minerals, Metals & Materials Society 2017 973

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_117
974
macrosegregation during the production of cast products
cannot be understated. Considered a major defect in DC
cast aluminum alloys, the occurrence of this defect is
determined uniquely by solidification conditions. In gen-
eral, it is known that macrosegregation is influenced by
solid-liquid flow conditions in the semi-solid region of the
casting [5, 9–13]. Complete reviews of the various mech-
anisms and their roles specifically in DC cast products have
been completed elsewhere [14, 15]. We propose a review
of the most relevant parameters in order to prepare the
reader for our subsequent modifications to current theory
and practice.
Perhaps one of the most striking features of macroseg-
regation patterns in large DC cast ingots is the severely
depleted centerline [16] which can exhibit up to 15% lower
concentration than the target composition. Excellent reviews
of all of the mechanisms driving segregation are available
[15, 17–19], and in this paper we will only remind the
potential driving mechanisms of the depleted centerline of
these ingots.
Shrinkage Flow
It has been well documented that one of the primary driving
mechanisms for negative centerline segregation is the flow
driven by shrinkage of the alloy as it solidifies (6–10 vol% in
aluminum alloys). This flow is only significant in the mushy
zone of the transition region. While these flow velocities are
small in magnitude (10−4 m/s), their effects can be signifi-
cant because they involve the transport of highly enriched
material. This material is drawn from the hotter part of the
transition region and is directed normal to the solidification
front, deeper into the mushy zone. It then contributes to
negative centerline segregation by “robbing” the centerline
of rejected solute [12, 20, 21]. Eskin et al. [22] have pro-
posed a model to estimate the magnitude of the macroseg-
regation caused by shrinkage flow. The shrinkage flow,
which is always normal to the solidification front can be
decomposed into horizontal and vertical components.
Negative centerline segregation occurs due to the horizontal
component uniquely [9, 23]. The solute transport from the
centerline to the surface occurs very slowly, and gradually a
bulk solute transport is generated. The centerline becomes
depleted because there is no horizontal influx of additional
enriched material. The result of Eskin’s analytical solution
have been applied to simplified computational solutions
incorporating uniquely heat transfer conditions (ignoring
convection). The results indicate the potential to produce
centerline segregation in castings absent of other effects. In
reality, such a model would be difficult to apply using
experimental data because it assumes a uniform composition
at the solidification front, and requires the careful
S.R. Wagstaff and A. Allanore
measurement of the mushy zone thickness. While shrinkage
flow can explain some of the observed centerline segrega-
tion, it is not the only cause of such segregation.
Sedimenting Grains
The movement of free moving grains from the slurry region,
also called sedimenting or free-floating grains, has long been
identified as one of the dominant mechanisms behind cen-
terline segregation in DC cast ingots. The original theory
was proposed in 1929 by Voronov [24]. He proposed that
solute-depleted crystals detached from the solidified shell
and were then carried to the center of the ingot by the
advancing solidification front (particle pushing). This theory
was largely proposed due to the appearance of a duplex
structure made of fine and coarse dendrites in the center of
these castings. However, the validity of this theory was
questioned in the 1940’s due to experimental evidence
illustrating the presence of centerline segregation in the
absence of the aforementioned duplex structure. The role of
shrinkage flow illustrates how centerline depletion in the
absence of a duplex structure could exist. However, The
theory was re-instated in the 1980s by Yu and Granger [10]
and Chu and Jacoby [11] due to the persistent observation of
the duplex structure in some castings [25–29]. There has
been some debate on the source of depletion originating in
the duplex structure, but it has been determined that coarse
dendrites are more depleted in solute compared to the fine
dendrites [15, 30]. Researchers have used numerical mod-
eling approaches to investigate how the movement of grains
can influence macrosegregation [31, 32]. Modelling results
indicate that the gravity-driven sedimentation of grains to the
center of ingots can result in centerline segregation.
Today there is little debate on the presence of sediment-
ing grains in large castings. The primary open question
however, is why a duplex structure is present in only some
castings. It has been well documented from early works to
the present [3, 10, 25–28], that the severity of macrosegre-
gation tends to increase with casting speed. While this is
easily explained by the deepening of the sump, it has also
been noted that an increase in casting speed also leads to an
increased volume fraction of sedimenting grains [33]. This
effect has led us to hypothesize that there is an additional
effect beyond normal convective flow driving the transport
of mobile grains.
Avalanche Effect
It is generally assumed that the transport of sedimenting
grains is driven by convective flow conditions within the
slurry region. However, convective flow conditions are
Minimization of Macrosegregation Through Jet Erosion …
present in all castings, and thus the transport of solid phase
should always be an observable phenomenon. It is however,
not consistently observed. We have previously noted that
increasing the casting speed not only increases the degree of
centerline segregation, but also the amount of sedimented
grains along the centerline. We propose that the deepening
of the sump causes the angle of the walls of the sump to
exceed the angle of repose of the growing grains within the
slurry region. Due to avalanche dynamics, exceeding the
angle of repose of any granular material causes a catas-
trophic movement of particles until the angle of inclination is
once again below the static angle of repose. Using the
relations presented by Myhr and Hakonsen [34], and prop-
erty values for the Al4.5Cu alloy, we have plotted the angle
of inclination of the sump as a function of ingot width and
casting speed. This has been produced in Fig. 1.
In this figure, we can see that as casting speed and ingot
width increase, the angle of inclination also increases. In the
1970s Livanov et al. [35] performed a series of tests on a
variety of molds at different casting speeds in order to
determine the optimum casting speed for zero centerline
segregation. They found that operating at speeds lower than
Fig. 1 Representation of the angle of inclination of the sump as a
function of both casting speed and ingot width. The color scale is such
that higher angles of inclination are red, while lower ones are blue. The
colorbar at right represents this scale from 0 to 90° of inclination, with
975
this (for a given width) generated positive centerline
segregation, while operating faster generated negative
centerline segregation (white dashed line). While this bears
resemblance to the segregation conditions proposed by
Flemings et al. [36] involving flow conditions, we propose
that this shift is due to the increase in sedimenting grains
once the angle of inclination is exceeded. As previously
mentioned, it has been determined that fine-cell dendrites are
richer in solute than coarse-cell dendrites. It is important to
realize that fine-celled dendrites represent coarser particles
while the opposite is true for coarse-celled dendrites. As the
sump depth increases, it is the coarser-dendrites (smoother
particles) that will begin to avalanche first. Since these grains
are depleted in solute, there is a preferential accumulation of
solute-lean grains in the center of the ingot leading to
increased solute depletion. As the sump becomes deeper,
more of these grains sediment thereby increasing this effect.
The non-generalized observation of the duplex
microstructure could be due to several effects. Firstly, it is
necessary to have a sufficient thickness of the slurry zone in
order to generate sufficient sedimenting grains to have an
observable impact on structure even though it may still be
labels for the angle of repose of smooth and coarse media for reference.
The dashed line and labels in the lower plot represent the findings of
Livanov [35]
976
occurring. Secondly, depending on the alloy in production,
different speeds may be used for similar ingot dimensions.
Thus in addition to the slurry zone thickness difference
(through alloy change), the change in speed will result in a
sump geometry change either promoting or inhibiting the
avalanche effect. This makes comparison between casting
conditions very difficult, and potentially explains why
duplex structure was not always observed even though
centerline depletion was present.
If the dominant mechanism of centerline segregation in
DC cast aluminum ingots is the sedimentation of grains
during the casting process; we can infer that a reduction of
the number of these grains would lead to a corresponding
reduction in centerline segregation. We can therefore pro-
pose that a controlled removal of the grains which sediment,
we can minimize the degree of centerline segregation in DC
casting.
Analytical Framework
An eulerian fluid dynamic approach to two-phase flow and
in particular grain erosion from granular beds is a topic that
has received significant prior attention, for example with the
goal of understanding sediment removal and transport or
designing pipe or reactor flow conditions for suspensions.
The relevant governing parameters have all been experi-
mentally determined for horizontal flow over a horizontal
bed, and a pertinent review is presented by Wagstaff and
Allanore [37]. Nonetheless, we can redefine the corre-
sponding parameters for a jet impinging perpendicularly
onto a granular bed. Figure 2 is a schematic representation
of this condition, specifically referenced to the case of
Fig. 2 Schematic of a liquid
metal jet with volume flux Q0,
impinging on a granular bed
through a nozzle of radius b0. The
velocity of the jet exiting the
nozzle is U0. The jet is situated a
height, H0 above the coherency
isotherm. Above this is a granular
bed (grain diamete of d) of
material forming the slurry region
of height h0
S.R. Wagstaff and A. Allanore
solidifying metal, though valid for other fluid/grain
relationships.
The primary goal of the impinging jet is to remove the
excess grains which may be found along the ingot centerline
due to avalanche events. This requires a fundamental
understanding of the rate of grain transport as a function of
jet power. We can visualize as in Fig. 2, that an arbitrary jet
impinging on a granular bed will promote the re-suspension
of grains within a certain radius. As these grains are trans-
ported from the center due to the influence of the jet they
form a crater, whose radius and deepening rate are functions
of the grains and the jet itself. In a previous study [37] we
have derived an equation for the deepening rate of the
formed crater as a function of these aforementioned
parameters:
 
3=2 Uth =Uj
Uc  C1 Uth Reg 1  C2 ð1Þ
Reg
where Uc is the descent velocity of the bottom of the crater,
Uth is the terminal settling velocity of the grains, Reg is the
granular Reynolds number, and Uj is the velocity of the jet at
the surface of the granular bed (slurry region). The deriva-
tion of this equation, and the definitions of relevant param-
eters can be found in the relevant publication [37]. While
this equation is valid for any jet impacting a non-cohesive
granular bed, it is important to recast these parameters into
the DC casting space and appropriate terminology. The
granular Reynolds number and terminal settling velocity of
the grains are related to the shape, size, and relative density
of the solid aluminum grains in the liquid aluminum. We
have performed a series of experiments to determine these
parameters for the sedimenting grains [1]. The velocity of
the jet at the surface of the slurry region can be determined
Minimization of Macrosegregation Through Jet Erosion …
from the theory of turbulent jets [38]. Explicitly, Uj is
described as:
 
b0 b0 1
Uj ¼ U0 H 0  h0 þ ð2Þ
/ 2/
where b0 is the nozzle radius and U0 is the mean velocity of
the fluid at the nozzle outlet in the bulk fluid, expressed as a
function of the volumetric flow rate Q0:

(diameter) varies as a function of casting speed. In the pre-
U0 ¼ Q0 = pb20 ð3Þ
H0 and h0 represent overall depth of the fluid and the
granular bed respectively (See Fig. 2). For a turbulent jet,
the entrainment constant a can be taken to be a = 0.08 [38].
In the case of DC casting, H0 is typically taken to be the
sump depth measured at the coherency isotherm, because the
slurry zone is difficult to probe. Numerous relationships exist
for the depth of the sump as a function of casting parameters,
but the authors have found good agreement between that
proposed by Myhr and Hakonsen [34] and experimental
results. It is important to realize that the fundamental gov-
erning parameters of the sump depth (and thus the jet
velocity at the bottom of the sump) are the physical
dimensions of the mold, the alloy, and the casting speed.
These parameters are fixed by the specific casting recipe and
mold used thus, we can treat the sump depth as constant.
Correspondingly, having fixed the casting speed and the
dimensions of the mold, we have also fixed the volumetric
flow rate of the jet. Upon careful consideration of Eqs. 2
and 3 we can see that the only remaining variable we can use
to specify the velocity of the jet is its radius, b0. This means
that when seeking to optimize a jet velocity to minimize the
effects of sedimenting grains, the diameter of the nozzle is
the key variable to change the jet velocity, while maintaining
all other parameters constant.
Returning to the thought of an optimized jet to minimize
centerline segregation, we can visualize the optimum result.
Given steady state casting conditions, viewing the sump of
the ingot in the reference frame of the mold, we will have a
stable sump of a given shape. The jet impinges downward on
the slurry region to maintain a certain volume fraction of
grains. Avalanche events along the inclined walls of the
sump draw volumes of grains to the center of the ingot. As
these grains reach the bottom, they are re-suspended by the
jet and forced away from the ingot centerline. A jet that is
too weak will allow the avalanching grains to remain in the
center, while a jet that is too strong will actively erode the
bottom of the sump, and cause it to be deeper than normal
conditions. In order to actively balance these two conditions
we need to provide a jet whose crater descent velocity (Uc in
Eq. 1) precisely matches the velocity of our reference frame,
otherwise known as the casting speed. By specifying the
descent velocity to be the casting speed, we can guarantee no
977
accumulation of grains in the center of the ingot, and that the
power of the jet is then dissipated in the re-suspension of
grains.
Model Application
With fixed alloy composition and mold dimensions, we are
most interested in seeing how the required jet power
vious section we have described how we wish to equate the
crater descent velocity Uc in Eq. 1 with the casting speed.
Using our mold dimensions and alloy properties we can
calculate the sump depth (H0–h0) as a function of this casting
speed. Since the granular Reynolds number Reg, and hin-
dered terminal settling velocity Uth, are functions of the fluid
and grains themselves, this means the final variable left to
specify in Eq. 1 is the jet velocity at the bed surface (bottom
of the sump) specified by Uj. Normally one could simply
pick any arbitrary jet which fits this parameter Uj, but by
fixing the casting speed, we have also inadvertently fixed the
volumetric flow rate, Q0. This means by implementing
Eqs. 2 and 3, there is a unique jet diameter which generates
the appropriate jet velocity at the surface of the bed in order
to generate a crater descending at the same velocity as the
casting speed. Using appropriate material parameters [39] it
is possible to predict this desired jet power as a function of
casting conditions as shown in Fig. 3 for AA3104.
This figure represents the range of predicted jet Reynolds
numbers as a function of mold Reynolds number, respec-
tively defined as:
2Ml Mw Uc 2Ml Mw Uc
Rej ¼ Rem ¼ ð4Þ
pbo m mðMl þ Mw Þ
where Ml and Mw represent the mold length and width
respectively. The curve represents the relationship between a
changing casting condition (mold bore or speed) and the
requisite change in jet power to ensure minimum centerline
segregation.
Experimental Trials
In order to test the proposed model, an experiment was
designed in order to compare our jet-processed results
against standard experimental data on macrosegregation.
Utilizing the mold size (0.6985 m  1.5875 m) and alloy
AA3104, we performed a series of experiments whose
conditions were identical to those described in [14, 16]. One
ingot was cast using the standard DC technique with a
combination bag, while a twin ingot was cast using the
predicted optimum jet power from Fig. 3. Based on the
predictive plot, the minimum macrosegregation should be
978
Fig. 3 Predictive plot for jet
processing parameter for an
AA3104 alloy. The mold
Reynolds number is based on an
equivalent hydraulic radius, and
casting speed. The jet Reynolds
number is based on the jet
velocity and diameter. The square
represents the conditions tested
on a commercial DC caster
observed for AA3104 with a jet characterized by a Reynolds
number of approximately 114,000 for a mold Reynolds
number of approximately 1760.
Following the casting, cross sections were taken from
each of the ingots at a cast length of 1800 mm, and then
analyzed using an Olympus Alloy Plus XRF Analyzer
according to the procedure outlined in [1].
Results
Figure 4 is a surface plot of the top left quadrant of a hori-
zontal section of a slab (seen from the top), showing the
relative deviations from furnace composition for the
Fig. 4 Surface contour representing deviation from furnace composi-
tion as observed in one quadrant of a horizontal section taken at
1800 mm of cast length. This standard AA3104 procedure can be
directly compared to previously investigated macrosegregation profiles
S.R. Wagstaff and A. Allanore
standard DC condition. While this profile is similar in form
to that previously discussed [16] we can see immediately
that the centerline region is still present but less distinct than
for the Al4.5Cu trial ([16], Fig. 3). The size of this depleted
region is nearly identical to that of previous investigations,
extending 550 mm from the center towards the short face
and 75 mm from the center towards the long face. In addi-
tion, we can see the distinctive enrichment zone found lying
adjacent to the depleted centerline region parallel to the long
face.
Figure 5 is a contour plot of the top left quadrant of the
jet stirred AA3104 ingot. Here we can see that the centerline
depletion zone is significantly decreased in size and
magnitude as compared to the standard cast in Fig. 4.
[16]. The color code is based on relative deviation from furnace
composition (in \%), positive values corresponding to solute enrich-
ment, while negative values represent solute depletion. All X and Y
axes are identical with (0, 0) representing the center of the cross-section
Minimization of Macrosegregation Through Jet Erosion …
Fig. 5 Surface contour representing deviation from furnace composi-
tion as observed in one quadrant of a horizontal section taken at
1800 mm of cast length. This jet processed AA3104 ingot was
produced using the predicted jet Reynolds number from Fig. 3. The
The enriched region normally found parallel to the depleted
region has also been effectively dispersed.
Discussion
The qualitative analysis of Figs. 4 and 5 illustrate the
potential for jets to modify centerline segregation in rolling
slab ingots. The fact that the centerline segregation zone
itself is reduced is a successful outcome of our hypothesis.
However, in order to perform a more quantitative analysis of
the process performance, we have calculated the
Macrosegregation Index (MI described in [37]) of each of
the cross-sections investigated during this series of trials.
The standard profile exhibited a MI of 0.13. The stirred cast
was characterized by a MI of 0.035, a 75% reduction in
centerline segregation. While there is some scatter in the data
obtained from the XRF analyzer, we can say conclusively
that the error margin is small enough to not interfere with the
analysis. The original derivation of Eq. 1 relied on the
presence of an optimum jet whose crater erosion rate mat-
ched the casting speed. Based on the improved performance
of the best performing jet we can simultaneously confirm the
validity of the analytical model and the presence of an op-
timum jet.
Conclusion
The experimental results of Livanov et al. [35] illustrated the
presence of an optimum casting speed for a specific mold
dimension in order to generate zero centerline segregation.
We postulated that these results were due to the static angle
979
color code is based on relative deviation from furnace composition (in \
%), positive values corresponding to solute enrichment, while negative
values represent solute depletion. All X and Y axes are identical with
(0, 0) representing the center of the cross-section
of repose of the grains and by increasing the casting speed
beyond a certain threshold, the sump walls became
sufficiently steep to promote avalanche events driving the
sedimentation of coarse grains.
If the sedimentation of mobile grains through avalanche
dynamics generates the intense centerline segregation
observed in Fig. 4, then the removal of these grains should
significantly impact the size and severity of the centerline
segregation found in DC cast ingots. We have proposed the
use of a downwardly impinging circular jet to re-suspend
these sedimented grains and preven their bulk accumulation
along the ingot centerline. By performing a blind test on our
analytical approach with new casting conditions and a
unique alloy, we have been able to demonstrate that down-
wardly impinging turbulent jets do significantly reduce the
size and magnitude of the depleted region along ingot
centerlines (see Fig. 5).
Given the potential of a turbulent jet to mobilize grains,
we postulated the existence of an optimum jet which would
minimize centerline segregation in DC cast ingots. Utilizing
the casting speed as the crater descent speed Uc in Eq. 1 we
create a careful balance where the bottom of the sump is
washed by the impinging jet. Any excess grains are resus-
pended while a certain allowed fraction remain thereby
preventing the severe crater formation predicted by other
researchers [40]. We have validated this prediction in an
AA3104 alloy (see Fig. 5) which exhibited over 75% less
segregation than the standard case.
While we postulated the existence of the avalanche effect,
more robust experiments are required to analyze the angle of
stability of grains along an inclined sump wall and the fre-
quency of avalanche events. A more detailed sampling of
the mobile grains (re-suspended or sedimenting) is also
980
necessary to definitively prove the existence of sedimenting
grains in situ and better understand their suspension
dynamics.
All of our calculations have been the result of a
zero-dimensional model we have derived. Without an
appropriate model incorporating grain nucleation, migration,
and attachment a fully computational model will not
accurately reflect our experimental results. Additional work
is needed to empirically and computationally model the
lifecycle of these grains within the molten pool.
Acknowledgements We would like to thank the kind support of the
Novelis Solatens Casting Center for their help and resources during the
completion of this project.
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Rolling Slab Ingots. MIT MS Thesis (2015)
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 Full Size Measurement and Simple Prediction
on Macro Segregation of Aluminum Alloys
Elements in Industrial Direct Chill Casting Slab

Tatsuya Yamada, Nobuhito Ishikawa, Takashi Kubo,

and Koichi Takahashi

Abstract
In direct chill casting of aluminum alloys, negative macro segregation of eutectic elements
and positive macro segregation of peritectic elements can occur at the center of the slab. It
is very important to investigate the mechanism of these macro segregations because they
influence the mechanical and chemical properties of the wrought products. The authors
have performed a two-dimensional measurement of the macro segregation by optical
emission spectroscopy, and important characteristics of this phenomenon were observed.
They are explained qualitatively and quantitatively by our proposed hypothesis, the
partially swept solute model. The model assumes that the sump flow penetrating into the
mushy zone will sweep out the enriched or diluted liquid solute until the critical solid
fraction fs
is reached, when the dendrite arms begin to sufficiently entangle with each other,
making it difficult for the sump flow to penetrate into the mushy zone. Then, the ordinary
solidification process continues. In case of severe segregation, the microstructure at the
center of the slab becomes a granular crystal because the enriched or diluted solute in front
of the solidification interface is swept out by the penetration flow and dendrite growth is
inhibited.

 
Keywords
DC casting Macro segregation Microstructure

Introduction
In direct chill casting of aluminum alloys, negative macro
segregation of eutectic elements and positive macro segrega-
tion of peritectic elements can occur at the center of the slab. It
is very important to investigate the mechanism of these seg-
regations because they can result in inhomogeneous
mechanical and chemical properties of the wrought products.
In general, macro segregation can be understood as the
transport of alloy elements by the relative movement of the
liquid and solid phases. Many experimental or numerical
studies have been conducted on macro segregation over the
T. Yamada (&)  N. Ishikawa  T. Kubo  K. Takahashi
Research & Development Division, UACJ Corporation,
Tokyo, Japan
e-mail: yamada-tatsuya@uacj.co.jp
last few decades [1–12], especially for 2xxx or 7xxx alloy
billets. Recently, Chu et al. and Wagstaff et al. reported
remarkable results on measuring the macro segregation of Al–
Zn–Cu–Mg and Al–4.5Cu rolling slabs, respectively [3, 12,
13]. Some mechanisms of macro segregation have been pro-
posed in these studies, and can be roughly divided as follows:
(i) Sump flow, caused by thermo-solutal convection.
Metallostatic pressure or pouring penetrates into the
mushy zone washes out the enriched eutectic solute
and the diluted peritectic solute [1, 5–8];
(ii) Primary phase grains or free-floating crystals are
transported by gravity or melt flow and sediment at
the bottom of sump [2, 3, 7–9, 12, 13];
(iii) Shrinkage-induced flow into the mushy zone trans-
ports the segregated solute [4, 7–11].

© The Minerals, Metals & Materials Society 2017 981

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_118
982
Fig. 1 Schematic illustration of the mechanism of macro segregation.
a Washed out solute in the mushy zone by sump melt flow,
b sedimentation of the primary phase grains, and c moving of solute
in the mushy zone by shrinkage flow
Schematic illustrations of each mechanism are shown in
Fig. 1. Some studies [8, 14] have shown that macro segre-
gation can be predicted by numerical simulation based on
the above mechanisms individually or in combination.
However, many past studies still measured macro segre-
gation one-dimensionally, i.e., in the radial direction or
along the width. Thus, it is still difficult to understand macro
segregation patterns over the entire slab in detail. In addition,
numerical simulations are sophisticated and complex
because of coupling thermo-hydraulic flow, free-floating of
crystals, shrinkage-induced flow, and so on. In this study, we
have proposed a simple model which can predict macro
segregation quantitatively. In order to do that, the distribu-
tion of each alloying element in full size 5xxx alloy slab
slices has been measured in detail. In addition, the mi-
crostructure and micro segregation were investigated in a
region of remarkable macro segregation.
Experimental Procedure
Macro Segregation Measurement
In this study, commercial purity 5xxx series of Al alloy slabs
of size 400–600 mm  800–2200 mm were produced at a
casting speed of 30–60 mm/min. As shown in Fig. 2, cross
Fig. 2 Schematic illustration measuring macro segregation of DC slab
T. Yamada et al.
sectional slab slices were cut from steady state region in the
withdrawal direction, and chemical elements were analyzed
at intervals of 25–30 mm by 50–60 mm using portable
optical emission spectroscopy (OES). Each measured con-
centration of the chemical elements C was normalized by the
average value C0 of the entire slab slice using following
equation.
C
Cm ¼  100 ð%Þ ð1Þ
C0
In this study, the minimum value of Cm for the eutectic
elements or the maximum value for the peritectic elements in
a slab are regarded as the degree of macro segregation.
Observation of Microstructure and Micro
Segregation
The microstructure at the center of the slabs, where
remarkable macro segregation occurs, was observed in a
plane parallel to the casting direction by optical microscopy.
In addition, distribution of Mg and Ti in the observation area
was analyzed by electron probe micro analysis (EPMA). The
effort of the degree of macro segregation on the micro
characteristics was investigated.
Results
Macro Segregation
Figure 3 shows the results of the two-dimensional macro
segregation analysis of Fe, Si, Mg, Mn, and Ti at a cross
section of a commercial 5xxx series of Al alloy slab of size
of 500 mm  1600 mm. Table 1 shows the partition coef-
ficient k, the degree of segregation, and the maximum and
minimum value of Cm for each element. Negative macro
segregation was observed in the eutectic elements Fe, Si,
Mg, and Mn, and positive segregation was observed in
peritectic element Ti at the center of in the thickness direc-
tion. In the eutectic elements, the element with lower
k showed greater negative segregation, and Ti, with a k much
higher than 1, showed a remarkable positive segregation. In
addition, it was found that the inverse segregation was dis-
tributed around the center macro segregation area.
Figure 4 shows the relationship between the degree of
Mg segregation and the withdrawal of the melt flow rate
during casting. It was found that a faster casting speed and a
larger slab size can cause greater macro segregation.
Figure 5 shows the relationship between the degree of
macro segregation of Fe, Si, Mg, Mn, and Ti and the par-
tition coefficient k of the three different slabs. It is notable
that the five plots in each slab are almost linear, and the slope
Full Size Measurement and Simple Prediction on … 983

of the line becomes steeper with an increase in the degree of

segregation.

Characteristics of the Microstructure and Micro

Segregation

The microstructures at the center of the two slabs that

showed mild and severe macro segregation are shown in
Fig. 6. There was a remarkable morphological difference
between the two. For mild macro segregation, equiaxed
dendrite growth can be seen, whereas for severe segregation,
granular crystals were formed with little dendrite growth.
EPMA images of Mg and Ti obtained from the same
samples are shown in Fig. 7. In the case of severe segre-
gation, there was a remarkable difference in the concentra-
tion of both Mg and Ti between the inside and the edge of
the grains. While this difference was also seen in the case of
mild segregation, it was less obvious.

Discussion

As shown in Fig. 3, macro segregation was seen at the center

Fig. 3 Measured macro segregation of Fe, Si, Mg, Mn, and Ti of 5xxx
series of Al alloy slab in the casting condition A shown in Fig. 4, is
normalized by the average solute concentration of the whole slice of a
slab
of in the width direction, and inverse segregation was
observed around the macro segregation. It is believed that
sedimentation of the primary phase grains, as shown in
Fig. 1b, can cause center segregation. However, it is not
easy to explain the inverse segregation by this mechanism
because the primary phase grains are intrinsically
eutectic-enriched and peritectic-diluted. If the inverse seg-
regation is formed only by this mechanism, grains or den-
drite segments must be separated and slide down intensively
at the inverse-segregated area. However, it has been reported
that intensive separation of grains or dendrites can occur
where a melt alloy is remarkably undercooled [15], for
example, near the meniscus or mold surface. Therefore, it is
hard to explain that macro segregation is formed by only
sedimentation of the primary phase grains. It has also been
reported that shrinkage flow, as shown in Fig. 1c, causes
center segregation. Shrinkage flow is believed to occur in a
direction perpendicular to sump geometry [1]. Thus, this
flow is induced in the vertical direction at the center of the
thickness, which implies that the enriched eutectic solute and
the diluted peritectic solute are not easily forced to move in

Table 1 Degree of macro segregation shown in Fig. 3, normalized to the average composition
Mg Fe Si Mn Ti
k: partition coefficient 0.45 0.034 0.11 0.93 7.8
Maximum Cm 109.4 137.3 127 105.7 306.5
Minimum Cm 82.5 61.1 73.3 96.1 26.3
Bold values show the degree of center segregation
984
Fig. 4 Degree of macro segregation of Mg versus the withdrawal melt
flow rate in different slabs: A, B, and C are slabs that have different
degrees of macro segregation, as shown in Fig. 5 and Table 2. A is also
shown in Fig. 3, and B is shown in Figs. 6b and 7b as an example of
severe segregation. X is a slab that has mild segregation as shown in
Figs. 6a and 7a. Y is the slab that has most severe segregation in this
study, as shown in Table 2
Fig. 5 Degree of macro segregation of Fe, Si, Mg, Mn, and Ti versus
k in each of the three slabs A–C shown in Fig. 4
T. Yamada et al.
the horizontal direction in theory, relative to the area around
there. It has been reported that Zn concentration slightly
increases at only center in 7050 billets [10]. In this study, the
concentration of each eutectic element decreased and that of
Ti increased most in the center of the thickness. Therefore, at
least in this study, it is also hard to believe that only
shrinkage-induced flow cause the macro segregation.
Figure 8 shows the result of numerical simulation of
sump flow using the 1/4 thermo-hydraulic model in the same
condition as the slab shown in Fig. 3 and the measured
macro segregation of Mg. This numerical model is con-
structed by the conservation of mass, energy and momen-
tum. Here, Darcy’s law is considered, while
shrinkage-induced flow or free-floating crystals are not
taken into account. This has been described in reference [14]
in detail. Figure 8a shows the flow velocity in the sump and
(b) is the distribution of flow velocity just above the coherent
mushy zone corresponding to (a). Figure 8c shows the
measured macro segregation of Mg at the 1/4 cross-sectional
slice, same as in Fig. 3. As indicated by a red arrow in
Fig. 8a, the flow from a distributor is toward the bottom of
the sump, where fast melt flow occurs as shown in (b). This
area is surrounded by the dashed black line in (b) and (c),
which coincides with the center segregation area. In addi-
tion, it has been suggested that the fast flow stagnates around
the center segregation area, surrounded by the continuous
black line in (b) and (c). These regions correspond approx-
imately to the inverse segregation area, as shown in (c). In
summary, when observing areas near the center of the slab
along the thickness direction, the center segregation occurs
where the melt alloy flows faster just above the coherent
mushy zone, and the inverse segregation occurs where the
melt flow stagnates.
From these results, the mechanism of macro segregation
observed here, such as in commercial-sized 5xxx series
slabs, is simply explained as follows: (i) fast sump flow from
distributor penetrates into the mushy zone at the bottom of
the sump, (ii) enriched eutectic solute and diluted peritectic
solute are washed out from the mushy zone, forming the
center segregation, (iii) the penetrating flow stagnates just
around the center segregation area, and (iv) the washed
solute settles there, forming the inverse segregation. This
mechanism is similar to Fig. 1b. Even though there is no
certainty that other mechanisms do not cause macro segre-
gation, the sump penetration flow mentioned above is
thought to contribute most to the macro segregation, at least
in this study. In addition, it is suggested that patterns of
macro segregation can be qualitatively predicted from the
pattern of the sump flow. The reason why the microstructure
at the center of the slab becomes a granular crystal in case of
severe segregation, as shown in Fig. 6b, is considered to be
because the enriched or diluted solute in front of the
Full Size Measurement and Simple Prediction on … 985

Fig. 6 Microstructure at the center of the slab in a plane parallel to the withdrawal direction. a At mild segregation shown in Fig. 4 X and b at
severe segregation shown in Fig. 4 B

Fig. 7 EPMA images of Mg obtained at the center of slab in a plane parallel to the withdrawal direction. a At mild segregation shown in Fig. 4 X
and b at severe segregation shown in Fig. 4 B
986 T. Yamada et al.

solidification interface is swept out by the penetration flow

and dendrite growth is inhibited.
In order to explain the degree of macro segregation at the
center of the slab thickness, a simple model, the partially
swept solute model, is proposed as shown in Fig. 9. In this
model, formation of a tentative open cell is assumed at the
center of the slabs during solidification until the critical solid
fraction fs
is reached, at which dendrite arms begin to
entangle with each other enough, so that sump flow finds it
hard to penetrate into the mushy zone. Before fs
, the liquid
solute concentration is assumed to be equal to the bulk solute
concentration because sump flow can easily penetrate into
the mushy zone and sweep out the enriched eutectic solute
and diluted peritectic solute. When the solid fraction
becomes greater than fs
, these phenomena are assumed to be
prohibited perfectly and ordinary solidification process
occurs in a closed cell.
Using this model, the average solute concentration in the
cell can be calculated according to following:
 ¼ f
kC0 þ ð1  f
ÞC0
C ð2Þ
s s

where C  is average solute concentration in the cell, k is the

partition coefficient, and C0 is the solute concentration in the
sump, i.e., bulk liquid. Therefore, the degree of macro seg-
regation is expressed:

C
¼ 1  ð1  kÞfs
ð3Þ
Fig. 8 Result of numerical simulation of sump flow with 1/4 C0
thermo-hydraulic model in casting condition A and a comparison to
measured macro segregation. a Flow velocity in sump, b flow velocity It is thought that fs
depends on the mushy thickness and
just above coherent mushy zone, and c macro segregation of Mg at 1/4 speed of the penetrating sump flow; fs
seems to increase
cross-sectional slice, same as in Fig. 3
with an increase in the slab size and casting speed. Thus, the

Fig. 9 Schematic illustration of partially swept solute model, a hypothetical mechanism of the macro segregation
Full Size Measurement and Simple Prediction on … 987

Table 2 Critical solid fraction estimated to reproduce the measured macro segregation of Mg and calculated value of the macro segregation of Fe
and Ti, using Eq. (3) and fs

Chemical element k: partition coefficient Casting condition shown in Fig. 4
Y A B C
fs
: critical solid fraction 0.35 0.32 0.29 0.20
Calculated value (%) Mg 0.45 80.6 82.5 83.9 89.1
Fe 0.034 65.9 69.3 71.7 80.9
Ti 7.8 339.9 316.4 299.1 234.8
Measured value (%) Mg – 80.6 82.5 83.9 89.1
Fe – 56.2 61.1 68.3 74.7
Ti – 314.6 306.5 244.5 195.2

negative correlation between the degree of Mg segregation
and the withdrawal melt flow rate shown in Fig. 4 is con-
sistent with this model. In addition, the linear relationship
between k and the degree of segregation in each element
shown in Fig. 5 is also suggested by Eq. (3).
Using Eq. (3), the degree of macro segregation of each
element can be calculated if fs
is determined. Table 2
shows the fs
estimated to reproduce the measured macro
segregation of Mg and the calculated result of Fe and Ti
segregation in the four different slabs, Y and A–C shown
in Fig. 4. Each calculated value is close to the measured
value, regardless of whether it is a eutectic or peritectic
element.
From these results, it was found that the partially swept
solute model can represent the mechanism of macro segre-
gation in DC casting slab to some extent.
Conclusions
Two-dimensional distribution of alloy element concentration
in commercial 5xxx series slab slices were measured by
OES, and the important features of macro segregation were
obtained. Our proposed partially swept solute model can
explain the mechanism of macro segregation as follows.
Sump melt flow penetrating into the mushy zone will sweep
out the enriched eutectic solute and diluted peritectic solute.
This penetration flow is considered to continue until the
critical solid fraction is reached, which depends on the
thickness of the mushy zone and the sump flow rate. In case
of severe segregation, the microstructure at the center of the
slab becomes a granular crystal because the enriched or
diluted solute in front of solidification interface is swept out
by the penetration flow and dendrite growth is inhibited.
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123th JILM Annual Meeting, 11 Nov 2012, p. 67
15. A. Ohno: Kinzoku Gyoko Gaku (Chijin Shokan co. 1977),
pp. 87–96
 Ultrasonic Assisted Reduction of Hot-Tearing
During High-Speed DC Casting of 6000 Series
Aluminum Alloys

Sergey Komarov, Yasuo Ishiwata, and Yoshihiro Takeda

Abstract
This work presents results of preliminary investigations concerning the effect of ultrasonic
vibrations on the solidification structure and hot-tearing susceptibility of 6000 series
aluminum alloys in high-speed direct chill casting processes. A pilot DC caster was used to
produce billets of 82–97 mm in diameter. Ultrasonic vibrations were introduced directly
into the mold through a high-amplitude ceramic sonotrode, the tip of which was positioned
at different distances from the melt crystallization front. The cast billets were then
investigated for the microstructure and hot tearing susceptibility. It is shown that the
ultrasonic treatment leads to a significant reduction in hot tearing susceptibility, and at the
same time to a rise in mechanical properties of the alloys. The results suggest that at least
two ultrasonic effects contribute to these improvements. The first one is cavitation which
results in forming more refined and uniform microstructure of alloys. The second one is
acoustic streaming which is responsible for macro agitation of melt in the sump. This
causes the liquid-solid system to approach an equilibrium state that results in increasing the
fraction of eutectic phase solidified at the grain boundaries of a-Al phase.

Keywords

Ultrasonic vibration Hot-tearing susceptibility Microstructure Phase composition
Cavitation Acoustic streaming

Introduction investigations are summarized, for example, in [1, 2]. One of

High-intensity ultrasonic vibrations have been long recog-
nized as an attractive tool to improve the solidified structure
of light metals, particularly during DC casting of aluminum
alloys. A large body of literature in this area shows that
introduction of ultrasonic vibrations into molten aluminum
alloys results in significant refinement of their solidified
structure and improve their quality. The results of these
S. Komarov (&)
Graduate School of Environmental Studies, Tohoku University,
6-6-02 Aramaki Aza Aoba, Aoba-ku, Sendai, 980-8579, Japan
e-mail: komarov@material.tohoku.ac.jp
Y. Ishiwata
Y. Takeda
Casting Development Center, Nippon Light Metal, Co., Ltd,
161 Kambara, Shimizu-ku, 421-3297, Shizuoka, Japan
the mechanisms of structure refinement is ultrasonic cavi-
tation assisted dispersion of refiner particles in the melt just
before casting. In this case, ultrasonic vibrations can be
introduced in the melt flowing through a launder. An
example of such a process is ultrasonic DC casting of Al–Si
hypereutectic alloys where AlP particles are exploited as a
refiner of primary silicon [3, 4]. Another way to refine the
solidified structure is to introduce ultrasonic vibrations
directly into the melt in a mold. In this case, ultrasonic
cavitation can be helpful in dispersing the refiner particles or
breaking the growing dendrites in the sump just before or
during the metal solidification. However, care should be
taken to suppress acoustic streaming of melt in the sump,
and thus to prevent the melt overcooling inside the mold
which may result in coarsening the grains of primarily

© The Minerals, Metals & Materials Society 2017 989

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_119
990
solidified phases. A typical example where this problem
occurs is Al–Si hypereutectic alloys. As it has been shown in
our previous work [4], improvement in design of hot top
ultrasonic treatment unit can not only suppress the acoustic
streaming, but makes it controllable and useful for producing
billets with more refined and uniformly distributed grains of
primary silicon.
This study presents one more technique for ultrasonic
treatment where both the cavitation and acoustic streaming
are helpful in increasing the productivity of DC casting
process and improving the mechanical properties of the
produced billets. The goal of this study is to investigate the
effect of ultrasonic treatment on hot-tearing susceptibility of
6000 series aluminum alloys in high-speed direct chill
casting process. Ultrasonic vibrations were introduced
directly into the mold of a DC caster through a high-
amplitude ceramic sonotrode to produce 82–97 mm billets.
Then, the billets were investigated for the microstructure, hot
tears and mechanical properties.
Experimental and Instrumentation
A pilot DC caster was used to produce billets of 82–97 mm
in diameter and about 2 m in length using hot top molds.
The melt was supplied to the mold through a launder.
Casting temperature measured in the pouring launder was
kept constant at a level of 690 ± 10 °C. The casting speed
was varied in the range of 300–600 mm/min at an interval of
50 mm/min. The chemical compositions of alloys examined
in this study are presented in Table 1. A commercial
Al–5Ti–B master alloy was used as a grain refiner.
Ultrasonic vibrations were generated by an ultrasonic
sonoprocessor (DG2000, Telsonic, Swiss) with the maxi-
mum power of 2 kW, using a piezoceramic transducer
operated at a frequency of 20 ± 1 kHz. To introduce the
vibrations in the melt, a high-amplitude ceramic sonotrode
was used. The sonotrode was made of silicon nitride, had
length and diameter of 465 and 48 mm, respectively. The
vibration amplitude of sonotrode tip was measured by means
of a laser displacement sensor (Keyence, LK-G35) in air
conditions. Depending on the power supply, the vibration
amplitude was varied from 40 to 70 lm on peak-to-peak
base. Most of experiments in this study were performed at an
amplitude of 60 lm. As the sonoprocessor had a built-in
option to maintain the vibration amplitude at a constant level
Table 1 Chemical composition of alloys
Si Mg Cu Fe
Alloy 1 0.82 0.95 0.35 0.3
Alloy 2 0.7 0.85 0.35 0.3
Alloy 3 1.4 0.85 0.2 0.25
S. Komarov et al.
irrespective of the acoustic impedance of processing liquid,
it was considered that the amplitude in melt was the same as
that in air. Other details on the sonotrode characteristics can
be found in our earlier publications [4, 5].
The casting procedure was as follows. About 400 kg of
aluminum alloy was melted and superheated to a desired
temperature in an electric furnace. The grain refiner was
added to the melt in an amount of 2–4 kg/t, and then the melt
was agitated and degassed by argon with a rotary-injector
system. The tip of ceramic sonotrode was preheated up to the
melt temperature using a small electric furnace. After start-
ing the casting process, the sonotrode was moved to the hot
top area and immersed into the melt coaxially with the mold.
The sonotrode tip was fixed at a certain distance, LS from the
top edge of the mold. The ultrasonic power, transferred to
the melt, was ranged from approximately 500 to 1000 W
depending on the sonotrode vibration amplitude and
immersion depth. Ultrasonic vibrations were continuously
introduced into the melt sump during the casting process
until it is finished. After that, the sonotrode was moved back
to the preheating furnace.
As-obtained billets were investigated for the occurrence
of hot-tear cracks by using an ultrasonic non-destructive
testing equipment. Also, billets were cut at the appropriate
intervals to observe the crack morphology. Samples were cut
out of different areas of the billets to investigate the
microstructure of alloys. Besides, specimens for tensile test
were cut along the casting direction at the half-radius loca-
tion and machined according to JIS14A [6].
Experimental Results
Effect of Ultrasonic Treatment on Hot Tearing
Susceptibility
The results showed that the susceptibility to hot tearing
during the casting is significantly reduced when ultrasonic
vibrations are introduced into the melt sump. The results of
typical experiments are shown in Table 2.
As seen from the Table 2, the ultrasonic treatment allows
the casting speed to increase by 100–150 mm/min as com-
pared to conventional casting. The effect of ultrasonic treat-
ment depends on the alloy composition, billet diameter and
distance Ls (sonotrode immersion depth). The smaller the
diameter and the larger the immersion depth, the greater is the
Mn Cr Eutectic fraction (wt)
0.08 0.13 0.024
0.08 0.13 0.016
0.4 0 0.048
Ultrasonic Assisted Reduction of Hot-Tearing … 991

Table 2 Maximum casting speed for various alloys at different conditions

Alloy Billet diam (mm) Maximum casting speed (mm/min) US power (W) Distance LS (mm)
Conventional US casting
Alloy 1 82 350 450 520–550 40–20
82 350 500 760–880 0 to −20
97 300 400 750–900 0 to −20
Alloy 2 82 350 450 620 20
82 350 500 760 0
Alloy 3 82 400 550 640–970 0 to −20
97 350 470 620–950 0 to −20

increase in casting speed with ultrasonic treatment. Negative
values of Ls mean that the sonotrode tip was fixed below the
mold top edge. Exceeding the maximum casting speed
caused hot cracking which started from the billet center. In
most cases, the cracks had a three branch star shape.
Billet Microstructure
Investigation of microstructure at the billet center, surface
and half-radius distance revealed that a-Al grains tend to be
more rounded and finer grained after the ultrasonic treat-
ment. Typical images of the grain microstructure are shown
in Fig. 1. It is seen that some parts of grains at the billet
center (d) and half-radius (e) have dendritic branches. On the
other hand, in the billet obtained in ultrasonic assisted
casting, no dendritic branches are observed. Another
important finding is that the ultrasonic vibrations improve
the uniformity of grain microstructure. Table 3 presents
typical average diameter of a-Al grains, DAl and the corre-
sponding standard deviation, rD. This data was obtained by
image processing of several images taken at the center part
of a billet of alloy 3. It is seen that both the values of DAl and
rD significantly decreased after the ultrasonic treatment.
Also there was a tendency for DAl and rD to vary with the
sonotrode tip position, LS. However, this variation is sta-
tistically insignificant in the present experimental conditions.
Thus, the above improvement in the microstructure of aAl
grains can be one of the reasons for reduction of the hot
tearing susceptibility obtained in the present study.

Fig. 1 Microstructure of billet (Alloy 3) at the center (a, d), half-radius (b, e) and surface (c, f) obtained in ultrasonic assisted DC casting
(a–c) and conventional (d–f) casting
992
Table 3 Average diameter of a-Al grains, DAl and its standard deviation, rD for the center part of billet of alloy 3
Conventional casting
Average diameter, DAl (lm) 90.1
Standard deviation, rD (lm) 30.4
Effect of Ultrasonic Treatment on Phase
Composition
As readily seen from Fig. 1, the billet microstructure is
composed of aAl grains and a more low-melting films
formed on the grain boundaries. The films are viewed in
Fig. 1 as black areas. Prediction of the phase composition
with JMatPro software revealed that these films can contain
such phases as eutectic, Mg2Si, a- and b-AlFeSi compounds
and some other phases, depending on the alloy chemical
composition. However, for the sake of simplicity, hereinafter
these phases will be referred as to eutectic phase. The
eutectic fraction, thus determined, is presented in Table 1.
A more careful analysis of the microstructural data indi-
cated that the fraction of eutectic phase after ultrasonic
treatment becomes larger as compared to conventional
casting. Moreover, the fraction was found to vary with the
sonotrode immersion depth. Figure 2 shows the fraction of
surface area, ce occupied by eutectic phase at the billet center
as a function of the casting speed for a number of conven-
tional and ultrasonic casting process. Open dots correspond
to the data without hot tears, while the solid dots denote
those with hot tears. The data were obtained by image
processing of ten images for each experimental conditions.
The data reveal that when alloy 1 was cast at a speed of
400 mm/min with ultrasonic irradiation, switching the
Fig. 2 Fraction of surface area corresponding to eutectic phase as a
function of casting speed for different alloys
S. Komarov et al.
Ultrasonic assisted casting
LS = 0 mm LS = −20 mm
64.1 54.3
14.0 11.3
ultrasonic field off resulted in hot tearing and decreasing the
fraction of eutectic phase. Another example is ultrasonic
assisted casting of alloy 2. An increase of immersion depth
of sonotrode by 20 mm caused increasing the eutectic phase
fraction and made it possible to produce a hot-tear-free billet.
In the case of alloy 3, an increase of the sonotrode immer-
sion depth led also to increasing the value of ce. However,
too high of a casting speed caused hot tearing.
Tensile Test Results
Results of tensile test indicated two effects of ultrasonic
treatment on the mechanical properties of alloys. The first
one is an increase in tensile and yield strength, and in
elongation. The second one is a significant reduction in
scattering of all these mechanical properties. Typical data are
presented in Table 4 for alloy 3. The data were obtained by
performing several tensile tests of HO/T6 treated specimens
followed by statistical treatment of measurement results.
Similar improvements in mechanical properties have been
obtained for the other alloys. For example, the average
values of tensile strength, yield strength and elongation of
specimens cut out from the half-radius parts of as-casted
billets of alloy 2 are (conventional casting/ultrasonic casting)
370/372, 322/332 MPa and 12.3/15.5%.
Discussion
The above results can be explained as follows. It is well
known that ultrasonic irradiation in liquids causes cavitation
and acoustic streaming. As it has been shown in our previous
work [5], the threshold value of vibration amplitude neces-
sary for a stable cavitation to be generated in liquid alu-
minum is approximately 10 lm (p–p). Since the sonotrode
vibration amplitude in the present experiments is much
higher than the threshold one, it is evident that a
high-intensity cavitation field is formed in the melt
sump. Cavitation produces shock waves and microjets in the
sump that concentrate energy onto interfaces between the
melt and growing crystals in the mushy zone. This may
results in the aAl grain refinement and vigorous agitation of
melt in the mushy zone, causing the liquid-solid system to
Ultrasonic Assisted Reduction of Hot-Tearing … 993

Table 4 Mechanical properties of alloy 3 produced by conventional and ultrasonic casting

Experimental conditions Tensile strength Yield strength (MPa) Elongation (%) Casting speed (mm/min)
(MPa)
Average St.dev Average St.dev Aver St.dev
Conventional 387.6 6.8 320.4 3.8 16.2 5.1 400
UST LS = 0 mm 392.7 0.6 323.3 1.6 18.4 0.9 550
LS = −20 mm 391.9 0.7 322.6 1.3 18.2 1.3 550
St.dev standard deviation

approach an equilibrium state. Acoustic streaming is defined Conclusions

as a steady fluid motion caused by the attenuation of ultra-
sonic waves in fluids. In the present experimental conditions, The present investigation shows the potential of using ul-
the velocity of acoustic streaming in the sump can reach as trasonic vibrations to reduce ho tearing susceptibility during
high as 0.5 m/s. This assumption is based on the results of DC casting of 6000 series aluminum alloys. Ultrasonic
our earlier study on the acoustic streaming in molten alu- vibrations were introduced directly into the mold of a DC
minum [7]. Such a high velocity flow should efficiently caster through a high-amplitude ceramic sonotrode to pro-
agitate the melt in the sump at macro level that can cause the duce 82–97 mm billets. Then, the billets were investigated
tip rounding effect of aAl grains in a similar way as in for the microstructure, hot tears and mechanical properties.
semi-solid processing. Thus, the agitation and homogeniza- Based on the investigation results, the following conclusions
tion of the melt due to cavitation and acoustic streaming may were made.
lead to a faster approach to the equilibrium state may help
and, as a result, the amount of eutectic phase and film (1) Ultrasonic treatment leads to a significant reduction in
thickness between Al grains is increased. This phenomenon hot tearing susceptibility that allows to increase the
is assumed to be another reason for the reduction of hot casting speed from 300 to 400 mm/min typical for
tearing susceptibility in the present experiments. conventional casting to 450–550 mm/min for ultrasonic
Schematically, the variation in hot tearing susceptibility casting. Generally, the casting speed was dependent on
with the amount of eutectic phase can be represented by the alloy composition.
Fig. 3. When the amount of eutectic phase is relatively (2) Billets produced by the ultrasonic casting have higher
small, microvoids and micropores can be formed between tensile and yield strength, and elongation as compared
a-Al grains as shown in Fig. 3a. Such defects can originate with conventionally produced billets. In addition, scat-
cracks during solidification at high levels of thermal stress. tering in the mechanical properties was significantly
On the other hand, the probability of crack initiation is much decreased after the ultrasonic treatment.
less when the intergranular space is filled with the eutectic (3) These improvements are explained by the following
phase, as shown in Fig. 3b. Such a mechanism of hot tearing three effects induced by application of ultrasonic vibra-
is well known from relevant literature [8]. tions in the melt: refinement of a-Al grains, uniformity
of microstructure and approaching the liquid-solid sys-
tem in the melt sump to equilibrium state. It is suggested
that acoustic cavitation and acoustic streaming are
responsible for the above effects.

References

1. G.I. Eskin, D.G. Eskin, Ultrasonic Treatment of Light Alloy Melts

(CRC Press, 2014), p. 346
2. O.V. Abramov, High-Intensity Ultrasonics: Theory and Industrial
Applications (Amsterdam, Gordon and Breach Science Publishers,
1998), p. 692
3. G. Zhong, S. Wu, H. Jiang, P. An, Effects of ultrasonic vibration on
the iron-containing intermetallic compounds of high silicon alu-
Fig. 3 A representation of hot tearing mechanism minum alloy with 2% Fe. J. Alloy. Compd. 492, 482–487 (2010)
994
4. S. Komarov, Y. Ishiwata, I. Mikhailov, Industrial application of
ultrasonic vibrations to improve the structure of Al–Si hypereutectic
alloys: potential and limitations. Metall. Mater. Trans. A 46, 2876–
2883 (2015)
5. S. Komarov, K. Oda, Y. Ishiwata, N. Dezhkunov, Characterization
of acoustic cavitation in water and molten aluminium alloy,
Ultrason. Sonochem. 20, 754–761 (2013)
S. Komarov et al.
6. JIS handbook: Non-ferrous metals & metallurgy, Tokyo, Japanese
Standards Association, 1998
7. D.G. Eskin, Physical Metallurgy of Direct Chill Casting of
Aluminum Alloys (CRC Press, 2008), p. 328
8. Y. Ishiwata, S. Komarov, Y. Takeda, Investigation of acoustic
streaming in aluminum melts exposed to high-intensity ultrasonic
irradiation. Paper presented at the 13th International Conference on
Aluminium Alloys, Pittsburgh, USA, 3–7 June 2012, pp. 183–188
 Part XXIII
Cast Shop Technology:
Grain Refining and Solidification
 Effect of Ultrasonic Processing on a Direct Chill
Cast AA6082 Aluminium Alloy

G. Salloum-Abou-Jaoude, D.G. Eskin, C. Barbatti, P. Jarry, M. Jarrett,

and Z. Fan

Abstract
For many years now, ultrasonic melt treatment (UST) has proven itself to promote grain
refinement in aluminium alloys. The current work presents cavitation-aided grain
refinement obtained on commercial AA6082 DC-cast billets. Grain refinement was
achieved while applying UST in the crucible away from the sump, prior to casting. Since in
high strength alloys, Zr and Ti are commonly present as alloying elements for
anti-recrystallization and corrosion resistance properties, their as well as UST parameters
influence on the microstructure are studied and presented. Primary Al3(Zr1–x–y, Tix, Siy)
intermetallics were found in the centre of the a-Al grains. This suggests that UST may have
forced the nucleation and refinement of primary intermetallics influencing the subsequent
solidification process when Al3(Zr1–x–y, Tix, Siy) act as nucleation sites.

Keywords
DC casting Ultrasonic processing AA6082 Grain refiner CET Grain size
Microstructure Nuclei

Introduction giving better properties to the cast metal, it facilitates the

Direct chill casting of aluminium alloys, commonly known as
DC casting, is a technology that provides sound cylindrical
billets or flat ingots required for extrusion, forging, or rolling
in the automotive and aerospace aluminium industry [1].
Control of grain size in DC-cast billets and ingots is
essential to prevent hot tearing linked to the inadequate com-
pensation of the solidification shrinkage and mechanical
properties of the semi-solid material [2], shrinkage porosity
resulting from insufficient feeding of the gaps between the solid
dendrites [3], cold cracking is related to low ductility of the
as-cast material [4], and macrosegregation in the billet [5, 6].
As a result, fine and uniform, equiaxed grain structure is
highly beneficial for industrial casting processes. Other than
G. Salloum-Abou-Jaoude (&)
D.G. Eskin
Z. Fan
BCAST, Brunel University, Uxbridge, Middlesex UB8 3PH, UK
e-mail: georges.salloum-abou-jaoude@brunel.ac.uk
C. Barbatti
P. Jarry
M. Jarrett
Constellium, Parc Economique Centr’alp, CS10027, 38341
Voreppe Cedex, France
subsequent mechanical working [7, 8]. A full columnar to
equiaxed transition (CET) [9, 10] is required to achieve a
uniform equiaxed structure. Many methods are available to
trigger CET and reach a fully equiaxed microstructure.
A common industrial practice is to add grain refiner rods
containing potent nucleant particles like Al–Ti–B and Al–
Ti–C to promote the formation of a fine, uniform and
equiaxed grain structure [11]. Other methods to refine the
microstructure involve using a pulse magnetic field
(PMF) [12], pulse magneto-oscillation (PMO) [13, 14],
electric current pulse (ECP) [15–17], high shearing [18], and
ultrasonic melt treatment (UST) [19–22].
The challenge in applying an external field or mechan-
ical shearing during solidification in DC casting is purely
technical. Moving away from the solidification domain
(sump) during DC casting is advantageous from an indus-
trial point of view as it increases the productivity of treating
larger volumes and reduces the risk of technical failures. It
has been shown that high shearing can be applied before

© The Minerals, Metals & Materials Society 2017 997

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_120
998
casting to refine Fe bearing intermetallics that can serve as
nuclei for a-Al grains [23]. Similarly, UST has been also
applied prior to casting in permanent moulds on
Zr-containing aluminium alloys to force the nucleation of
Al3Zr intermetallics and promote CET of a-Al grains
reaching a very fine grain structure [20]. In this work we
present results obtained on the refinement of a commercial
AA6082 alloy obtained by applying UST prior to casting in
a DC-casting simulator.
Experimental Procedure
DC-Casting Simulator
In order to perform relatively easy and fast DC-casting
experiments, a DC-casting simulator was used. The
DC-simulator consists of a tapered steel sleeve (64 mm
bottom diameter and 75 mm top diameter) resting on a steel
base, surrounded by resistance heaters that will preheat it
20 °C above the pouring temperature (Tp) before each
experiment (Fig. 1a). The sleeve is well isolated to ensure
that at the moment of pouring the solidification will start at
the steel base at the bottom of the sleeve. When the steel
sleeve is full of liquid aluminium alloy, the water nozzles are
switched on and a constant pulling rate of 150 mm/min is
applied moving the sleeve downward through the quench
zone where the water nozzles come in direct contact with the
steel mould solidifying the aluminium indirectly from the
sides simulating the solidification during a standard DC
casting (Fig. 1c). The final cylindrical shaped billet can be
seen in Fig. 1c.
Melt Preparation and Treatment
To study the effect of ultrasonic processing on the
microstructural refinement of an AA6082 aluminium alloy,
approximately 100 kg of AA6082 were prepared by melting
commercial purity aluminium (99.98 wt%) and adding to it
precise amounts of Al–20 wt% Si, Al–10 wt% Fe, Al–20 wt
% Mn, 100 wt% Mg, 100 wt% Zn, Al–50 wt% Cu, Al–10
wt% Ti and Al–10 wt% Zr master alloys.
The AA6082 alloy cast was analysed with a
FOUNDRY-MASTER Pro optical emission spectrometer
(OES) and the composition achieved was in the range of a
commercial AA6082 as shown in Table 1.
From the 100 kg batch of AA6082, small 4 kg charges
were put in graphite–clay crucibles and remolten in an
electrical furnace. Variants were cast by adding small
amounts of Al–10 wt% Ti and Al–10 wt% Zr master alloys to
the re-molten AA6082 to increase the amount of Ti and/or Zr.
G. Salloum-Abou-Jaoude et al.
In some experiments, ultrasonic treatment (UST) was
applied in the crucible prior to casting to study the effect of
ultrasound cavitation on the solidified microstructure. UST
was applied in a temperature range well above the a-Al
nucleation temperature so that ultrasonic cavitation would
not fragment the a-Al dendrites [19]. Experiments were
performed with a magnetostrictive transducer at a resonance
frequency of 17.5 kHz, amplitude 25 µm and the input
power at the generator 3.5–4.0 kW (ultrasonic equipment is
made by Reltec, Yekaterinburg, Russia). A horn was made
of niobium.
Moreover, Al-5Ti-1B commercial grain refiner was also
added for some experiments. The melt was poured in the
DC-casting simulator at a pouring temperature (Tp) of 700 °
C. Table 2 shows the list of experiments performed in this
study.
Sample Preparation and Grain Size Measurement
After casting, 2 cm thick disk slices were cut at mid-length
of the billets for microstructure analysis (marked as “b” in
the photo in Fig. 1c). Samples were cut from the disk slices
in the longitudinal direction. Subsequently, they were
ground and polished to a mirror finish using silicon carbide
grinding papers and diamond suspension solutions before
the final OPS polishing. To reveal the grains, the samples
were electrolytically anodized at 20 VDC in a solution of
H2O + 3 pct HBF4. A Neophot-31 optical microscope (made
by Carl Zeiss, Jena, Germany) was used to take photos of the
grain structure and a random linear intercept technique was
applied to measure the grain size. Statistical analysis of the
results was performed.
Results and Discussion
Grain Refinement Induced by UST Prior
to Casting
Figure 2 displays a sequence of as-cast polarised micro-
graphs taken at half radius of the DC-simulator billets for all
experiments S1–S5 (Table 2). One can see that the mi-
crostructure of the reference experiment S1 without grain
refiner (Fig. 2a) consisted of big columnar grains >1000 µm
(Fig. 2f). The lack of nuclei in this experiment failed to
promote a Columnar to Equiaxed transition (CET) [24, 25].
On the other hand, when 0.1 wt% Al-5Ti-1B grain refiner
was added to the AA6082 melt before casting (S2), a
completely equiaxed microstructure was obtained (Fig. 2b)
and the grain size was reduced significantly down to 250 µm
Effect of Ultrasonic Processing on a Direct … 999

Fig. 1 Sketch of the DC-casting simulator experimental setup as a sleeve at t = t0 before c starting the constant pulling of the sleeve down
function of the experimentation time t. a The UST processing is applied to the quench zone shaping the final billet (left photo in c)
in the crucible prior to casting, b then poured entirely into the steel

Table 1 Aluminium association 6082 composition range

Element Si Fe Cu Mn Mg Cr Zr Ti Al
Composition range (wt%) 0.7–1.3 0.0–0.5 0.0–0.1 0.4–1.0 0.6–1.2 0.0–0.25 0.0–0.05 0.0–0.1 Balance

(Fig. 2f). It is well known that an Al3Ti two-dimensional In experiment S3, no commercial grain refiner was added
compound can adsorb on the TiB2 particle making it a but the concentrations of Zr and Ti were increased (see
perfect seed for a-Al nucleation [26]. Table 2). Figure 2c shows that the microstructure obtained is
1000 G. Salloum-Abou-Jaoude et al.

Table 2 List of DC-casting simulator experiments

Exp. name Base alloy Zr (wt%) Ti (wt%) Al-5Ti-1B (wt%) UST UST DT (°C) TP (°C)
S1 6082 0.05 0.04 – – – 700
S2 6082 0.05 0.04 0.1 – – 700
S3 6082 0.2 0.10 – – – 700
S4 6082 0.2 0.04 – Yes 750–705 700
S5 6082 0.2 0.1 – Yes 750–705 700

Fig. 2 Micrographs showing the as-cast polarised microstructures revealing the grains obtained in the experiments a S1, b S2, c S3, d S4 and
e S5. The grain size is plotted in f the error bar is the standard deviation obtained during the measurements

fully equiaxed and comparable in size to that of experiment S2
(Fig. 2f). As a matter of fact, when the Zr content is increased
to 0.2 wt% in an AA6082 alloy, thermodynamic calculations
using PandaT software show that an Al3Zr intermetallic phase
nucleates at a higher temperature (TL(Al3Zr) = 710 °C) than
that expected for the a-Al phase (TL(a-Al) = 650 °C),
thus forming primary particles. This Al3Zr phase has been
reported to be a nuclei for the a-Al phase especially when Ti is
present [20], contributing to the grain refinement seen in
experiment S3. In addition, the increase of Ti content to 0.1 wt
% in S3 increases significantly (by 20 points) the value of the
growth restriction factor QTi = mL(k − 1)CTi, where
mL = 34 °C/wt% is the liquidus slope, k = 9.71 the partition
coefficient of a binary Al–Ti, and CTi = 0.1 wt% is the com-
position of the Ti in experiment S3. It is well known that a
large growth restriction factor will significantly reduce the
grain size of a solidified material [11].
Figure 2e shows the microstructure of the AA6082
material with 0.2 wt% Zr and 0.1 wt% Ti (S5), but after UST
applied in the crucible in the temperature range of 750–705 °
C before pouring in the DC-caster simulator. One can see
that a fully equiaxed microstructure is achieved and a dra-
matic reduction in grain size down to * 100 µm is obtained
(Fig. 2f). Similar to experiment S3 the high amount of Zr in
the cast allows Al3Zr to nucleate before the a-Al, therefore
facilitating the nucleation of the latter and promoting CET.
Also the high Ti content increases the growth restriction
factor limiting the growth of the grains, which results in a
small grain size. But clearly there is a significant reduction in
the grain size between S3 and S5. This can only be achieved
due to the UST applied in the temperature range where the
Al3Zr intermetallics nucleate, resulting the multiplication of
the Al3Zr intermetallics and thus creating abundant potent
nucleation sites for the a-Al phase to grow on.
Effect of Ultrasonic Processing on a Direct … 1001

Fig. 3 Micrographs showing the as-cast polarised micrographs (mag- light micrographs at a magnification of 100 showing the same
nification 20) revealing the intermetallics detected at the centre of the intermetallics detected in a, b and c respectively
grains in the experiments a S3, b S4, c S5. d, e and f are bright field

(b)
(a)

(c) Al (d) Zr (e) Ti (f) Si

Fig. 4 Scanning electron microscopy images of intermetallics detected magnification of 10 K, the blue rectangle indicates the region where
at the centre of the a-Al grain in the experiment S4. The intermetallics the average EDS measurement was performed (Table 3). EDS mapping
appeared in bright white in the backscattered image at a magnification reveals the c Al, d Zr, e Ti and f Si distributions in the intermetallics
of 600 (a). b Shows a secondary electron SEM image at a
1002
Table 3 EDS analysis of an Element Weight (%)
intermetallic at the centre of the
grain in experiment S4 Al 53.98
Si 4 5.36
Zr 36.63
Ti 5.4
By contrast, in experiment S4 with a lower concentration
of Ti (Fig. 2d), the equiaxed grains have a larger size
of *150 µm compared to S5 (see Fig. 2f). This highlights
the effect of Ti as a growth restrictor on the a-Al grains.
Figure 3 shows several micrographs at a magnification
of 20 polarized imaging (Fig. 3a–c) and 100 bright field
imaging (Fig. 3d–f) revealing the intermetallics detected at
the centre of the a-Al grains. These intermetallics were
numerous in the microstructure and were observed in all
three experiments S3 (Fig. 3a, d), S4 (Fig. 3b, e), and S5
(Fig. 3c, f) where the alloys contained 0.2 wt% Zr.
Further SEM investigation of the sample S4 showed how
the intermetallics were abundant and easy to find in the
microstructure. In backscattered (BSE) mode, they appear as
bright intermetallics in the image (Fig. 4a), with the bright
colour indicating that they contain a higher concentration of
heavy elements compared to aluminium.
Figure 4 shows an example of EDS mapping performed
on multiple intermetallics. A mean EDS measurement was
done in the blue rectangle indicated in Fig. 4b and reveals
the intermetallic composition (Table 3), thus the estimated
stoichiometry is about Al3 (Zr0,6, Ti0.2, Si0.2).
One can see from Fig. 4d, e that the Zr and Ti are
homogeneously distributed in the intermetallics. This comes
in line with the observation done by Atamanenko et al. [20],
were he found that the Zr and Ti are homogeneously dis-
tributed in the small intermetallics detected in an aluminium
alloy with 0.6 wt% Zr–0.06 wt% Ti alloy. They also found
that the Ti content was between 3.6 and 6 at. pct. In addition,
Fig. 4f shows that Si is present in the intermetallics and is
homogeneously distributed in them with an atomic compo-
sition comparable to the Ti one.
Conclusion
This work has proved that significant grain refinement of
DC-cast 6082 commercial alloy can be achieved by applying
ultrasonic melt treatment prior to casting on a Zr containing
6082 alloy without any commercial grain refiner addition.
The Zr and Ti content required to achieve such a grain
refinement are low enough to lie in the range of a com-
mercial 6082. The temperature range where the UST is
applied is crucial for the grain refinement because it need to
be in the interval where the Al3Zr intermetallics nucleate.
G. Salloum-Abou-Jaoude et al.
Atomic (%) Error (%)
75.29 3.44
7.55
15.11 4.2
4.24 3.86
This technique is relatively easy to apply on a production
line because there is no interference with the DC-caster, the
UST is applied far from the sump prior to solidification. The
next step is to perform additional SEM analyses on experi-
ments S3 and S5 to detect any differences in the inter-
metallics detected at the centre of the grains in terms of
stoichiometry or element distribution homogeneity. In
addition, work is being carried out to validate the experi-
ments on an 80 mm diameter conventional DC-caster.
Acknowledgements The authors gratefully acknowledge all their
colleagues at Constellium (especially E. Beslin) and BCAST (espe-
cially A. Fitzner, J. Gadd), for their support and technical help. The
authors wish to thank the Engineering and Physical Sciences Research
Council (EPSRC) for funding the project.
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 Shear Induced Grain Refinement
of a Continuously Cast Ingot

Samuel R. Wagstaff and Antoine Allanore

Abstract
In previous investigation [1] has demonstrated the wide variation of grain size found
through the cross-section of a Direct-Chill (DC) cast ingot due to the location-dependent
solidification rate inherent to the process. Recently we have demonstrated [2] that the use of
a turbulent jet as a metal entrance method has the potential to significantly reduce grain size
and its variability upon location. We herein report a series of experiments investigating the
influence of jet power on the grain size and distribution in Al4.5Cu DC cast ingots. Our
findings indicate that significantly increasing the jet power does not appreciably decrease
the grain size. Instead, a threshold jet power required for grain refinement is anticipated,
beyond which only marginal improvements are anticipated.

Keywords
DC casting Grain refinement Turbulent jet Stirring

Introduction However, non-dendritic grains have been reported in DC

A fine and uniform grain structure is desired for optimum
formability and homogenous mechanical properties in
wrought aluminum products. Grain structure (size, distribu-
tion, and morphology) is an important parameter influencing
defects, e.g. hot cracking. In Direct-Chill (DC) castings, the
grain structure depends on the alloy composition, the intro-
duction of heterogeneous nucleation sites (grain refiner),
growth conditions, and cooling rate [3–5]. Due to the shape
of the solidifying interface (sump) formed during DC casting
(see Ref. [6] for examples), the solidification rate of an
individual grain is extremely position dependent. This vari-
ation in solidification rates can lead to large variances in
grain size and structure through large rolling slab ingots [1].
In general, grain morphology in commercial,
grain-refined castings is equiaxed and dendritic [7–15].
S.R. Wagstaff (&)
A. Allanore
Massachusetts Institute of Technology, 77 Massachusetts Ave,
Cambridge, MA 02139, UK
e-mail: swagstaff@gmail.com
cast aluminum alloys upon grain-refining [7, 9, 16, 17]. Yu
and Granger [7] reported that within the central portion of a
grain refined AA2024 alloy, isothermal dendrites (‘floating
grains’) appear to be non-dendritic compared to the rest of
the structure, which is dendritic.
In an early attempt to modify macrosegregation patterns,
Wagstaff and Allanore utilized a turbulent jet generated with
a special mixing nozzle to mobilize grains which had sedi-
mented to the bottom of the sump [2]. The turbulent stirring
caused non-dendritic grains to be found, and an increase in
grain refinement and homogeneity of the solifidied structure
was observed. Similar to these results, in electromagnetic
casting (EMC), unlike conventional DC casting, the grain
size is more homogeneously distributed throughout the cross
section of the ingot, which is a result of forced convection,
lower thermal gradients, and more intensive transport of the
solid phase within the slurry zone [18].
The formation of non-dendritic structure is known to be
beneficial for the structural homogeneity of DC cast prod-
ucts, improving their mechanical properties in the vicinity of
the solidus, diminishing macrosegregation, and decreasing
cracking susceptibility [19]. On the other hand, there are

© The Minerals, Metals & Materials Society 2017 1005

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_121
1006
reports that the formation of very fine globular grains can
increase the hot tearing susceptibility due to the limited
permeability of the mushy zone [20, 21]. The important
feature of the non-dendritic grains that are formed during
solidification is the unique dependence of the non-dendritic
grain size on the cooling rate. The size of a non-dendritic
grain at a certain cooling rate is the same as the dendrite arm
spacing of a dendritic grain formed at the same cooling rate
[19].
These observations are for the most part, non-unique to
DC casting. In 1971, Spencer was investigating the viscosity
of partially solidified melts using a couette viscometer [22].
Unintentionally, he had sheared and broken up the dendritic
structure and found that the partially solidified material
exhibited thixotropic behavior. He and his advisor M.C.
Flemings, went on to develop rheo-casting, an extrusion and
die casting technique which leverages this property and
unique microstructure. For the past 45 years, this has spurred
a research interest in solidification under forced convection.
In an attempt to put the present work into perspective, a
highlight of this research is presented.
Solidification Behavior Under Forced
Convection
Nearly all alloys of commercial importance solidify den-
dritically, with either a columnar or an equiaxed dendritic
structure [23]. During dendritic solidification of castings and
ingots, a number of processes take place simultaneously
within the semi-solid region. These include crystallization,
solute redistribution, ripening, interdendritic fluid flow, and
solid movement. The dendritic structure is greatly affected
by the interdendritic flow and solid movement, which, in
conventional solidification, is caused by internal factors such
as density difference and heterogeneous distribution of
temperature. The effects of those processes on the solidified
microstructures have been reviewed previously by Flemings
[24], and more recently by Boettinger et al. [25].
In studying conventional solidification, transparent
organic alloys have been intensively used to investigate the
solidification behavior at microstructural level by direct
observation. However, this may not be possible for solidi-
fication under forced convection, even using organic ana-
logue, due to the blurred image caused by intensive stirring
[26]. For this reason, current understanding of the solidifi-
cation behavior under forced convention is obtained indi-
rectly by examination of the final solidified microstructures.
It has been conclusively established from experimental
observations that solidification under melt stirring produces
non-dendritic structures, as discussed in previous reviews
[23, 27]. The early work by Spencer et al. [28] and Joly and
S.R. Wagstaff and A. Allanore
Mehrabian [29] on the Sn–Pb system using rotational
rheometers confirmed that the solid phase in the semisolid
state has either a degenerated dendritic structure or rosette
morphology. With prolonged stirring time, such particles
change to a more or less spherical morphology containing
entrapped liquid by a ripening process. Increasing the
shear rate accelerates this morphological transition and
reduces the amount of entrapped liquid inside the solid
particles [29]. The rosette morphology of solid particles has
also been observed in many stirred alloys by other investi-
gators [30–33] using rod and impeller types of stirrer.
Later work on solidification under magnetohydrodynamic
(MHD) stirring confirmed the formation of a fine and
degenerated dendritic structure (see summary in Refs.
[24, 25]).
Grain Density
It has been observed that under forced convection, larger
grain densities are present than under conventional solidifi-
cation techniques [24]. The grain refinement is attributed to
the fact that the convection associated with the mold filling
remains strong as solidification commences. Bower and
Flemings performed experiments which showed that if
convection is present at the onset of solidification, a structure
with many smaller grains will form. Superheated liquid
Al4.5Cu alloy was drawn into a thin-plate copper mold [34].
The dendritic structure on the surface of the cast plates was
visible to the naked eye. If metal was drawn into the mold
with a large amount of superheat, large dendrites were
observed on the surface of the cast plates. If the metal was
drawn with significantly less superheat, a far greater number
of smaller dendrites were observed. Bower and Flemings
believed that during an experiment, the tip of the metal in the
channel would freeze first, stopping flow. For metal cast
with a higher superheat, the metal behind the frozen flow tip
would be quiescent when it began to solidify. Since con-
vection was not present during solidification, the final grain
size was large. For the case of metal cast with significantly
less superheat, it was likely that the metal behind the flow tip
already began to solidify before the flow tip froze, which
resulted in a finer grain size throughout the casting.
The “big bang” theory originally proposed by Jackson
et al. is one way to explain the effect of convection on grain
refinement [35]. These researchers used carbon tetrabromide
with salol, a transparent analog casting system, and video
equipment to show that when convection was present during
solidification, many solid particles would suddenly be
emitted from the mushy zone and would move into the bulk
melt. The “big bang” theory explained this observation by
postulating that convection caused thermal fluctuations
Shear Induced Grain Refinement of a Continuously Cast Ingot
which in turn lead to fluctuations in growth rate and
re-melting of dendrite arms. The detached arms were then
thought to be transported by convective flows or buoyancy
into the bulk melt, resulting in a structure with many smaller
grains. To explain the observed grain refinement by melt
stirring, Vogel et al. [30] have proposed a dendrite arm
fragmentation mechanism to account for grain multiplica-
tion. They suggested that dendrite arms bend plastically
under the shear force created by melt stirring. Plastic
bending introduces large misorientations into the dendrite
arms in the form of ‘geometrically necessary dislocations’.
At high temperature, such dislocations rearrange themselves
to form high angle grain boundaries through recrystallisa-
tion. Any grain boundary with an energy greater than twice
the solid/liquid interfacial energy is then wetted by liquid
metal, resulting in the detachment of dendrite arms.
Following the early suggestion by Flemings [24], Hella-
well [36] suggested that secondary dendrite arms can detach
at their roots because of re-melting due to solute enrichment
and thermosolutal convection. To explain the crystal multi-
plication in semisolid processing, the author suggested that
temperature fluctuations in the MHD rheocasting process
play a significant role in the structural evolution. A contin-
uous nucleation might take place in the absence of a distinct
recalescence where each volume element of the liquid passes
periodically through different temperature zones.
The dendrite fragmentation mechanism attempts to
rationalize the final microstructural features observed in
the solid, but the important remaining question is how likely
is it that shearing can exert such a high bending moment to
small dendrite arms to fracture them. According to the
theoretical work by Vogel [37], the microscale of turbu-
lence has to be of the order of particle size for the viscous
forces to be active on bending the dendrite arms, and that is
possible only at a very high shear rate. Moreover, frag-
mented dendrite arms are expected to grow dendritically in
the melt, at least during the initial period of growth, until
impingement of diffusion fields occur. This is not compatible
with experimental observations, where primary particles can
be seen to be few in number but exhibit a degenerated
dendritic or spherical microstructure [38].
In light of some of the difficulties with existing dendrite
fragmentation theory, the experimentally observed grain
refinement under high degrees of convective turbulence has
been explained by a copious nucleation mechanism [39, 40].
Under intensive mixing action, both temperature and com-
position fields inside the liquid alloy are extremely uniform.
During continuous cooling under forced convection,
heterogeneous nucleation takes place at the same time
throughout the whole liquid phase. Compared with con-
ventional solidification, the actual nucleation rate may not be
1007
increased, but all the nuclei formed will survive due to the
uniform temperature field, resulting in an increased effective
nucleation rate. In addition, the intensive mixing action will
disperse the clusters of potential nucleation agents, giving
rise to an increased number of potential nucleation sites.
Ironically, this theory is strikingly similar to the “big bang”
nucleation theory initially proposed by Jackson [35] and
discussed earlier.
The purpose of this research is to investigate the appli-
cation of a turbulent mixing jet as a method to homogenize
and refine the grain structures found within DC cast alu-
minum ingots. By leveraging our understanding of convec-
tive solidification, our first attempt will investigate the
influence of jet (shear) power on grain refinement and
homogeneity in Al4.5Cu rolling slab ingots.
Experimental Apparatus and Procedure
The experimental preparation was coupled for this investi-
gation with a similar trial on the effects of stirring on
macrosegregation [41]. More detailed explanations of
apparatus choice can be found in the corresponding refer-
ence. For each experiment, charges were loaded into a
commercial gas burner furnace. The melt was degassed and
filtered to commercial standards. The charge was inoculated
with 25 ppm TiB grain refiner in order to maintain consis-
tency with our previous investigations. A typical “coffin
type” bottom block was used along with a 600  1750 mm
WAGSTAFF LHCTM open top mold. The steady state
casting speed was 65 mm/min. The casting speed and metal
level were varied during the first 500 mm of the cast before
reaching steady state values.
In order to vary the degree of jet power utilized to refine
grain structure, a series of fused silica downspouts were
prepared, each with a unique diameter. The unique diameter,
along with the flow rate, and physical properties of the
Al4.5Cu alloy led to a unique turbulent Reynolds number for
each trial. The Reynolds numbers investigated during this
series of experiments were: 64,000, 69,000, 81,000, 97,000,
and 121,000. In order to maintain the intensity of the mixing
jet, no combination bag was used during these trials.
Following casting, the cold ingots were each cross sec-
tioned at 1800 mm of cast length. Each cross section was
divided into quadrants by symmetry, and a series of 45
samples were removed using a 1-inch core drill for metal-
lographic analysis (see Fig. 1).
The metallographic samples were etched with a dilute
solution of hydrofluoric acid and analyzed for grain size and
dendrite arm spacing using an optical microscope according
to the established line-intercept method [42].
1008
Fig. 1 Location of samples taken for metallographic analysis. Nota-
tions A, C, and E correspond to micrograph images found in Fig. 6
Results
Figure 2a is a surface plot representing one quadrant of the
standard cast (SD cast) Al4.5Cu alloy. The grain size varies
from about 50 lm at the short face where solidification is
most rapid, to over 250 lm near the center where the sump is
steepest and solidification rates are the slowest. Figure 2b–f
represent the spatial grain size distribution measured at
1800 mm of cast length for Jets cast ingots (JT cast) char-
acterized by Reynolds number of 64,000, 69,000, 81,000,
97,000, and 121,000 respectively. All scale bars are colored
identically for ease of comparison. The grain size pattern
from each of these trials appears to be fairly similar in its
distortion of the standard result. Regardless of the jet power,
we can see a trend towards slower cooling (and thus larger
grain sizes) towards the center of the ingot similar to that
observed in the standard. However, the range of grain sizes
observed is greatly reduced. For each of the slices, the
majority of grains are approximately 100 lm, with the lar-
gest barely reaching 150 lm in diameter.
Figure 3a is a representation of the spatial secondary
dendrite arm spacing (DAS) profile from a SD cast ingot.
We can see small dendrite arms of approximately 25 lm
surrounding the periphery of the ingot, and growing to
approximately 55 lm near the center. Figure 3b–f represent
profiles taken from the JT cast at 1800 mm of cast length
for jets of Reynolds number 64,000, 67,000, 81,000, 97,000,
and 121,000 respectively. We can see that for each of the
stirred casts, the maximum DAS is lower than that of the
standard. We can also see that for the jets of the lowest
Reynolds numbers (64,000, 69,000, 81,000) the range of
DAS is much smaller, with the periphery being approxi-
mately 35–40 lm and growing to 50 lm in the center.
The DAS is also much more homogenous for these casts
than the standard or higher Reynolds number jets. For these
jets (97,000, and 121,000) the periphery of the ingot
exemplifies DAS of only 25 lm and grows to perhaps
50 lm in the center. While the profiles may be similar to the
S.R. Wagstaff and A. Allanore
standard case, the average DAS is smaller for these casts
than the other samples.
In order to better quantify the effects of turbulent jet
stirring, we have utilized the standard distribution bag
dimensions and velocities specified in [43], to generate an
effective Reynolds number of 15,000 for the standard case.
Figure 4 represents the average grain size and DAS as a
function of Reynolds number. What we can observe is that
there seems to be little influence of the power of the jet on
the respective dimension. The simple addition of the mixing
jet realized a 25% reduction in grain size for all mixing jets.
The DAS was slightly less responsive, only exhibiting a
10% reduction for the most powerful jets (97,000 and
121,000), the other mixing jets exhibited minimal deviation.
Figure 5 is a representation of the spread (range) of grain
size and DAS as a function of Reynolds number. We can see
in this plot that the spread of DAS is nearly unaffected by the
introduction of a turbulent jet. However, the grain size
exhibited a drastic change, the standard case having a grain
size distribution of nearly 200 lm (100–300 lm) while the
introduction of a turbulent jet reduced this range to only
75 lm (100–175 um). There seemed to be little impact of jet
power on this range, the simple presence of the jet imme-
diately reducing the grain size distribution.
Figure 6 is a sample series of micrographs for the stan-
dard case and Rej = 97,000. The locations of A (Center), C
(Mid-thickness), and E (Edge) are displayed in Fig. 1. While
quantifiable data has been presented in this section, there are
other qualitative observations on these samples. For the
standard case, we can see that locations E and C exhibit
dendritic structure, with E being much finer than that of C.
Sample A for the standard case is seemingly non-dendritic in
structure. Samples A and C for the stirred case are charac-
terized by a fine non-dendritic microstructure, while sample
E seems to be a mix of non-dendritic and dendritic
microstructure, also very fine.
Discussion
It appears from our experimental results that there seems to
be little impact of the power of a turbulent jet to increase the
degree of grain refinement. This is a similar to observations
made by Vogel [30], who found that increasing stirring
speed did not influence particle density or size significantly.
Instead, the simple presence of stirring promoted grain
refinement and non-dendritic structures. It is worthy of note
that Smith et al. [44] found that increasing the shear rate
caused the particle density to increase while decreasing the
average particle size. It seems that the mixing by a turbulent
jet is enough to homogenize temperature isotherms to pro-
mote the copious nucleation mechanism [39, 40] mentioned
Shear Induced Grain Refinement of a Continuously Cast Ingot 1009

Fig. 2 a–f From top to bottom

are grain size (lm) distribution
plots of quadrant 1 of an ingot
cross section. All color bars are
identical for ease of comparison.
a Standard DC cast with
combination bag. b Rej = 64,000.
c Rej = 67,000. d Rej = 81,000.
e Rej = 97,000. f Rej = 121,000
1010 S.R. Wagstaff and A. Allanore

Fig. 3 a–f From top to bottom

are Dendrite Arm Spacing (DAS
lm) distribution plots of quadrant
1 of an ingot cross section. All
color bars are identical for ease of
comparison. a Standard DC cast
with combination bag.
b Rej = 64,000. c Rej = 67,000.
d Rej = 81,000. e Rej = 97,000.
f Rej = 121,000
Shear Induced Grain Refinement of a Continuously Cast Ingot
Fig. 4 Variation of the average grain size and DAS as a function of
Rej. The standard Rej has been represented as 15,000
Fig. 5 Variation of the grain size and DAS spread (range) as a
function of Rej. The standard Rej has been represented as 15,000
above. The increased survival rate of the nuclei restricts the
growth of the grains and generates a smaller overall grain
size.
It is worthy of note to illustrate that the most turbulent jets
(97,000 and 121,000) generated the most homogenous grain
profile, with the least homogenous dendrite arm spacing
profile. While the lower Reynolds number jets de-stratified
the molten pool enough to generate uniform solidification
rates (hence similar microstructure), the most turbulent jets
somehow segregated microstructure while generating
homogenous grain size. The most turbulent jets from the
macrosegregation investigation [41] were designed to sus-
pend grains from the center and inhibit preferential sedi-
mentation by redistributing “superfluous” floating grains.
While this trend seems to be observed by the homogenous
grain size, there does seem to be a disconnect from the DAS.
One possible explanation is that there is cross-talk between
the grain size data and the DAS data because DAS is difficult
to isolate in non-dendritic structures. This could artificially
1011
Fig. 6 Example micrographs from positions A, B, and C (see Fig. 1)
for Rej = 97,000 (left column) and Standard cast (right column)
skew the distribution of DAS in these jets because they
would be the most likely to generate a spheroidal structure
(i.e. DAS = Grain Size).
Conclusion
We have examined the influence of a turbulent jet on the
microstructural properties and distribution of Al4.5Cu roll-
ing slab ingots. We have found that the introduction of a
turbulent jet promotes grain refinement, while effecting the
DAS very little. Even the most turbulent jets do not display a
noticeable increase in grain refinement from the least tur-
bulent jet. This seems to indicate that there is a threshold
Reynolds number of a turbulent jet which de-stabilizes the
isotherms and promotes grain refinement below the lowest
evaluated during this investigation. While the influence of
the turbulent jet is clear, it is perhaps best suited for a
numerical investigation since the effects are so robust and
independent of fine fluid-dynamic parameters. Also worthy
of investigation is a system to increase shear in a DC casting
system, which should increase the grain refinement as a
simple increase in velocity could not.
Acknowledgements We would like to thank the kind support of the
Novelis Solatens Casting Center for their help and resources during the
completion of this project.
1012
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 Microstructure Control in A356 Al–Si Alloy Via
Ultrasonic Melt Treatment

Waleed Khalifa, Mahmoud T. Abdu, Maiada S. Abdelrahman,

and Yoshiki Tsunekawa

Abstract
Ultrasonic treatment was conducted to study its effect on the size and morphology of the
α-Al phase of the A356 Al–Si–Mg alloy. Treatments were carried out in the temperature
range from 700 to 614 °C, i.e. from above the liquidus temperature (619 °C) to semisolid
temperatures. The treatment times varied from 15 to 180 s. The results showed that
ultrasonic treatment could control the alloy microstructure when applied in the liquid or
semisolid states, and was most efficient when applied at a few degrees above the liquidus
temperature, e.g., 620 °C, where globule size of 57 μm and roundness between 0.62 and
0.70 were obtained. Ultrasonic treatment times in the order of 15–30 s were sufficient to
dramatically refine the size and alter the morphology of the α-Al phase. The refining effect
observed in samples treated in semisolid state was due to solid fragmentation and
dispersion, while in the liquid state, refining occurred most likely as a result of activation of
non-equilibrium nucleation events which was confirmed from experimental simulations
performed using succinonitrile polymer.

Keywords
Ultrasonic treatment Al–Si alloys Microstructure Non-dendritic Semisolid

Introduction
Aluminum–silicon alloys are important class of aluminum
alloys owing to their low shrinkage and high fluidity in
casting, brazing, and welding applications, in addition to
their high specific strength and good corrosion resistance [1,
2]. These alloys come to prominence in producing auto-
motive parts such as pistons, engine blocks, and other
components for reduced vehicle weight and improved fuel
economy [2, 3]. The commercial hypoeutectic compositions
of these alloys contain α-Al, Al–Si eutectic, Fe-intermetallic
phases, and other minor phases in their microstructure [4].
W. Khalifa
M.T. Abdu (&)
M.S. Abdelrahman
Mining, Petroleum, and Metallurgical Engineering Department,
Cairo University, Giza, 12613, Egypt
e-mail: mahmoud.t.abdu@gmail.com
Y. Tsunekawa
Toyota Technological Institute, 2-12-1, Hisakata Tempaku,
Nagoya, Japan
The grain size and morphology of the α-Al phase are critical
microstructural parameters. The control of these two
parameters imparts better distribution of porosity and second
phase particles, improved surface finish and machinability,
greater fatigue strength, better pressure tightness, and
improved and isotropic mechanical properties [5, 6]. As a
results of the latter benefits, most aluminum cast alloys are
grain refined [6]. Control of grain size and morphology is
also critical in certain processing routes such as semisolid
metal (SSM) forming where fine, non-dendritic α-Al grains
constitute the ideal starting condition [7].
There are two main methods of grain refinement of alu-
minum–silicon alloys: chemical grain refinement and phys-
ical grain refinement. Chemical grain refinement involves
addition of certain inoculant intermetallic phases in the form
of master alloys. The chemical grain refiners are based on
Al–Ti, Al–Ti–B, etc. [8]. By contrast, the physical grain
refinement is carried out by applying mechanical vibrations
or other external fields to the melt during solidification [9].

© The Minerals, Metals & Materials Society 2017 1013

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_122
1014
One important physical grain refinement method is the use
of high-intensity ultrasonic vibrations to refine and modify
the alloy microstructure [10].
The technology of ultrasonic treatment (UST) is not
complex, and offers a variety of advantages such as degas-
sing, and enhanced grain refinement. UST was found eco-
nomic and easy to integrate with several casting techniques
without substantial technological changes [10, 11]. Recent
ultrasonic research works [12–16] were carried out on alu-
minum alloys, and several others were devoted to magne-
sium alloys, steels, composites manufacturing, and
degassing of alloy melts. Despite the increasing amount of
work already done, there is still a need to study the potentials
and limitations of the grain refinement achieved by UST of
aluminum–silicon alloys in the molten state. Through qual-
itative and quantitative metallographic observations, the
present investigation provides new explanations to the effect
of different ultrasonic treatments on the size and morphology
of the primary aluminum globules in the A356 Al–Si–Mg
cast alloy.
Experimental Procedures
Ultrasonic melt treatments (USTs) of the A356 alloy (JIS
AC4CH) were carried out in this study. The chemical
composition of the used material is shown in Table 1. As
can be seen in Table 1, the initial composition contained Ti
whose addition brings about a grain refining effect. The
treatment temperatures were varied from about 80 °C above
the liquidus temperature (619 °C) down to the semisolid
temperatures, namely: 700, 620, and 614 °C. Different
treatment times (15–180 s) were investigated as well. Alloy
pieces weighing 230–245 g were melted in alumina cru-
cibles using electric resistance furnace. When the melt
temperature reached about 30 °C above the specified treat-
ment temperature, the crucible was transferred to the ultra-
sonic treatment setup (Fig. 1). The ultrasonic horn and the
treatment furnace were kept at the same temperature of the
melt. The horn was lowered down and immersed in the melt
to a depth of about 5–10 mm. The furnace temperature was
adjusted so that the system cools down slowly to the spec-
ified treatment temperature, giving an opportunity to apply
ultrasonic vibrations for short periods at isothermal condi-
tions. At long treatment periods, it was observed that the
melt temperature slightly increased, e.g., 1 or 2 °C, because
of the energy transferred to the melt during the ultrasonic
vibrations, so that treatment takes place within very narrow
Table 1 Chemical composition of A356 (JIS AC4CH)
Element Si Mg Fe Ti Zn Al
wt% 7.02 0.37 0.10 0.19 0.01 bal.
W. Khalifa et al.
Ultrasonic Source
Thermocouple
Alumina Crucible .
Ultrasonic Horn
Resistance Furnace
Movable Stand
Fig. 1 Ultrasonic treatment setup
temperature range (usually 2 or 3 °C around the nominal
treatment temperature). After treatment, the melt was cast
directly into a steel cup-mold kept at about 90–100 °C.
The UST setup (Fig. 1) consists of an electric resistance
furnace, an ultrasonic source and horn, an adjustable-height
stand, a crucible containing the molten sample, and a ther-
mocouple. The ultrasonic system consisted of a 600-W
generator, a water-cooled 19.5 kHz transducer, a hot-work
tool steel horn, and spray-coated with MoB/CoCr material.
The ultrasonic intensity used was about 85 W/cm2 of the
horn projected area.
The small castings solidified in the cup-mold were then
cut into two halves, and the cross-section was polished and
deep-etched using Keller’s reagent for microstructural
investigation. Image analysis was carried out to determine
the area, and equivalent size of the α-Al globules/grains. The
equivalent size is defined as the diameter of a circle with the
same cross-sectional area of the feature or globule of the
α-Al phase in section.
About 7 fields were analyzed in the inner zone of the
sample cross section, which extended beyond *2.5 mm
from the surface. A filter for the smallest size of globules to
be analyzed was used to avoid considering the eutectic
aluminum remaining after etching.
To explain the effect of ultrasonic treatment on the α-Al
globule size and the responsible operating mechanisms two
types of experiments were carried out. Quenching experi-
ments in which A356 alloy samples were treated by ultra-
sonic vibrations at 623 °C for 5 s and (i) some droplets were
quenched immediately in water, (ii) sample was cooled in
furnace to 620 °C then some droplets were quenched in
water, or (iii) sample was heated in furnace to 627 °C then
some droplets were quenched in water. The other group of
experiments was applying ultrasonic vibrations to liquid and
semisolid succinonitrile polymer at different temperatures
(51–72 °C). Succinonitrile is a transparent organic material
which melts at about 57 °C.
Microstructure Control in A356 Al–Si Alloy Via Ultrasonic … 1015

Results It is clear that the ultrasonic treatment (UST) for 15 s at

Effect of Treatment Temperature
Figure 2 shows the microstructure of untreated (to the left)
and ultrasonically treated (to the right) A356 samples. The
microstructures of untreated and treated samples cast at
700 °C are shown in Fig. 2a, b. The figures show dendritic
structures and no big difference can be discerned between
both cases. Figure 2c, d shows the microstructures obtained
by identical casting conditions at 620 °C (i.e., same thermal
treatment of the liquid metal before and after pouring in the
mold), with applying ultrasonic vibration to only one sample
of them.
620 °C has modified the microstructure (Fig. 2d), so that the
α-Al grains become mainly non-dendritic and their sizes
become much finer. Similar microstructures for samples cast
at semisolid temperature (614 °C) are shown in Fig. 2e, f.
Both microstructures contain two types of grains coarse and
fine, which may be due to the slow cooling encountered in
the semisolid state before casting. However, the fine grains
are dendritic in the untreated sample, Fig. 2e, and
non-dendritic in the UST treated sample, Fig. 2f. It can be
inferred from the latter observations that under the latter
experimental conditions, isothermal UST at semisolid state
could partially affect the α-Al grains, i.e. forming partially
non-dendritic structure.

Fig. 2 Microstructure of A356

alloy after various casting
conditions: a cast at 700 °C (no
UST), b UST for 15 s at 700 °C,
c cast at 620 °C (no UST), d UST
for 15 s at 620 °C, e cast at
614 °C (no UST), f UST for 15 s
at 614 °C. All samples were cast
in metallic mold

500 μm 500 μm
(a) (b)

500 μm 500 μm
(c) (d)

500 μm 500 μm
(e) (f)
1016
Fig. 3 Average globule size of α-Al phase in ultrasonic treated
samples
The effect of different ultrasonic treatments on the α-Al
globule size is shown in Fig. 3. As can be seen, the α-Al
globule sizes obtained are large at both high and low treat-
ment temperatures, and decrease gradually and become
minimum at the intermediate temperature (at a few degrees
above liquidus temperature), i.e., 620 °C. The average
globule roundness is highest in the samples treated by
ultrasonic vibrations at the intermediate temperature as
compared to those treated at other temperatures (diagram not
shown for the sake of brevity). These results indicate that the
ultrasonic treatment could control the microstructure of the
A356 alloy when applied in the liquid or semisolid states,
and was most efficient when applied at few degrees above
the liquidus temperature, i.e., at 620 °C, where fine and
non-dendritic globules are formed.
Effect of Treatment Time
Figure 3 also shows the variation of the α-Al globule sizes
with ultrasonic vibrations for treatment times of 15, 30, 90,
and 180 s. At 700 °C, which is *80 °C above the liquidus
temperature, increasing the treatment time did not change the
globule size significantly which was *92 μm. It can also be
observed with the aid of Fig. 2 that at 700 °C, which is again
well above the liquidus temperature, the grain morphology
was still dendritic at all treatment times. At the low tem-
perature level where the material is kept in the semisolid
state (614 °C), increasing the treatment time from 15 to 30 s
caused a dramatic increase in the globule size from 58.5 to
79.5 μm which agrees with the partial effect the UST had on
α-Al as described in Fig. 2. Further increase in the treatment
time at 614 °C did not cause a major effect on the globule
size which was 86.8 and 83.1 μm for the treatment times of
90 and 180 s.
W. Khalifa et al.
In comparison to the above two temperature limits, short
UST treatments (15 and 30 s) produced fine, uniform,
non-dendritic globules at the intermediate temperature
(620 °C), which was 1 °C above the liquidus temperature. It
can be observed from Fig. 3 that a minimum α-Al globule
size of 56.7 μm was obtained from UST treatment at 620 °C
after treating the A356 for 30 s. It is also worth mentioning
that the globule roundness (roundness ¼ 4pA=P2 , where A is
the area and P is the perimeter) for the specimens treated at
620 °C was 0.62–0.70 with less obvious effect of treatment
time. It can also be noticed that the samples treated for
shorter times, i.e., 15 and 30 s exhibited finer α-Al globules
than those treated for longer times, i.e., 90 and 180 s, see
Fig. 3. The reason for this phenomenon is that the refine-
ment is likely due to the formation and dispersion of fine
solidified alloy phases at high cooling potential positions at
the horn surface or due to the collapse of cavitations during
treatment, and part of these solidified particles melts at
holding for long period in the liquid state. This indicates that
short ultrasonic treatments in the order of few seconds are
sufficient to control the size and morphology of α-Al phase
in the grain-refined A356 alloy.
Discussion
The effects of ultrasonic treatment in the semisolid and liq-
uid states are discussed in view of model experiments done
for this purpose.
Ultrasonic Treatment in the Semisolid State
The refinement obtained by ultrasonic vibrations in the
semisolid state is attributed to the fragmentation of dendritic
arms, due to the stresses produced by the collapse of cavi-
tation bubbles and the acoustic streaming [17–20]. The
injection of ultrasonic vibration into the succinonitrile was
done at several temperatures in the liquid and semisolid
states.
The experiments, in the semisolid state, showed that at
temperatures lower than the solidification temperature (57 °
C), the acoustic streams originating from the horn severely
fragment and destroy the solidified layer of succinonitrile
around the horn, and mix the fragments vigorously with the
bulk liquid away from the horn (Fig. 4). This observation is
in good agreement with the suggestions of Abdel-Reihim
and Reif [21] who proposed that the nucleation of crystals
during ultrasonic treatment is due to that the probe has a
greater cooling effect on the melt and from which crystals
separate and distribute into the melt.
Microstructure Control in A356 Al–Si Alloy Via Ultrasonic …
UST
Solidified
horn
succinonitrile
Thermocouple
Liquid
succinonitrile
10 mm
(a)
Fig. 4 Ultrasonic treatment of semisolid succinonitrile at 51 °C: a before ultrasonic vibrations, b suddenly after start of vibration, c after *3 s of
treatment
Similar effects are expected to take place in semisolid
aluminum alloys, thus, this observation seems satisfactory to
explain the refinement effect of ultrasonic treatment in
semisolid state and also indicates that the growth of phases
to large sizes will be very limited under these conditions.
Thus, the refining effect observed in samples treated at 614 °
C is most likely due to the solid fragmentation and disper-
sion taking place under the ultrasonic field.
Ultrasonic Treatment in the Liquid State
Concerning the refinement effect of ultrasonic treatment in
the liquid state, two main theories were proposed: (i) acti-
vation of uncontrolled inclusions and oxide particles in the
melt, so that they become potential nucleation sites upon
solidification, and (ii) formation of solid alloy phases (e.g.,
α-Al) at few degrees above the liquidus due to the high
pressure caused by collapse of cavitation bubbles [17, 18,
22–25]. In addition, the dispersion of the nucleant particles
(of either origin) throughout the liquid phase before solidi-
fication can be achieved effectively by the acoustic
streaming.
The direct experimental verification of any of these two
theories in aluminum alloys is difficult because of the diffi-
culty to observe the nucleation process taking place very
early during phase crystallization, and because of the
masking effect of phase growth, which contributes to the
final phase morphology. Therefore, the nucleation effects
can be estimated by analysis and comparison of mi-
crostructures obtained by different treatment conditions that
have slight or no effect on growth rate. Quenching
1017
(b) (c)
experiments of alloy A356 were done for this purpose, and
comparison of the α-Al grain sizes was done. In addition,
observations of ultrasonic treatment of the succinonitrile in
the liquid state can also assist in understanding this process.
Ultrasonic treatment of the liquid succinonitrile showed
that applying ultrasonic vibrations in this transparent mate-
rial caused acoustic streams of liquid to happen. These
streams show foggy or cloudy appearance, due to the for-
mation of tiny white particles originating from the horn
surface and their movement away into the bath for a distance
of up to 70 mm (in the vertical down direction). It was
difficult to determine the identity of the white particles;
either cavitation bubbles or solidified succinonitrile caused
by the pressure associated with the collapse of cavitations.
The density of foggy streams observed increased with
decreasing the temperature of the bath closer to the solidi-
fication temperature (i.e., 57 °C), and was less severe at
higher temperature, 72 °C. The foggy streams disappear
immediately after stopping the ultrasonic vibrations, so if
these white particles were solid succinonitrile, they would
not survive after stopping the vibrations and would not likely
affect the solidification microstructure (note that the latent
heat of fusion of the succinonitrile is 4.62 kJ/kg [26]). The
situation may be different in aluminum alloys, having larger
latent heat of fusion (398 kJ/kg).
The results of quenching experiments of A356 samples
showed no significant difference between globule sizes of
the α-Al phase in the samples quenched directly after UST at
623 °C (Fig. 5a), treated and cooled down in the furnace
after treatment to 620 °C within 30–40 s then quenched in
water (Fig. 5c), or treated and heated up to 627 °C within
30–40 s then quenched in water (Fig. 5b). The first
1018
Fig. 5 Microstructures of
quenched droplets of
grain-refined A356 alloy after 5 s
ultrasonic treatments at 623 °C,
a quenched immediately,
b heated to 627 °C within 30–
40 s and quenched, c cooled to
620 °C within 30–40 s and
quenched
a b
condition was expected to give the finest globule sizes if the
refining effect of ultrasonic treatment is mainly due to for-
mation of solid particles upon treatment (i.e., second theory
listed above), since larger population of particles will survive
melting and can act as nucleation sites upon solidification.
The other two samples were expected to give larger grain
size since the time elapsed in the liquid state after treatment
either on heating or cooling is believed to cause some
melting of the tiny solid particles, lowering down the pop-
ulation of active nucleation sites during solidification. The
sample heated up to 627 °C might be worse because heating
up for 30–40 s can dissolve greater number of the tiny solid
particles dispersed in the molten alloy.
With the results presented in Fig. 5, it is believed that the
refinement obtained by ultrasonic treatment is not mainly
due to formation of solidified alloy particles during ultra-
sonic treatment, but rather due to the contribution of other
factors, which may include the activation of the uncontrolled
inclusions such as oxide particles, active and inactive grain
refiner particles, and to a lesser extent the formation of
solidified alloy particles, and maybe other factors.
Conclusions
A systematic study of the effect of ultrasonic liquid-
metal-treatment on the structure of the A356 Al–Si–Mg
alloy was carried out over a large temperature range of
700–614 °C. The results showed that:
W. Khalifa et al.
(1) Ultrasonic treatment could control the alloy
microstructure when applied in the liquid or semisolid
states, and it is most efficient when applied at few
degrees above the liquidus temperature, i.e., at 620 °C,
where a minimum globule size of 56.5 μm and round-
ness between 0.62 and 0.70 were obtained.
(2) Short ultrasonic treatments in the order of few seconds
were sufficient to control the size and morphology of
α-Al phase.
(3) Refining effect observed in samples treated in semisolid
state was most likely due to the solid fragmentation and
dispersion caused by ultrasonic treatment.
(4) Refining obtained by ultrasonic treatment in the liquid state
was unlikely due to formation of solidified alloy particles
during ultrasonic treatment, but due to other factors, which
may include the activation of the uncontrolled inclusions
such as oxides, active and inactive grain refiner particles.
Acknowledgements The present work was partially supported by
Grant-in-aid for Scientific Research (No. 20360344) from the Ministry
of Education, Culture, Sports, Science and Technology of Japan.
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 Grain Refiner Sedimentation in the Launder
System of Twin Roll Casting and Application
of Electromagnetic Stirring

Onur Birbasar, Murat Can Erdemir, Vedat Topaloğlu, Cemil Işıksaçan,

Onur Meydanoğlu, Mert Günyüz, Hatice Mollaoğolu Altuner,
and Murat Dündar

Abstract
Al–Ti-B grain refiners are used as a grain refining agents in twin-roll casting. Although
Al3Ti particles in the rod dissolve, principal inoculant of TiB2 remains undissolved and
initiate heterogeneous nucleation. TiB2 particles with higher density than liquid Aluminum
are in tendency to settle as they are released from the melting grain refiner rod.
Experimental studies showed that Ti concentration varies at different depth of the liquid
metal in the launder. As samples were gathered from the bottom, not only the chemical
content, but the metallographic analysis of the samples clearly exhibited that melt at the
bottom of the launder heavily bear TiB2 particles and oxides. The trajectories of the
particles upon revealing from different position of the depth and their settlement were also
simulated in finite element analysis (FEA) and experimental findings were confirmed.

Keywords
Electromagnetic stirring Grain refiner Twin roll casting TiB2 particle

Introduction matrix. Small additions of such master alloys in aluminum

Achievement of a fine grain size and structural uniformity is
generally favorable for mechanical properties of most metals
and alloys. In order to achieve such a fine microstructure in
aluminum alloys, inoculants of micrometer size, such as
TiB2, TiC, or TiAl3, have been added to aluminum melt to
act as substrates for heterogeneous nucleation of aluminum
grains during solidification. Grain refiners are usually added
as Al-based master alloys that are rich in at least one of the
following elements: titanium, boron and carbon. There are
several types of grain refiners. Those produced by reaction
of molten aluminum with halide salts (K2TiF6 and KBF4)
and containing 5 wt% Ti and 1 wt% B, are the most widely
used by industry. Their typical microstructure consists of
TiB2 particles, TiAl3 needles and Ti solute in an aluminum
O. Birbasar (&)
M.C. Erdemir
V. Topaloğlu
C. Işıksaçan

O. Meydanoğlu
M. Günyüz
H. Mollaoğolu Altuner
M. Dündar
ASSAN Aluminum, Yayla Mh. D-100 Karayolu Ruya Sk. No.2,
34940 Tuzla, Istanbul, Turkey
e-mail: onur.birbasar@assanaluminyum.com
alloys result in a fine and equiaxed microstructure [1–4].
Continuous casting being younger than direct chill casting
technology, grain refinement applications are less understood.
Al–Ti-B grain refiners, having different stoichiometry, are
used as a grain refiner in twin roll casting. It is fed into the
liquid metal in the launder system extending to the caster. One
of the main problems seen in grain refining mechanism is the
agglomeration of grain refining particles in the components of
molten metal delivery system. Long distances covered by
these grain refiner particles in the launders contribute them to
settle and agglomerate at the bottom of the launder system.
Agglomerated particles becomes large in size with the pres-
ence of oxide film in the liquid metal. They can be revealed to
the stream with mechanical agitation of the melt. The results
can be detrimental for thin gauge foils, pre-painted products
and other applications in which surface appearance is crucial.
Also, these agglomerates can block filters, settle down in caster
tips by leading to feeding problems during casting. In addition
to this, even flush into cast strips, result in surface defects in
aluminum sheets and foils [1, 4–6].

© The Minerals, Metals & Materials Society 2017 1021

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_123
1022
In metallurgical processing, effective and reliable stirring of
the melt is one of the requirement for higher productivity and
improved process performance. Magnetic field, as a contact-
less processing technology, has been extensively applied in
materials science and engineering, such as the refinement of
microstructure of alloys [7–10]. By electromagnetic stirring
(EMS) it is possible to achieve effective stirring through the
interaction between the magnetic field from the static induc-
tion coil placed on the outside of the launder and liquid metal.
Heterogeneous distribution and agglomeration of TiB2 parti-
cles in liquid aluminum can be eliminated by using electro-
magnetic stirring system on launder.
In this study, TiB2 particle formations in the launder were
characterized and particle trajectories in the launder system
were simulated by finite element analysis (FEA).
Experimental Studies
In the present study, samples gathered from the different
depths of the launder were investigated to see the distribution
of TiB2 particles. Apparatus for taking sample from the dif-
ferent depth of the liquid metal is seen in Fig. 1a Samples
taken from the liquid metal were analysed by optical emission
spectrometer in order to understand the Ti concentration dif-
ferences. Also these samples (Fig. 1b) were metallographi-
cally prepared according to standard metallographic methods.
The microstructure of the samples were examined by using
optical microscope (Zeiss Axiotech and scanning electron
microscope (SEM-JEOL 5600) equipped with secondary
electron (SE), back-scatter electron (BSE) and energy dis-
persive spectroscopy (EDS) detectors in order to determine the
TiB2/TiAl3 particles, oxides etc.
In order to clarify the particle movement in the liquid
metal simulation studies were conducted via finite element
analysis (FEA). Finite element model including the regions
of launder, liquid metal and TiB2 particles has been con-
structed by ANSYS software. The trajectories of TiB2 par-
ticles with different diameter were calculated.
The computations were carried out with the incompressible
RANS equations. Menter’s SST x turbulence model was
used in the simulations, which is based on the Boussinesq
Fig. 1 a Apparatus for taking
sample from the launder,
b samples taken from the bottom
and top of the liquid metal in
launder
(a)
O. Birbasar et al.
hypothesis and is considered as an improved version of the
standard k x model [11, 12]. A segregated algorithm was
used with the finite volume method to solve the momentum
and turbulent transport equations [13]. The pressure-
correction-based SIMPLE technique was chosen to couple
the pressure and velocity fields [14]. The spatial discretization
of the convective terms of the Navier-Stokes and turbulent
transport equations were solved with a second-order-upwind
scheme as well as a second-order central differencing scheme
was used for the viscous terms [15].
An unstructured mesh was created for the full-scale
computational model. The near-wall grid sizes were con-
trolled carefully. Non-dimensional wall distance values (y+)
of about 1 were selected for the majority of the computa-
tional domain, in order to solve viscous sub-layer. The
design mass flow rate was selected to be 0.471 kg/s.
Results and Discussion
Optical emission spectrometer test results of the samples
taken from the different depth of the liquid metal in the
launder are given in Table 1. Samples were taken from the
closest region of the launder (just before headbox) to the
caster rolls where the liquid metal solidifies. Test results
showed that Ti concentration varies at different depth of the
liquid metal. Ti concentration is higher in the bottom of the
launder than that of top. This heterogeneity of the Ti element
in liquid metal can lead to different solidification conditions
at the top and bottom of the as-cast sheet. In this case, dif-
ferent grain structures can occur at the top and bottom sur-
faces of as-cast sheet, resulting surface segregations, TiB2
particle agglomerations etc.
Figure 2 shows optical microscope images of the sam-
ples, which were taken from the bottom and top of the
launder. Optical images reveal that all the samples investi-
gated have eutectic like structures comprised of intermetallic
particles having different size and morphology. In addition,
Fig. 2b clearly shows that the bottom side contains oxide
like regions and agglomerated particle formations.
To make further studies, the same regions were examined
via the scanning electron microscope. As seen in Fig. 3 back
(b)
Grain Refiner Sedimentation in the Launder System of Twin Roll … 1023

Table 1 Chemical compositions Alloy/sample Element, wt%

of the samples
Si Fe Cu Mn Ti
8006 Top 0.14 1.42 0.02 0.64 0.16
Bottom 0.14 1.43 0.02 0.63 0.26
1050 Top 0.12 0.26 – – 0.18
Bottom 0.12 0.27 – – 0.25

(a) (b)

Fig. 2 Optical microscope images of the samples taken from a top and b bottom of the launder

+1
Counts

keV
+2
Counts

keV

Fig. 3 Back scattered electron images and EDS analysis of the sample taken from the bottom of the launder, showing TiB2 particle
agglomerations
1024 O. Birbasar et al.

scattered electron images reveal that these regions contain

aluminium oxide in the centre and TiB2 particles on the outer
surface. These kind of agglomerates could cause any kind of
problems during casting process. During casting these
agglomerates may be dislodged and introduced into the cast
strips. Small amounts of those particles which could escape
into the cast strips, can cause defects during the rolling.
As the strip thickness decreases, the clusters induce a
much further negative influence. In contrast to the ductile Fig. 5 Distributions of TiB2 particles with various particle diameter
aluminum matrix, which can be easily elongated during
rolling, TiB2 particles have limited ability to deformation.
TiB2 particles having different dimensions were used for
Therefore micro vacancies could occur on the vicinity of the
simulation studies. Particle dimensions determined by using
TiB2 particles and results in early failure initiation points.
metallographic investigations of grain refiner rod. The sizes
These points can lead to formations of small cracks/
of TiB2 particles vary from 6–16 lm according to the optical
segregations on the surface of the sheet products and pin-
microscope images taken from the cross-section of the rod.
holes on the foil products.
The distribution of TiB2 particles at the front of the
Figure 4a shows the launder system between ceramic
transition region of two launder is given in Fig. 5. We
foam filter and headbox. Particle simulation studies were
observe a different sedimentation behavior according to the
performed on this launder section due to the short distance to
particle diameter. Mostly TiB2 particles having relatively
the caster rolls where the solidification occurs. Also typical
larger sizes (100 µm) are more likely to settle down where
sectional view of the launder is given in Fig. 4b.
smaller TiB2 particles can move without settling.

Conclusions

The results of this study can be summarized as follows:

It was found that the liquid metal at the bottom of the
launder contains more TiB2 particle agglomerations than
that of the top and some oxides.
Simulation results showed that TiB2 particles have set-
tling velocity in liquid aluminum due to combination effect
of the submerged weight and turbulence in launder. How-
ever, depending on the size of TiB2 particles, there are dif-
ferent efficiencies of settling potency.
It is assumed that the application of magnetic stirring in a
launder will inhibit the settling of these particles. In a further
study a well known method of electromagnetic agitation of
liquid aluminum will be implement to the typical geometry
of launder systems to keep the particles suspended.

Acknowledgements Authors wish to thank Mr. Nihat Yılmaz, tech-

nician of Assan Alüminyum Laboratory, for his valuable help with
metallographic studies. Also we wish to thank Mr. Ertan Karaismail
and Mr. Ahmet Yusuf GÜRKAN (FIGES A. S. Company) for per-
forming simulation studies.

References

1. D.A. Houshang, D. Dominique, T. Pascal, Behavior of boron in

molten aluminum and its grain refinement mechanism. Metall.
Mater. Trans. A 44A (2013)
Fig. 4 a Launder system between ceramic foam filter and headbox, 2. M. Dundar, O. Keles, Aluminum foil: its typical quality problems
b sectional view of the launder and their causes. J. Mater. Process. Technol. 125–137 (2007)
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3. S. Lakhwinder, G. Geetesh, S. Rupinderpreet, Review of the latest
developments in grain refinement. Int. J. Mod. Eng. Res. (IJMER)
2, 2724–2727 (2012)
4. K. Kim, The effect of melt conditioning on segregation of solute
elements and nucleation of aluminum grains in a twin roll cast
aluminum alloy. Metall. Mater. Trans. A 45A, 4538–4548 (2014)
5. C. Vives, Electromagnetic refining of aluminum alloys by the crem
process: part I. Working principle and metallurgical results. Metall.
Trans. B 20B, 623–629 (1990)
6. M. Dundar, O. Keles, A Study on surface defects caused by grain
refiners. Proceedings International Conference Continuous Casting
Non-Ferrous Metals (2005)
7. Y. He, Q. Li, W. Liu, Separating effect of a novel combined
magnetic field on inclusions in molten aluminum alloy. Metall.
Mater. Trans. B. 43B, 1149 (2012)
8. J. Szajnar, Casting structure change caused by magnetic field.
J. Achievements Mater. Manufact. Eng. 24(1) (2007)
9. J. Dong, J. Cui, X. Zeng, W. Ding, Effect of low-frequency
electromagnetic vibration on cast-ability, microstructure and
1025
segregation of large-scale dc ingots of a high-alloyed Al. Mater.
Trans. 46(1), 94–99 (2005)
10. Z. Zhao, J. Cui, J. Dong, H. Zhang, B. Zhang, Effects of
low-frequency magnetic field on grain boundary segregation in
horizontal direct chill casting of 2024 aluminum alloy. China
Foundry 2(1), 44–47 (2005)
11. H. Tennekes, J.L. Lumley, A First Course in Turbulence (MIT
Press, Cambridge, 1972)
12. D.C. Wilcox, Reassessment of the scale-determining equation for
advanced turbulence models. AIAA J. 26(11), 1299–1310 (1988)
13. J. Blazek, Computational Fluid Dynamics: Principles and Appli-
cations (Elsevier, Oxford, 2001)
14. S. Patankar, Numerical Heat Transfer And Fluid Flow
(McGraw-Hill, New York, 1980)
15. L. Davidson, Numerical Methods For Turbulent Flow, Lecture
Notes, Department Of Thermo And Fluid Dynamics. Chalmers
University of Technology Goteborg, Sweden (2005)
 Thermal Analysis of Grain Refining in A319
Alloys

Waleed Khalifa

Abstract
Grain refining is an important technology in the modern aluminum foundry, since it
provides several advantages to mechanical behavior and integrity of castings. In this
chapter, thermal analysis of the A319 alloys was studied for the purpose of obtaining
precise and repetitive cooling curves and hence accurate thermal analysis parameters. The
main casting parameters such as cooling rate, alloy composition, and grain refiner level
were considered and evaluated. The results showed that the cooling conditions during
thermal analysis need to be suitable to rapidly reach equilibrium between the solidifying
melt and the mold. The time parameters gave better control of grain refining than
temperature parameters since they spread over wide ranges. The variation of Si and Cu
levels resulted in composition-related changes of the thermal analysis parameters. It was
also found that the sensitivity of the thermal analysis parameters to the variation of grain
refiner level was highly impaired at slow cooling rates of 0.27–0.40 °C/s.

Keywords
Si Cu Thermal analysis parameters Refiner Cooling curve Cooling rate

Introduction Fig. 1. Three regions are of significance in this curve: region

The quality and properties of Al–Si cast products; such as
the mechanical properties, the hot tearing susceptibility, the
surface finish, the machinability, and the pressure tightness
of products; are based mainly on certain microstructural
characteristics. Therefore, the assessment and prediction of
such microstructural characteristics before pouring is of
prime interest. Of these characteristics are the levels of melt
quality including the extent of grain refining; the level of
modification [1]; and the level of dissolved hydrogen.
The thermal analysis using cooling curves is called con-
ventional thermal analysis. In this technique, the molten
alloy is allowed to cool down slowly (0.1−0.8 °Cs-1 [2]),
and the cooling curve is recorded, then the thermal param-
eters are identified from the thermal analysis curve, see
W. Khalifa (&)
Cairo University, Giza, 12613, Egypt
e-mail: wkhalifa@eng.cu.edu.eg
A indicating the extent of grain refining, region B indicating
the level of modification attained, and region C which
determines the end of solidification. The general shape of the
cooling curve gives an indication on level of grain refine-
ment and if the grain morphology is columnar or equiaxed
[3]. The thermal analysis can be done using either one or two
thermocouples. The first thermocouple is placed at the center
of the cub mold and the second one is placed near the mold
wall.
The grain refining process provides several advantages to
alloy properties and processing: including better distribution
of porosity and second phase particles, improved surface
finish and machinability, greater fatigue strength, better
pressure tightness, and reducing tendency of ingot cracking,
and provides improved mechanical properties and several
other beneficial effects. This is why monitoring of extent of
grain refining is necessary for quality assurance before
pouring the melt. Other uses of cooling curves in predicting

© The Minerals, Metals & Materials Society 2017 1027

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_124
1028
Fig. 1 Typical cooling curve of Al–Si cast alloys
microstructure of Al–Si cast alloys are briefly reviewed in
Ref. [4].
In addition, thermal analysis can be used as a technique to
control the grain size in castings, and to determine the
dendrite coherency point [5]. The relevant thermal analysis
parameters used in the grain-size prediction of the
hypo-eutectic Al–Si alloys [6], are either time or temperature
parameters. Several research works were carried to study
grain refining potential using this technique [7]. The break-
ing points of cooling curves were calibrated against the
growth temperature. One of the complexities that face this
approach is that the growth temperature is a function of the
cooling rate. Therefore, constant cooling rate should be
experienced to obtain consistent data [5, 8].
When the nucleation undercooling is large, a relatively
large grain size is obtained, and when this value is less than
0.3 °C this indicates that there is no barrier for nucleation
and the grain size is relatively fine [1]. Hence assessment
and comparisons of the grain refining potential of the melt
may be done. In addition, it was reported that grain refine-
ment affects the other thermal analysis parameters such as
nucleation and growth temperatures of various phases, e.g.,
eutectic Si, the solidification range and total solidification
time [9].
In the current work, the thermal analysis parameters as
affected by cooling rate, alloying addition and grain refiner
levels were investigated to reach deeper understanding of the
effect of these interconnected parameters, and hence find the
appropriate parameters that best reflect the level of grain
refinement.
W. Khalifa
Experimental
The thermal analysis experiments of this study were done for
various compositions around and beyond that of alloy 319.
The specified composition of alloy 319 is Si = 5.5–6.5,
Cu = 3–4, Fe  1, Zn  1, and Mg  0.1 wt%. Three
levels of each of Si and Cu were investigated separately.
Table 1 lists these targeted compositions. About 450 g of
each alloy composition were prepared from commercial pure
aluminum alloy AA1050 (containing *0.5% Fe) and com-
mercial pure Si (99% Si) and Cu (99.9% Cu) additions.
Small ceramic crucibles and electric resistance furnace were
used for this purpose. When the melt temperature was raised
at about 800 °C, manual stirring with graphite rods
(/ = 15 mm) commenced and continued until dissolving of
all alloying additions and homogenous melts obtained. The
melt was then degassed for 5 min with dry argon using
Pyrex tube. After skimming, the grain refiner (Al-5Ti-1B
master alloy) was added with the specified level and the melt
was stirred for 3 min. The melt (at about 750 °C) was then
poured into a 500 °C-heated graphite mold with a K-type
thermocouple (/ = 0.127 mm) inserted from the mold bot-
tom, as shown in Fig. 2. The characteristic cooling rate
encountered in this first batch of experiments was about 0.8–
1.1 °C/s. The second batch of thermal analysis experiments
was carried out via remelting of the previous ingots and
recording cooling curves at much lower cooling rates
(*0.27–0.40 °C/s). The latter rates were achieved through
cooling in the graphite crucible where remelting was done.
The acquisition rate was 10 Hz, and the cooling curves were
recorded down to 400 °C in all experiments.
The cooling curves were then drawn using Microsoft
Excel, and the main grain refining parameters shown in
Fig. 3 were determined. These grain refining parameters
obtained from thermal analysis were then compared and
related to the level of refiner used and to the alloy compo-
sition and cooling conditions encountered during the
experiment.
Results and Discussion
In this part of the study, we discuss the effect of alloying
additions (Si and Cu), the effect of cooling rate, and the
refiner level on the thermal analysis parameters pertinent to
the grain refining process. Before discussing these important
issues, it is appropriate to show how these parameters were
identified from the cooling curves.
The nucleation point (identified by temperature TN and
time tN) was identified from the second derivative curve,
while the undercooling (TU, tU) and recalescence (TR, tR)
Thermal Analysis of Grain Refining in A319 Alloys 1029

Table 1 Targeted compositions Exp. # Si Cu Fe Zn Refiner*

of the thermal analysis samples
1 5 3.5 0.5 0.0 no
2 5 3.5 0.5 0.0 md
3 5 3.5 0.5 0.0 hi
4 6 3.5 0.5 0.0 no
5 6 3.5 0.5 0.0 md
6 6 3.5 0.5 0.0 hi
7 7 3.5 0.5 0.0 no
8 7 3.5 0.5 0.0 md
9 7 3.5 0.5 0.0 hi
10 6 2.5 0.5 0.0 no
11 6 2.5 0.5 0.0 md
12 6 2.5 0.5 0.0 hi
13 6 4.5 0.5 0.0 no
14 6 4.5 0.5 0.0 md
15 6 4.5 0.5 0.0 hi
*
no, md and hi refiner levels mean 0.0, 0.4 and 0.8 wt% of the molten sample

easily identified in the slow cooling experiments (Fig. 4b)

Fig. 2 Schematic diagram of the graphite cup mold and thermocouple
arrangement during thermal analysis. Dimensions are in mm
points were determined from the first derivative curve:
where the first derivative equals zero at these points [8]. The
most used parameters for assessing grain size in Al castings
are DTR-U and t1, see Fig. 3a, b.
However, in the current investigation, it was sometimes
difficult to identify the nucleation point of the curve for the
first batch of experiments (high cooling rate), see Fig. 4a. It
is believed that equilibrium between mold and sample was
not reached before cooling down to the nucleation point, so
that the latent heat released during nucleation was not suf-
ficient to alter the overall heat that can be sensed by the
thermocouple. In the other hand, the nucleation point was
were the cooling curve was recorded in the melting crucible,
and hence equilibrium was already achieved during the
entire record of cooling curve. It is also worth mentioning
here that the nucleation points of eutectic and the copper
phases can be identified on both curves of Fig. 4. This
indicates to that equilibrium was reached late during the
experiment of the higher cooling rate of Fig. 4a. Therefore it
is recommended that cooling conditions during thermal
analysis need to be suitable to rapidly reach equilibrium
between the solidifying melt and the mold.
The other thermal analysis parameters can be determined
based on the previous ones (Fig. 3c), such that: KF16 is the
difference between the temperature when the cooling rate is
2 °C/s and the temperature recorded 16 s later than the
undercooling point; and tf,Th-Al is the time difference
between the moment corresponding to the minimum in
temperature and the time at which that temperature is again
reached after recalescence [6]. These two parameters are
mainly used when sand mold (cooling rate = 2 °C/s) is used
for thermal analysis.
Effect of Grain Refiner Level
Figure 5 shows the effect of grain refiner level on the shape
of the cooling curves at the nucleation arrests. This figure
shows the cooling curves at three nominal compositions of
6Si-3.5Cu, 7Si-3.5Cu and 6Si-4.5Cu. It is clear that at the
same composition, the shape of the curve changed with the
level of refiner. At the no-refiner condition, the under-
cooling (DTR-U) is large, and it decreased with refiner
1030 W. Khalifa

Fig. 3 Thermal analysis parameters related to the grain refining of aluminum alloys: a temperature parameters, b time parameters, and c other
parameters

Fig. 4 Second derivative plot on cooling curves of a alloy 9 (cooling rate 1.1 °C/s) and b alloy 10 (cooling rate of 0.35 °C/s)

Fig. 5 Effect of grain refiner level on the nucleation arrest of the cooling curve. (cooling rates of 0.8—1.1 °C/s)
Thermal Analysis of Grain Refining in A319 Alloys 1031

Table 2 Thermal analysis Sample DTR-U t1 tf

parameters for the 6Si-3.5Cu and
7Si-3.5Cu samples for cooling 6Si-3.5Cu-no refiner 1.986 4.1 12.8
rates of 0.8–1.1 °C/s 6Si-3.5Cu-md refiner 0.0605 1.7 2.2
6Si-3.5Cu-hi refiner 0.173 1.4 2.8
7Si-4.5Cu-no refiner 0.7701 4 8.3
7Si-4.5Cu-md refiner 0.028 0.1 0.2
7Si-4.5Cu-hi refiner 0 0 0

Fig. 6 Effect of Si level on the

shape of cooling curves. (cooling
rates of 0.8–1.1 °C/s)

addition. In some cases, no undercooling can be identified
on the curve.
The values of DTR-U, t1 and tf of these samples are shown in
Table 2. It is clear that all these parameters decreased with
increasing the refiner level. The other parameters of Fig. 3 did
not show consistent trends with the refiner level. It was also
noticeable that both of t1 and tf spread over wide ranges. This
gives these time parameters a merit for better control of grain
refining, even though their values are composition dependent.
Effect of Si and Cu Levels
Figure 6 shows the effect of Si level on the shape of cooling
curves for both of no-refiner (Fig. 6a) and high-refiner levels
(Fig. 6b). It is clear that the higher the Si level the higher the
undercooling temperature, e.g., the undercooling of highly
refined alloys increased from 0, to 1.4 to 3.8 °C with the
increase of Si from 5 to 6 to 7%, respectively. At no-refiner
condition, undercooling can still be seen to increase with Si
level (see Fig. 6a). This observation can be explained with
the Si poisoning effect on the grain refiner particles, meaning
that nucleation and hence grain-refining are negatively
weakened by the addition of Si and this effect is higher at
higher levels of Si.
Similar effect can be observed with Cu level, as can be
seen from Fig. 7. Both of Figs. 6 and 7 show composition-
related variation of the thermal analysis parameters pertinent
to grain refining. Actually these intrinsic effects may com-
plicate the use of thermal analysis parameters as
microstructure prediction tools in aluminum foundry, so that
automatic and online prediction systems based on thermal
analysis might suffer difficulties in dealing with melts with
varying levels of alloying additions, even within the tolerable
specification limits of composition. However, the effect of
alloying additions on grain size of the grain refined alloys
(shown in Figs. 6 and 7) is yet to be determined.
Effect of Cooling Rate
More evident undercooling values can be seen in the
cooling curves of the remelted samples (Fig. 8) which were
recorded at slower cooling than those shown in Figs. 5, 6
1032 W. Khalifa

Fig. 7 Effect of Cu level on the

shape of cooling curves. (cooling
rates of 0.8–1.1 °C/s)

Fig. 8 Cooling curves for

remelted samples of a 6Si-3.5Cu
and b 7Si-3.5Cu. (cooling rate of
0.27–0.40 °C/s)

and 7. It is obvious that the undercooling values (listed in
Table 3) are higher than those shown above. The thermal
analysis parameters exhibited less consistent trends with the
grain refiner level as compared to those of the faster cooling
rates (see Table 2). The same was also observed with
varying the Si or Cu levels, see for example Fig. 9 and
Table 4. In this respect, it can be concluded that the sen-
sitivity of the thermal analysis parameters to the level of
grain refiner additions is highly impaired at slow cooling
rates (i.e., 0.27–0.40 °C/s). Hence, it can be recommended
that the thermal analysis data be taken at characteristic
cooling rates of about 1 °C/s.
Thermal Analysis of Grain Refining in A319 Alloys 1033

Table 3 Thermal analysis parameters for the remelted 6Si-3.5Cu and 7Si-3.5Cu samples for slow cooling conditions (cooling rate of 0.27–0.40 °C/s)
Sample DTR-U t1 tf
6Si-3.5Cu-no refiner 2.408 9.9 30.1
6Si-3.5Cu-md refiner 1.379 7.9 24.6
6Si-3.5Cu-hi refiner 1.11 6.8 20.4
7Si-4.5Cu-no refiner 2.37 13.6 37.4
7Si-4.5Cu-md refiner 1.793 8.5 22.1
7Si-4.5Cu-hi refiner 1.8 10.2 28.9

Fig. 9 Cooling curves for

remelted samples of 6Si with
various Cu levels at a medium
refiner, and b high refiner levels.
(cooling rate of 0.27–0.40 °C/s)

Table 4 Thermal analysis parameters for the remelted 6Si alloys with various Cu levels at two grain refiner additions. (cooling rate of 0.27–0.40 °C/s)
Sample DTR-U t1 tf
6Si-2.5Cu-md refiner 1.16 8.5 22.1
6Si-3.5Cu-md refiner 1.379 7.9 24.6
6Si-4.5Cu-md refiner 0.842 8.7 19.9
6Si-2.5Cu-hi refiner 1.07 8.5 23.8
6Si-3.5Cu-hi refiner 1.11 6.8 20.4
6Si-4.5Cu-hi refiner 1.309 9.7 26.6

Conclusions • Time parameters gave better control of grain refining

The following conclusions can obtained for the current
work:
• Cooling conditions during thermal analysis experiments
need to be suitable to rapidly reach equilibrium between
the solidifying melt and the mold.
than temperature parameters since they spread over wide
ranges.
• Variation of Si and Cu levels resulted in composition-
related changes of the thermal analysis parameters.
• Sensitivity of the thermal analysis parameters to the level
of grain refiner is highly impaired at slow cooling rates of
0.27–0.40 °C/s.
1034
Acknowledgements The financial support of the Egyptian Science and
Technology Development Fund, grant No. 14902 is highly appreciated.
References
1. D. Apelian, G.K. Sigworth, K.R. Whaler, AFS Trans. 92(2), 297–
307 (1984)
2. N. Tenekedjiev, J. Gruzleski, AFS Trans. 99, 1–6 (1991)
3. L. Arnberg, L. Backerud, H. Klang, Grain refinment in Castings
and Welds, ed. by G. Abbaschian, S. David, (1983)
W. Khalifa
4. W. Khalifa, O-87, In Proceedings of the 72nd World Foundry
Congress, ( Nagoya, Japan, 21–25th May 2016)
5. M. Johnsson, Thermochim. Acta 256, 107–121 (1995)
6. J. Lacase, D. Ferdian, I. Lizarralde, A. Niklas, S. Eguskiza, A.I.
Fernadez-Calvo, World Foundry Congress (2014)
7. M. Johnsson, L. Backerud, G. Sigworth, Metall. Trans. 24A, 481–491
(1993)
8. D. Gloria, J. E. Gruzleski, Light Metals (1999), Met Soc., ed. by M.
Bouchard, A. Faucher
9. S.G. Shabestari, M. Malekan, J. Alloy. Comp. 492, 134–142 (2010)
 Peritectic Coupled Growth Solidification—
a Review

Peiman Shahbeigi-Roodposhti and Harold Brody

Abstract
Initiation and growth mechanisms of peritectic coupled growth (PCG) structures have been
reviewed to clarify parameters that play a significant role in PCG formation and stability.
Three important alloys of Fe–Ni, Ni–Al and Ti–Al have been studied to reveal mechanisms
contributing to PCG formation. Types of PCG, the stability of lamellar coupled growth and
their morphological behavior are strongly dependent on G/V ratio (G: thermal gradient, V:
growth rate), lamellar spacing and composition. Analogy between peritectic coupled
growth (PCG) and eutectic coupled growth (ECG) is also a point of interest in this study.
Further investigations in Ni–Al and Cu–Sn are necessary to clarify the PCG formation
(nucleation/growth mechanism) in conventional G/V versus composition diagram.

Keywords
Peritectic reaction Coupled growth Isothermal growth

Introduction and peritectic (secondary) phases at the peritectic reaction

Directional solidification of peritectic systems results in the
formation of a wide range of microstructures, including:
isothermal peritectic coupled growth, cellular peritectic
coupled growth, discrete and island banding structures, bulk
supersaturated peritectic product phase and oscillatory
tree-like structure [1–13]. In this review, mechanisms that
are contributing in nucleation and growth of peritectic cou-
pled growth structures in Fe–Ni, Ni–Al and Ti–Al were
studied with more emphasize on isothermal PCG.
PCG during directional solidification in which two phases
aligned parallel to the growth direction form simultaneously
at the solid liquid interface has been point of interest for
more than five decades [3, 5, 9, 14–17]. In a 1959 text
Chalmers [14] postulated that simultaneous solidification of
primary and peritectic phases is applicable for any peritectic
system in the composition range between Ca and Cp except
Cb (Ca, Cp and Cb are the compositions of primary, liquid,
P. Shahbeigi-Roodposhti (&)
H. Brody
University of Connecticut, Storrs, USA
e-mail: pshahbe@ncsu.edu
temperature, respectively) at sufficiently sharp thermal gra-
dient (G) and slow growth rate (V); i.e. a high G/V ratio.
Formation of primary phase dendrites in advance of the
peritectic isotherm can be suppressed at relatively high
thermal gradient to growth rate ratios to stabilize isothermal
PCG development. In his 1964 text [18], Chalmers reported
on directional solidification experiments by Uhlman and
Chadwick [5] on Ag–Zn and their arguments that duplex
structures in peritectic systems will always form over a
temperature range.
Later, Livingston [16] and Flemings [15] proposed that
high G/V ratio can provide applicative conditions for PCG
formation in peritectic alloys between Ca and Cb. Almost
concurrently with the publication of these predictions,
directional solidification experiments by Boettinger [19],
Barker and Hellawell [20] and Brody and David [21] on Sn–
Cd and Pb–Bi at high G/V ratios produced duplex bands
transverse to the growth direction and plane front growth of
the peritectic product phase (b). Up to 1990 directional
solidification experiments on peritectic systems did not
support isothermal peritectic coupled growth. After that PCG

© The Minerals, Metals & Materials Society 2017 1035

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_125
1036 P. Shahbeigi-Roodposhti and H. Brody

Fig. 1 Schematic of a banded structure b isothermal coupled growth

c cellular coupled growth d plane front growth. Black and white lines
illustrates ß and a phases in peritectic systems, respectively. Red arrows
are growth direction
Fig. 2 Calculated Ccritic for Ni-Al peritectic system [28]

formation has been reported in various metallic and organic

materials [3, 9, 12, 22–26].
Lamellar structure forms when both a and b phases are
morphologically stable. Isothermal lamellar coupled growth
is usually observed at compositions between Ca and Cb
when both phases grew under plane front conditions at rel-
atively high G/V ratio. Another form of PCG is
non-isothermal coupled growth (or weakly coupled growth)
that forms when G/V is decreased beyond the morphological
stability of the a phase. Cells grow at similar velocity (but
different temperature) than the intercellular plane front
peritectic phase (b). Figure 1 reveals the difference between
transverse banding structure in which layer of bands are
perpendicular to the growth direction, isothermal PCG,
cellular PCG and plane front growth.
As it has been postulated by Biswas [27] and Ma [28] and
then tested experimentally by Kurz et al. [3, 12, 22, 23],
there is a critical composition, Ccritic, between Ca and Cb that
separates the peritectic plateau into two regions where cou-
pled growth and banded structure dominate. Coupled growth
structure forms close to Cb and banded structure next to Ca.
Figure 2 shows the critical composition for Ni-Al system
that has been calculated by Ma et al. [28]. a* in this figure is
a dimensionless parameter that is defined as a ¼ aL =aLa
where aL is a parameter that depends on the difference
between liquid/a and liquid/ß interfacial energies, liquidus
slopes of a and ß phases and the ratio of half-widths of two
phases; and aLa is the liquid/solid interfacial energies of
liquid/a interface. At the left side of the Ccritic, where a* has
a negative value, the coupled structure is not stable, while at
the right side of that, where the a* is positive, coupled
structure is stable. Figure 2 shows that the PCG structure
forms close to Cb that increases the volume fraction of b
phase. For consistency, a and b are used to represent the
primary and peritectic product phases, respectively. Details
of calculation have been provided in Ref. [28].
Table 1 [28] reveals good agreement between calculated
critical composition and experimental results for Sn–Cd [19],
Ti–Al [8], Ni–Al [9], Cu–Zn [6] and Fe–Ni [3] systems; and
poor agreement for Pb–Bi [29] and Sb–Sn [6]. The discrep-
ancy in the latter two systems could be due to Ma et al.’s

Table 1 Calculated critical composition and observed experimental composition for coupled or banded structure in peritectic systems
(compositions in at.%)
System Peritectic reaction* Ca Cb CCritic Observation
Coupled Banded

Sn-Cd 223 C 0.75%Cd 2.1%Cd 1.55%Cd 1.0–1.3%Cd [19]
L þ a ! b
Pb–Bi 184 C 23.3%Bi 33.0%Bi 29.5%Bi 24–35%Bi [29]
L þ a ! b

Sb-Sn 246
Lþb
C
! b 60.0%Sn 89.8%Sn 79.6%Sn 85–89%Sn [6]

Cu-Zn 425 C 88.3%Zn 97.25%Zn 95.84%Zn 96.5%Zn [6]
L þ e ! g
Ti–Al 1463 C 37.3%Al 40.7%Al 39.6%Al 39.2%Al [8]
L þ a ! c

Ni-Al 1382 C 11.1%Al 12.4%Al 12.0%Al 11.9–12.4%Al [9] 11.7–11.9%Al [9]
L þ c ! c
Fe-Ni 1517 C 4.03%Ni 4.55%Ni 4.38%Ni 4.4%Ni [3]
L þ d ! c
*
Symbols for primary and peritectic phases have been left as they are in the references
Peritectic Coupled Growth Solidification—a Review
assumption about negligible influence of interfacial energies
of a/liquid ðaLa Þ and b/liquid ðaLb Þ that could be more reliable
in cases that both constituent phases have similar composi-
tions, crystal structures and solid/liquid interface atomic
structures. While, in Pb–Bi and Sb–Sn systems, the aLa is less
than aLb . Moreover, two important limitations are attributed to
this method: the influence of G/V ratio and convection that
have not been considered. G/V plays a significant role to
obtain a coupled growth zone in binary peritectic systems.
Also, thermal and solutal convection have a strong effect on
the local composition especially at smaller growth velocities
that remains to be investigated [28].
Fe–Ni Alloy System
PCG formation in Fe–Ni alloys has been a point of interest
during last two decades. Experimental results developed by
Vandyoussefi et al. [30, 31], Hunziker et al. [3], Dobler et al.
[12], Karma et al. [32], Luo et al. [33, 34] and Feng et al.
[35] revealed continuous growth of primary and peritectic
phases with both plane front or cellular front of one phase
and plane front of other phase.
Fig. 3 Fe-Ni peritectic a phase
diagram with metastable
extensions of liquidus and
solidus, and b experimentally
observed microstructures as a
function of G/V and C0
microstructure limits according to
the NCU model [12]
1037
In Fe–Ni alloy, due to similar densities of solute (Ni) and
solvent (Fe), solutal convection in the liquid was expected to
be minimal. Also, the difference between the composition of
the primary solid phase and the liquid is small; i.e., the
partition ratio (k) is close to one, and the freezing range
(ΔTf) is narrow. Achieving morphological stability for the
primary phase would require moderate, readily achievable
thermal gradient to growth rate (G/V) ratios. Therefore
isothermal peritectic coupled growth of Fe–Ni alloys was
considered likely.
A schematic of the Fe–Ni phase diagram is presented in
Fig. 3a. To keep consistency in this chapter, the conven-
tional d and c symbols have been substituted by a and b for
primary (ferrite) and peritectic (austenite) phases, respec-
tively. Figure 3b shows the influence of G/V ratio and solute
concentration on the microstructure formation in Fe–Ni
system. The dashed red line shows the critical composition
for PCG formation calculated by Ma et al. [28].
To develop stable PCG structure, rapid solidification
technique was employed by researchers to avoid peritectic
transformation that appear after solidification. Dobler et al.
[12] directionally solidified Fe3.5–4.5 at.% Ni alloys and
postulated three essential conditions for stable PCG devel-
opment. First of all, the phase with more solute rejection
1038
Fig. 4 a Isothermal peritectic coupled growth in Fe-4.3Ni alloy,
V = 5 lm/s b schematic map of diffusion paths of Ni. The inset in
(a) is a backscattered SEM image showing the irregular liquid/a
interface [37]
should have a steady state growth with planar/cellular front.
Second of all, G/V ratio should be more than a critical values
to develop a stable growth front; and finally, because of the
oscillatory instability of the phases, lamellar spacing should
remain in a specific range [36]. Figure 4 reveals PCG for-
mation in Fe-4.3 at.% Ni. As is the case in eutectic coupled
growth (ECG) the near plane front a and b phase grow
isothermally in the liquid. As indicated by the arrows in
Fig. 4, due to dissolution of a during peritectic reaction [1]
(usually appears for fine a-phase), the L/a interface is con-
cave near the trijunctions of L/a/b. a grows with less solute
(Ni) compared to b, leads to solute atom diffusion from L/a
to L/b interface [37]. Parallel to this, diffusion of solute to
L/b interface may cause lack of solute atmosphere next to
Fig. 5 Stable cellular coupled
growth in Fe-4.0Ni alloy,
V = 15 lm/s. a Longitudinal
section b cross section and
c schematic map of diffusion
paths of Ni Arrows A and B
indicate the peritectic reaction and
direct solidification, respectively
[37]
P. Shahbeigi-Roodposhti and H. Brody
the L/a interface which leads to solute (Ni) adsorption from
liquid. A dynamic motion appears in trijunction due to these
two opposing diffusion fluxes, making the PCG unstable
[37].
The second most abundant type of PCG that appear in
Fe-Ni alloy is known as non-isothermal cellular coupled
growth [37] in which cells of primary a phase form when
G/V is decreased to lower than morphological stability of the
a phase (6  108 < G/V <1.4  109 (Ks/m2) for Fe–Ni
alloy). In fact, G/V decreases below the planar growth limit
of the primary phase (a), however it is above the stability
limit of the peritectic phase (b). In this limited range of G/V,
cells grow at the same velocity and different temperature
than the intercellular plane front peritectic phase (b) (Fig. 5).
Figure 5c shows the concave L/a interface and diffusional
coupling between a cells and near plane front b. The con-
cave shape of L/a interface is due to dissolution of a during
peritectic reaction that decreases the volume fraction of a
near the L/a/b trijunctions. Distance “l” in Fig. 5c is another
important parameter that influences the morphological sta-
bility of the cellular PCG. At l more than a critical length of
lc, the peritectic reaction cannot influence the growth of the
cell tip, and cells reach to steady state condition. However
for l less than lc the growth behavior of a cells tip can be
influenced by peritectic reaction near trijunctions and make
them unstable [38]. Figure 6 reveals unstable cellular PCG
in directionally solidified Fe–Ni alloys.
The PCG formation mechanism as proposed by Dobler
et al. [12] consists of three steps. Island banding formation,
1-k oscillatory instability and finally oscillation decreases
leading to stable PCG formation. However, another mech-
anism has been postulated by Feng et al. [36] in which PCG
originates directly from the primary a phase. The primary
a-phase rejects solute to the liquid, increasing solute con-
centration at the solid/liquid interface. The temperature of
the interface reduces as a function of time that can facilitate
nucleation of the peritectic phase (b) at the a/L interface. At
Peritectic Coupled Growth Solidification—a Review
Fig. 6 Unstable cellular PCG in
directionally solidified Fe-Ni
alloys. a Fe-4.3Ni, V = 10 lm/s
and b Fe-4.5Ni, V = 10 lm/s
[37]
Fig. 7 Peritectic coupled growth in directionally solidified
a Fe-4.20Ni b Fe-4.34Ni and c Fe-4.51Ni (G = 30 K/mm,
V = 15 µm/s) [36]
high nucleation rates, the distance between nuclei decrease
and b island bands appears. This is the initiation of the PCG
[23]. Then growth is developing by squeezing of the primary
phase through peritectic phase at constant velocity. Figure 7
reveals Feng’s experimental results for three different Ni
compositions.
Ni–Al Alloy System
Peritectic coupled growth in Ni–Al alloys was observed
prior to Fe–Ni alloy. Lee and Verhoeven [39] developed
cellular coupled growth of a + b at low G/V ratio in which a
cells were surrounded by b intercellular phase [9]. Isother-
mal peritectic coupled growth in Ni–Al system bear mor-
phological resemblance to two phase cellular growth.
However unlike typical peritectic cellular, they are isother-
mal. Cells are smaller in thickness, the cell walls are not
1039
Fig. 8 Transition from single phase c growth through banded growth
to cellular peritectic growth in Ni-Al alloy [9]
straight and the structure formation is not in the constitu-
tional super cooling for two phases growth [9]. As it is clear
in Fig. 8, a transition from banded structure to cellular
coupled growth appears in the sample. a-phase appears at
the bottom, then bands of peritectic phase and finally verti-
cally oriented cells. Curved bands of b phase first formed at
the outer surface of the sample and continued to the center to
give the curved band of ß observed at the bottom of Fig. 8.
The b phase at the top of the micrograph (white horizontal
band), developed during quenching [39], terminates the
cellular coupled growth. The lower border of this band is the
solid/liquid interface during quenching.
Ti–Al Alloy System
Laser resolidification technique was employed by Liu et al.
[40] to investigate possible peritectic coupled growth in Ti–
Al alloy. In this method, the exact growth velocity could be
measured [1]. PCG in the form of lamellar structure, parallel
to the growth direction, appear in the bottom region of the
1040
Fig. 9 SEM micrograph of
resolidified hypoperitectic
Ti47Al53 alloy, a lamellar
structure at the bottom, b irregular
blocks at the middle, and
c equiaxed structure at the upper
section [40]
Fig. 10 Schematic diagram of morphology evolution in the laser resolidified Ti–Al peritectic alloy, a lamellar at the bottom, b blocks formation at
the middle, and c surrounding of the c-phase by a-phase at the upper part [40]
laser remelt pool as demonstrated in Fig. 9a. At the middle
part (Fig. 9b), irregular blocks and at the upper region
(Fig. 9c), equiaxed morphology are observable. Morpho-
logical evolution of the resolidified sample has been
described in Fig. 10. At the bottom, the coupled phase
arrayed regularly, analogues to that has happened in the Fe–
Ni alloy followed by initiation of irregular blocks of c-phase
that eventually surrounded by black phase of b [40].
Conclusion
Various peritectic coupled growth mechanisms in three
important peritectic alloys (Fe–Ni, Ni–Al and Ti–Al)
have been investigated. In Fe-Ni alloys, isothermal
P. Shahbeigi-Roodposhti and H. Brody
lamellar PCG forms at relatively high G/V ratio and
non-isothermal cellular PCG develops at lower G/V. Two
different mechanisms are involved in PCG initiation in
Fe–Ni: (1) island seeding and (2) directly from primary
phase. PCG in Ni–Al is isothermal and cellular with
non-straight cell walls at low G/V ratio. First primary
phase solidifies, followed by some bands of peritectic
phase and final transition to isothermal cells. In Ti–Al,
there are two peritectic phases (b and c). First the reg-
ular lamellar phase, analogous to PCG in Fe–Ni appears
then irregular blocks of c initiated and surrounded by b
phase.
Acknowledgements The authors are grateful for the support of the
office of the provost, University of Connecticut.
Peritectic Coupled Growth Solidification—a Review
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 Part XXIV
Cast Shop Technology: Casthouse
Management and Automation
 Overpressure Due to a Molten Aluminum
and Water Explosion in a Casthouse

Jennifer Woloshyn, Andrew Gerber, Tom Plikas, Duane Baker,

and Adam Blackmore

Abstract
Explosions of molten aluminum and water are a very serious safety risk in aluminum
casthouses. Although prevention of these explosions is of paramount importance,
understanding the overpressure resulting from an explosion is important for worker
protection and to the design of blast-proof control rooms and protection of other equipment.
Overpressure has traditionally been assessed using a simplistic principle of decreasing
overpressure with distance, which neglects the significant, complex interactions of the blast
wave with walls and other bodies, resulting in regions of high overpressure not captured
using simpler hand calculations. Computational fluid dynamics (CFD) modeling presents a
method to analyze the problem in three dimensions. Blast analysis of a full casthouse with a
conventional commercial CFD code can be time-prohibitive. This chapter presents a
methodology to predict overpressure due to a molten aluminum-water explosion in a
casthouse using a new manycore CFD solver—EXN/Aero developed by Envenio Inc.
Results for a casthouse explosion are presented to demonstrate the use of this analysis in
developing explosion-proof designs for control rooms and other equipment.

Keywords
Casthouse Explosion Overpressure CFD

Introduction emerging, manycore high-performance computing (HPC)

The analysis of pressure blast waves in air resulting from
industrial explosions can be modeled with compressible
transient computational fluid dynamics (CFD) methods. To
obtain these CFD solutions with appropriate mesh resolution
in a time frame supportive of industry design cycles can
involve a relatively large multi-core CPU supercomputer in
the range of 100 cores. An alternative is to take advantage of
new high throughput GPU co-processors, working in concert
with low latency CPUs, to accelerate solutions. The CFD
code EXN/Aero was designed entirely for the rapidly
J. Woloshyn
T. Plikas (&)
D. Baker
A. Blackmore
Hatch Ltd, 2800 Speakman Drive, Mississauga, ON, Canada
e-mail: tom.plikas@hatch.com
A. Gerber
Enveno, 46 Dineen Drive, Fredericton, NB, Canada
resources. Solutions such as the casehouse explosion are
then possible on powerful desktop scale systems.
The commonly used engineering approach to determine
overpressure on structures and equipment subjected to a
blast wave is to estimate explosion maximum overpressure
at the source, and then calculate a decreasing overpressure
with distance thereafter. One-dimensional methodology
typically considers a semi-infinite environment (with a rigid
floor). In this simplified domain, the maximum overpressure
decreases exponentially with distance from the source. This
methodology neglects to take into account the complex
interactions between the blast wave and surrounding struc-
tures, equipment, or bodies, which could alter the magnitude
and duration of the overpressure locally.
A CFD analysis can be performed to provide a more
representative assessment of the overpressures that a par-
ticular casthouse may experience in the event of an

© The Minerals, Metals & Materials Society 2017 1045

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_126
1046
explosion. Such an analysis inherently takes into account the
interactions between the blast waves originating from the
explosion event, and the surrounding structures, bodies,
equipment etc. The analysis is done in 3D, and consequently
provides an assessment that is unique to the particular
casthouse.
Past efforts to solve these types of problems using CFD
analysis have been plagued by exceptionally long computer
run times, often far in excess of the typical engineering
design cycles, making them prohibitive for evaluating sev-
eral design iterations. Making simplifying assumptions in
the modeling to accelerate the turn-around time only creates
uncertainty in the accuracy of the results, rendering them
inappropriate for engineering deployment. To this effect,
CFD modeling of blast wave propagation has mostly been
the domain of the academic and research communities.
As earlier outlined, EXN/Aero offers the potential to
solve these types of problems within typical project timeli-
nes and required levels of engineering accuracy. The soft-
ware has been designed specifically to deal with
computationally intensive CFD applications, such as the
blast wave problem. The efficiency is achieved by a software
design that sends ‘all’ tasks, not just the solver task, in the
CFD solution to the processor resources most optimal for
reducing solution times. In this manner serialization of
portions of the CFD solution is avoided. Furthermore,
EXN/Aero allows for a varied combination of structured
and/or unstructured mesh elements with single and/or double
precision. This allows the CFD problem to emphasize
structured single-precision processing on GPUs, where
possible, which can lead to significant additional speed-up.
In the present case, the geometry of the casthouse allowed
for structured blocks to be used. Due to the strong blast
waves the explosion, the simulation require double precision
throughout.
Background
A molten metal and water explosion involves complex
physical and chemical processes, the details of which are
beyond the scope of the current study, and only summarized
here. The total energy from a liquid aluminum-water
explosion can be categorized into a Force 1, Force 2 or
Force 3 explosion [1], and is composed of several compo-
nents including: (1) the rapid vaporization of water and
expansion of steam; (2) the reaction of the water and oxygen
with the molten aluminum ðfor example; 2Al þ 6H2O !
2AlðOHÞ3 þ 3H2Þ; (3) reaction of the air with the hydrogen
evolved from the previously mentioned reactions; and (4) an
aerosol of dispersed aluminum droplets may form and
explode [2]. The details of these reactions are outside the
scope of the present analysis and do not add significant value
J. Woloshyn et al.
in terms of estimating the resulting pressure isobars.
Therefore, for the method presented a simplified approach is
taken whereby a specified pressure pulse is applied at the
source. The actual energy of the blast would be expected to
have a component from the steam explosion and a compo-
nent from subsequent chemical reactions. The imposed
pressure wave accounts for the energy from both of these
components in generating a single blast wave that is effec-
tively surrounding the detailed steam and chemical
explosion.
The result of this complex process at a distance of three to
five-times the near field explosion radius is a rapidly
increasing pressure pulse similar to the one shown in Fig. 1
[3, 4]. A pressure pulse is characterized by the peak over-
pressure, the rate of increase, and the rate of decrease after
the peak.
A detailed transient blast wave analysis is of great use
because it resolves the complex reflections off hard surfaces
such as walls, floors, large machinery blocks, etc.
One-dimensional analysis in idealized geometries such as a
semi-infinite environment cannot capture these effects. The
physics of these reflections and interactions are such that the
peak blast wave overpressure can easily be several times the
peak in an ideal, semi-infinite environment. For this reason,
capturing the reflections is very important for prediction of
the severity of injury to workers or damage to equipment.
The range of overpressure and severity of injury is [5]:
• <150 kPa: overpressure: minor injury, possible rupture of
tympanic membrane of the ear
• 150–350 kPa: moderate injury, low probability of pri-
mary lung damage
• 350–550 kPa: severe injury, primary lung damage and
probability of casualties
• >550 kPa: extreme injury and high probability of
casualties
Fig. 1 Typical explosion pressure pulse
Overpressure Due to a Molten Aluminum and Water Explosion …
Similarly, the full 3D, transient analysis is critical to a
proper assessment of overpressure on equipment and struc-
tures. The expected structural damage for a given over-
pressure is [6]:
• 2–5 kPa: Damage and shattering of glass
• 7–10 kPa: Corrugated steel or aluminum panels buckle
and may fail
• 14–20 kPa: Non-reinforced concrete panels fail
• 17 kPa: Moderate damage to light steel framed buildings
• 28 kPa: Moderate damage to medium steel framed
industrial buildings
The overpressure ranges for structural damage may
appear surprisingly low compared to those listed for human
injury. The difference in the ranges can be explained by three
considerations. Firstly, building structures (glass, metals,
etc.) have typically higher elastic stiffness compared to
human tissue and hence much higher force response to the
applied blast wave is expected. Secondly, although building
materials vary in their ductility and response to high strain
rates from blast pressure waves, they tend to dissipate no or
much less energy as compared to human tissue. Thirdly,
building structures typically have surface areas that are much
larger than human tissues most susceptible to damage, such
as lungs, bowel, and middle ear. Further detail can be found
in [7–9].
Blast analysis and calculation of overpressure is just one
tool used to understand the risk due to an explosion.
Important safety risks such as spraying of hot metal and
flying debris are not considered. Nevertheless, the blast
analysis provides detailed information on local overpres-
sures, which is valuable for making informed design deci-
sions for blast safety, including structural design, design of
relief vents, or informing safety practices for personnel.
Discussion of avoidance practices can be found in many
sources [10–13].
Methodology
A detailed discussion of CFD methods is beyond the scope
of this chapter. For more information refer to [14, 15].
A brief summary of EXN/Aero is described in this section.
The EXN/Aero solver employed for this study uses a cell
centered collocated finite-volume discretization approach.
The equation matrices are generated for an implicit in time
solution so that no restriction on time step is necessary
although choice of time step must be based on time scales
relevant to the problem at hand. Pressure velocity coupling is
handled using the SIMPLEC approach, and the solution of
equation matrices uses an algebraic multigrid approach to
accelerate the solution. The multigrid solver is specifically
1047
designed for concurrent CPU/GPU use [16, 17]. Second
order in time discretization is employed along with the Van
Leer scheme for advection and second-order central differ-
encing for diffusion terms.
The solution sequence per time step involves solving the
high-speed momentum, pressure (mass) and energy equa-
tions first, resolving the strong coupling between these
equations by inner coefficient iterations, followed by solving
the SST turbulence model equations. The high-speed flow
solution uses an ideal gas equation of state and specific heats
for air. Deploying this solution sequence using the
EXN/Aero software design for manycore architectures,
described in Gerber et al. [17], allows for a very efficient
solution. In this case, solutions are obtained utilizing two
NVIDIA K80 GPUs working concert with three CPUs. The
10.6 million node mesh completed 30,000 time steps in
8 days with a time step of 1e-5 s.
Casthouse Case Study
A case study was completed with a generic casthouse
arrangement to demonstrate the analysis and its potential for
use for evaluation of safety scenarios and for equipment or
control room design. The model geometry is shown in Fig. 2.
The explosion source is assumed to be in the cast pit, as
indicated. The layout includes a number of pieces of nearby
equipment, which are assumed to absorb energy from the
blast rather than cause a reflection. This behavior is indicative
of machinery with complex shape that allows some flow to
pass. The geometry also includes a blast-protected control
room, an outbuilding, and a tank, all of which are assumed to
be rigid. A section of the building roof and sidewall are
removed within a radius for which 1D analysis shows that the
high degree of building damage would be anticipated. This
approach avoids an unrealistic reflection at a location where
the surface would be destroyed, thereby allowing the blast
wave to continue into the surrounding environment.
The blast wave is initiated by the pressure pulse boundary
condition, which takes the form shown in Fig. 1. The case
study considers a relatively mild scenario of 290 g of water
interacting with 1000 kg of aluminum. To calculate the
pressure pulse, the TNT equivalent is determined from lit-
erature [18] to be 0.93 kg TNT. The magnitude of the
pressure pulse and duration of the ramp-up portion are based
on the Kingery-Bulmash equations, which are commonly
used by US military, but not publicly published. Calculators
for the Kingery-Bulmash equations are nonetheless avail-
able, such as [19]. The resulting pulse, as applied in the
model, is shown in Fig. 3.
On this basis, for 0.93 TNT equivalent in a hemispherical
environment (rigid floor/ground surface near the explosion
source), the pressure at 0.9 m (which is the size of the source
1048 J. Woloshyn et al.

Fig. 2 CFD model domain

12 along a constant radial position from the blast source. The

Applied Overpressure at

remaining points are on objects of interest including the

10
control room, outbuilding, and the tank to the west of the
Source (atm)

8 casthouse.
6 Figure 6 shows the overpressure versus time at monitor
points C1 through C6. The time delay for the blast wave to
4 reach the points farther from the blast source is evident.
2 Interestingly, the points farthest from the source do not
necessarily experience the lowest peak overpressure. For
0
example, point C6 has a peak overpressure of 4.9 kPa while
0 1 2 3
point C3 has a peak overpressure of 3.0 kPa even though C3
Time (s)
is significantly closer to the source. The pressure reflections
Fig. 3 Applied pressure at source cause this behavior, which further demonstrates the impor-
tance of accounting for these complex 3D effects.
face) is an estimated 10 atm. The time for the ramp up in Figure 7 shows the overpressure versus time at monitor
pressure is estimated to be 0.4 ms. points C3 and C7 through C9, along a radius of constant
The progression of the overpressure in and around the distance, 1.3 m, from the blast source. As expected, the blast
casthouse over the first 0.3 s following the initiation of the front reaches these points at approximately the same time
blast is shown in Fig. 4. By 0.125 s the pressure front has and the initial overpressure peak is of similar intensity. The
reached two of the casthouse walls as well as the control effect of the pressure reflections off of walls and objects
room. The intensification of overpressure due to reflections causes deviation in the overpressure behavior after this ini-
off of these rigid walls is clearly observed. Equally signifi- tial overpressure peak.
cant is the pronounced negative overpressure that follows the The overpressure versus time on the four sides of the
overpressure pulse. control room is shown in Fig. 8. The peak overpressure
An important advantage of performing the analysis in observed on the control room in this scenario is 4.8 kPa.
three dimensions is the availability of transient pressure data This level of overpressure can be expected to cause damage
throughout the domain. Using this data the pressure at to glass and metal paneling with standard construction.
locations of interest can be used to select appropriate loca- A blast-resistant control room would be recommended.
tions for key equipment. Forces on proposed control room A delay is observed between reaching peak pressure at
walls can be extracted to inform appropriate design criteria points C10 and C13 as compared to points C11 and C12.
to withstand a given blast scenario. This delay is due to the travel time of the blast front. The
Figure 5 shows the location of monitor points considered effect of pressure reflections moving back towards the con-
for this case study. In all cases the points were taken 1.5 m trol room can be seen from 0.25 s onward, where a second
above ground level. Points C1 through C6 are along an distinct peak in the overpressure occurs.
east-west line halfway between the blast source and south The rectangular outbuilding is representative of a nearby
wall of the casthouse. Points C3 and C7 through C9 are building such as an electrical substation or equipment shed.
Overpressure Due to a Molten Aluminum and Water Explosion … 1049

0.050 s 0.075 s 0.100 s

0.125 s 0.150 s 0.175 s

PosiƟve
Overpressure

NegaƟve
Overpressure

0.200 s 0.225 s 0.250 s

0.275 s 0.300 s

Fig. 4 Contours of overpressure over the first 0.3 s following blast initiation
1050 J. Woloshyn et al.

8
C10
C11
C11
6 C12
C9 C10
C12
C13
C13
C8
4

Over Pressure (kPa)

C20
C21 C7

2
C1 C2 C5 C6
C3 C4

0
C14 C15 C16

C17 C18 -2
C19

-4
Fig. 5 Monitor point locations
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
Time (s)
12
C1 Fig. 8 Overpressure through time on the four sides of the control room
10 C2 (points C10-C13)
C3
8 C4
C5 4.0
6 C6
Over Pressure (kPa)

C14
3.5
C15
4
3.0 C16
2 2.5 C17
C18
Over Pressure (kPa)

0 2.0
C19
1.5 C20
-2
1.0 C21
-4
0.5
-6
0.0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
Time (s) -0.5

-1.0
Fig. 6 Overpressure through time along the front of the casthouse
(points C1-C6) -1.5
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
Time (s)
8
C3 Fig. 9 Overpressure through time on the “outbuildings” (points
C7 C14-C21)
6 C8
C9
4
The cylindrical structure represents a tank or silo. The
Over Pressure (kPa)

overpressure on these structures is shown in Fig. 9. Once

again, access to the overpressure information on these
2
structures can greatly assist in design of the structures and
inform safety practices.
0

-2 Conclusions

-4 Employing CFD technology that can efficiently utilize mixed

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 architectures (multi-CPUs/GPUs working in concert) can
Time (s)
lead to faster solutions on a supercomputer configured at
Fig. 7 Overpressure through time at r = 1.3 m from the source (points desktop scale. This has been demonstrated in a full
C3, C7-C9) three-dimensional casthouse simulation of the transient
Overpressure Due to a Molten Aluminum and Water Explosion …
overpressure waves due to a molten aluminum-water ex-
plosion event. The case study presented demonstrates that
the important contribution of pressure reflections are fully
captured and overpressure is determined as a function of
time throughout the domain.
Although safety risks such as spraying of hot metal and
throwing of solid objects must be separately considered,
three-dimensional CFD blast analysis provides detailed
information that is valuable for making informed design
decisions for blast safety, including: (a) structural design of
control rooms or outbuildings to withstand an explosion,
(b) design of relief vents, and (c) informing safety practices
for personnel.
References
1. S. Epstein, An Update On The Reported Causes of Molten Metal
Explosions, Light Metals (2007)
2. I.V. Babaitsev, O.V. Kuznetsov, Energy of explosions occurring
when water falls onto a layer of molten metal. Metallurgist 45(5),
185–188 (2001)
3. L. Barnard, Flame and Combustion, 3rd edn. (1995)
4. D. Crowl, Understanding Explosions, (2003)
5. S.G. Mellor, The relationship of blast loading to death and injury
from explosion. World J. Surg. 16(5), 893–898 (1992)
6. S.G. Lipsett, Explosions from molten materials and water. Fire
Technol. 2(2), 118–126 (1966)
1051
7. L. Davidson, Fundamentals of Shock Wave Propagation in Solids,
(Springer-Verlag, 2008)
8. W.K. Nowacki, Stress Waves in Non-Elastic Solids, (Pergamon
Press, 1978)
9. J.L. Davis, Wave Propagation in Solids and Fluids, (Springer-
Verlag, 1998)
10. S. Epstein, The Aluminum Industry’s Efforts to Prevent Molten
Metal Explosions, Light Metals (2003)
11. R.T. Richter, J.M. Ekenes, Cause and Prevention of Explosions
Involving DC Casting of Aluminum Sheet Ingot, Light Metals
(2005)
12. J.M. Ekenes, R.T. Richter, Cause and Prevention of Explosions
Involving DC Casting of Aluminum Extrusion Ingot, Light Metals
(2007)
13. J.M Ekenes, Training for Preventing Molten Metal Explosions in
Aluminum Cast Houses, Light Metals (2007)
14. S.V. Patankar, Numerical Heat Transfer and Fluid Flow, (1980)
15. J. Ferziger, M. Peric, Computational Methods for Fluid Dynamics,
2nd edn. (2001)
16. A. Eghbal, A.G. Gerber, E. Aubanel, Algebraic multigrid
employing mixed structured–unstructured data on manycore
hardware. J. Comput. Sci. (2016, in press)
17. G. Gerber, K.W. Wilcox, J.T. Zhang, Benchmarking of a
massively parallel hybrid CFD solver for ocean applications. in
Proceedings of the ASME 2013 32nd International Conference on
Ocean, Offshore and Arctic Engineering OMAE2013, (Nantes,
France June 9–14, 2013)
18. I.V. Babaitsev, O.V. Kuznetsov, Energy of explosions occurring
when water falls onto a layer of molten metal. Metall. 45(5–6),
(2001)
19. http://www.un.org/disarmament/un-saferguard/kingery-bulmash/
 Automation and Optimization of Sow Casting
in Alouette

JF Desmeules, JB Néron, and JP Bérubé

Abstract
Sow casting in Aluminerie Alouette Inc have undergone many optimization projects in the
past few years. In the cycle time critical path, actual pouring of the metal in the moulds
from the crucibles remained one of the most important parts. This operation was done
manually, leading to variability in duration as well as for sow weight. Sow caster capacity
is a function of the average weight of the sows and a reduction of the standard deviation can
help improve the average weight hence the capacity. A formula was developed to predict
the quantity of metal transferred in function of the crucible tilt angle and an algorithm was
built to optimize the pouring time. Implementation of the program was made in a very short
time frame and the results show that a reduction of the pouring time as well as the weight
standard deviation was obtained.

Keywords
Sow casting Automation Crucible

Introduction As for most smelters, continuous creeping of reduction

The Aluminerie Alouette Inc (AAI) smelter, located in
Sept-Iles, QC Canada, produces approx. 610,000 metric
tonnes of aluminium per year with an expected increase to
630,000 t/y in the coming years.
The first year of Phase 2,437,000 metric tonnes were cast
with 3 air cooled sow casting machines with the remainder
produced on water cooled ingot casting machines. This project
was subject to a thorough analysis in terms of heat loads to the
building and heat extraction capacity [1]. In 2015, all the
production (603,300 metric tonnes) was transferred on the sow
casting machines after stopping the ingot casting machines.
J. Desmeules
J. Néron (&)
Dynamic Concept, 2400 Alexis-Le-Trotteur, Jonquiere,
QC G7X 0J7, Canada
e-mail: jbn@dynamic-concept.ca
J. Bérubé
Aluminerie Alouette Inc, 400 Chemin de La Pointe Noire,
Sept-Iles, QC G4R 5M9, Canada
cell performance increases the metal throughput in the
casthouse. The pressure for production capacity on the sow
casters is thus increasing accordingly. Many improvements
have been made over the years to optimize the cycle time
and cooling capacity of the casters. Equipment reliability has
also been optimized. However, the core of the process could
still be optimized. The actual pouring of the metal in the
moulds, directly from the crucibles, is still done manually.
Although the operators have access to visual indicators to
optimize the sow weight, some variability is inherent to the
process, as well as the occasional rejects caused by off-limits
weights. During summer time, students are employed for the
operations and since they are less experimented, either
greater sow weight variability or cycle time increases are
observed (Fig. 1).
In order to allow for some weight variability, the target
weight is set to 720 kg. This is a target that is quite easy to
reach for the operators. The typical standard deviation is
approximately 25 kg, depending upon the operator. This
target weight is below the maximum LME acceptable sow
weight of 787 kg (LME Standards Part 6 Article 2: “The

© The Minerals, Metals & Materials Society 2017 1053

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_127
1054
Fig. 1 Crucible pouring operation
weight of each sow shall not exceed 5% more than 750 kg)
[2]. Considering that the cycle time is already optimized,
reduction of the standard deviation by the means of
automation could allow increasing the target weight to
770 kg, a direct production capability increase of 7% with-
out significant capital expenditure.
Limitations of the Actual System
The sow casting machine, capable of producing one sow
every 67 s, have a “window” of approximately 30 s for the
crucible pouring sequence. When the mould indexing is
done, a splash guard is lowered on the edge of the mould and
the tilting table is allowed to tilt up. The operator then
commands the tilting of the table until the metal is flowing
from the crucible. A Precimeter laser, coupled to a visual
indicator, provides information to the operator on the liquid
metal level into the mould, allowing the operator changing
the angle of the table to increase or reduce the metal flow
and eventually back tilt the table to stop the metal flow. The
most performing operators can fill the moulds quickly and
accurately without causing the casting operation to be the
bottleneck. However, since it is a manual operation subject
to variation in skill level, it is possible that the casting
operation becomes the bottleneck occasionally and the
variability of the sow weight remains a problem.
J. Desmeules et al.
Challenges Related to the Automation
The automation of the sow casting operation will reduce
substantially this variability and improve the metal casting
throughput. However, as easy as it might seem, many
challenges are posed.
The first challenge is safety. A crucible containing
approximately 12 t of molten aluminum is poured using a
tilting table. Under no circumstances a metal spill is
acceptable. The automation system must ensure that the
tilting of the table is done in a safely manner and detect any
unsafe condition prior to authorizing the inclination of the
table. The machine stays under the surveillance of an oper-
ator at all times. The operator still has to monitor the activity
of the equipment and enter production data such as crucible
identification, but since no safe method was found to detect
the moment when the metal is close to the spout edge, it was
decided that the initial tilting of the table up to the point
where the metal is close to the edge will be made by the
operator. When this angle is reached, the value is “teached”
to the PLC and it is used as the initial angle value from
which the first sow will be poured.
Then the cycle time limitation requires that the control
must be done without direct control of the inclination rate of
the crucible. Indeed, the turbulence caused by the high metal
flow at the initial stages of the mould filling and the dynamic
effects of metal movements within the crucible makes it very
Automation and Optimization of Sow Casting in Alouette
difficult to relate the inclination rate with the rate of metal
level increase in the mould. The reliability of the level
sensors also initially caused problems due to the turbulences.
However, trials were conducted in cooperation with
Precimeter to optimize the sensor parameters and location to
avoid false readings. Still, the automation must be done
without the capacity of controlling the crucible pouring in
closed loop with the metal level reading in the mould
otherwise this would result in unacceptable cycle times.
A major point in the establishment of the strategy of the
project was that minimal capex should be used. Therefore,
the use of load cells, as it is already done in other applica-
tions, was out of question due to the cost and production
delays that would occur for the modification of 6 pouring
tables.
Analysis of the Actual Operation Parameters
The first step towards automation of the system was an
analysis of the existing manual operations. The initial
thought was that the difference between initial and final
tilting angles of the table could be correlated with sow
weight and then a simple software with target “delta” tilting
angles (that is, for any given angle when the metal is just
about to flow from the crucible spout, adding a “delta” angle
to this angle would cause a predetermined amount of metal
to flow from the crucible).
A thorough analysis of the operation parameters was
possible thanks to the availability of comprehensive data
from the sow casting machines.
It was found that it is very difficult to correlate the tilting
angles of the table to sow weight due to many factors,
including:
• The operators will back tilt the table more or less when
the mould is full. It could be from near zero to up to few
degrees.
• When pouring metal, to increase the flow some operators
will tilt the table further than required and then tilt back
to reduce the flow. Other operators will tilt the table until
the flow appears satisfactory and then back tilt when the
target mould level is almost reached.
• Crucibles have different cleanliness levels. A clean cru-
cible will require less tilting angle for a given sow weight
than a fouled crucible.
• The last sows poured from a crucible are susceptible to
receive greater amounts of dross and bath from the cru-
cible, which can impact the final weight after skimming.
The operation data from the plant database was exported
to an excel spreadsheet. After some treatment required to
assign a sow number to the time it was poured at the casting
1055
station, manual treatment had to be done to determine the
angle of the table between each sow. The “backtilted” angle,
after each sow was poured, was determined to be the ref-
erence value for which the metal was transferred to the
mould. The angle difference between two sows was thus
supposedly the required angle to extract the amount of metal
according to the weight of said sow. Unfortunately, no
relation was found between tilting angle and sow weight.
This was later found to be caused by the aforementioned
reasons (Fig. 2).
Developing an Hybrid Control Strategy
The metal flow is in transient mode for all of the duration of
the pouring (approximately 25 s) and waves inside the cru-
cible as well as turbulence inside the mould prevent using
the metal level as an accurate source of information for the
control of the inclination rate of the table. Due to the short
cycle times available, an hybrid control strategy had to be
established. First, pouring of the metal at low flow, based on
preset tilting angle values of the table allows to pour a
determined amount of metal based on geometric calculations
of the crucible shape. When metal level is detected in the
mould, the table then moves to the high flow inclination
(high flow angle based on a factor applied to the delta angle
required to pour the sow). Then, when the filling is almost
complete and the turbulence is reduced, accurate and reliable
monitoring of the metal level in the mould is possible and
accurate timing of the back tilting of the table is possible.
This timing is adjusted depending upon the distance required
for the low flow angle. For example, at 17° the table has to
backtilt of 2° so the metal level target is set to 235 mm to
activate the backtilt. At 45°, the table has to backtilt of 6° so
the metal level target is set to 230 mm in that case. The table
tilts back to the low flow value less a small safety factor to
avoid metal dripping from the spout.
Furthermore, the control system can be adaptative to
crucible cleanliness level. A clean crucible has a greater
internal volume than a fouled crucible. Since the tilting angle
required to pour a given weight from the crucible is inver-
sely proportional to the internal volume, a clean crucible will
require less angle than a fouled crucible. Thus, after each
sow is poured, the system can reset its values according to
the last level and angle readings so that a better accuracy of
the loop is reached.
Open Loop “Coarse” Control
The goal of the open loop “coarse” control is to pour metal
as close as possible to the target weight without requiring
feedback from the mould level control system. It must be
1056
Fig. 2 Inclination of crucible versus time. Note The idle time during mould indexing is not shown Comparison of many crucibles could not allow
to deduct a good correlation
noted that for safety and sequence control purposes, the
metal level is monitored even if the reading is 90% accurate
due to extreme turbulence. However, a false reading with a
duration in excess of 3 s is considered too risky and then the
sequence is stopped. As mentioned above, improvement
work was done with the laser type and location, with
encouraging results to reduce the occurences of false read-
ings using customized sensors with improved electronics.
From any given angle, knowing that the metal is close to
the edge of the spout (that is, the “teach” command provided
by the operator for the first sow and then the self-teach
command after each sow is cast), the table will tilt to a preset
value according to a transfer table. The theory behind that is
that at any given crucible angle, if the metal fills the crucible
to the edge of the spout, then the amount of metal transferred
from the crucible to the mould will be a direct function of the
“delta” angle.
It is obvious that the amount of metal transferred from a
cylindrical crucible will be variable as a function of the
angle, since this value will be proportional to the area of the
free surface of the metal which will be maximal when the
bottom corner of the crucible will be at the same level as the
spout edge.
A mathematical model of the crucible had to be devel-
oped to generate the transfer table.
Development of a Mathematical Model
The objective of the mathematical model is to generate a
relational table for which, at any given inclination, the
amount of metal that will be poured for an additional degree
of inclination is accurately known (if the shape of the cru-
cible is the same as for the model, which is obviously never
the case since there are dross and bath accumulations).
J. Desmeules et al.
The shape of the metal inside the crucible can be modeled
as a truncated cylinder for angles between zero and the angle
for which the surface of the metal intersects the bottom
corner of the crucible. The volume is easily calculated as the
surface area of the circle times the average distance between
the metal surface and the bottom. This average distance is
equal to the distance of the spout from the bottom from
which is subtracted the radius of the crucible multiplied by
the tangent of the inclination angle.
For angles above the angle at which the surface of the
metal intersects the bottom corner of the crucible, the shape
of the metal inside the crucible is modeled as a cylindrical
wedge. The formula is more complex and is illustrated
hereafter (Fig. 3).
 
h  R2 3sin;  3;cos;  sin3 ;
V¼
3 1  cos;
One interesting thing with this is that the metal transferred
for each additional degree will increase from the horizontal
angle up to the moment where the surface of the metal
intersects the corner of the crucible. At this point, the metal
transfer is maximal. Then the metal transferred for each
Fig. 3 Cylindrical wedge Image source wolfram.com
Automation and Optimization of Sow Casting in Alouette
additional degree will decrease until it is reduced to zero at
90°′ inclination.
Since the metal transfer reaches a peak before decreasing
and the volume versus angle function is not continuous (with
two separate functions depending upon the inclination
angle), the derivative could not be found analytically. Thus a
Mathcad spreadsheet was used to generate a table for which
the exact volume of metal inside the crucible is known for
each degree of inclination. Then, this table was exported to
Excel to calculate the volume difference for each additional
degree.
The crucible is not always as clean as a new one. Using
data based on the geometry of a clean crucible would lead to
underestimated tilting angle for a given sow weight.
The exact shape of the dross and bath accumulation is not
constant from one crucible to another, however it is possible
to estimate the internal volume of a fouled crucible by
reducing the internal diameter and height from an estimated
dross layer thickness. Then, by computing again the table we
get another set of values based on a dirty crucible.
When comparing the amount of metal transferred for the
first sow to the predicted value, having these two tables
makes it possible to compute a “dirtiness factor”.
The initial model supposed that the height of the spout
was constant over the whole cycle. However, during the
implementation, it was found that the accuracy was less than
expected. After analysis, it was found that the original
mathematical model was inaccurate with regards to the
height of the spout. Indeed, the spout protrudes horizontally
from the shell of the crucible. Thus, the apparent height of
the spout must be reduced from the tangent of the inclination
angle multiplied by the horizontal length of the spout. This is
true for angles between zero and the angle of the bottom of
the spout and then the value is fixed to the height of the
bottom of the spout. The following picture shows the tilting
crucible with both possible maximum metal level lines, the
accurate line being the bottom one and the original calcu-
lation being the top one. The geometry has been simplified
for clarity purposes (Fig. 4).
The model was thus corrected to compensate for the
variation of the height of the spout. The final formula to
Fig. 4 Metal level in crucible according to inclination
1057
compute the volume of metal inside the crucible is modeled
using Mathcad programming and then exportation of the
data to an Excel spreadsheet. The figures shown on the
graph represents the maximal possible metal when the
crucible is filled to the edge of the spout. In reality, there is
some freeboard left but for an easier calculation, the
crucible is considered as full to the edge of the spout
(Figs. 5 and 6).
The transfer rate is equal to the derivative of the metal
transferred as a function of the angle. Since the function is an
assembly of sub-functions (each one with its angle range),
the derivative was computed numerically.
The principle for computing the inclination angle for a
given sow weight is as described in the following example:
If a 735 kg sow is to be cast using a clean crucible at a
starting angle of 20°, the transfer table indicates that the
metal transferred will be 310 kg/°. Then the delta angle is
735 kg/310 kg/° or 2.37°. The final angle is thus 22.37°
(Fig. 7).
It is interesting to note that the curve becomes flat near
the end because the inclination required to cast a sow is
equal to the inclination remaining to reach 90°, and thus it is
useless for example to cast a new sew starting at 82°.
Closed Loop “Fine” Control
Since the process is too quick to control the inclination of the
table by using the level sensor, as said above, the level
measurement is only used to trigger automated sequences
during the initial filling of the mould. However, the metal
flow decreases during the filling and the level control is then
used at the final stages to decide when the table should be
tilted back to stop the metal flow.
For safety, alarms are also implemented on the calculated
flow. For example, if the table is in the low flow position and
no metal is detected, then a low flow alarm is triggered. If
the flow is too high in the low flow position, then the table
will not tilt up to the high flow position.
It is therefore possible to achieve accurate and consistent
sow weights, with reduced cycle times.
1058
Fig. 5 Metal transferred as a function of the angle
Fig. 6 Metal transfer rate as a function of the angle
Implementation
With all the mathematical model and transfer tables in hand,
a first functional description was drafted.
The initial sequence required the operator to “teach” to
the system the initial angle for which the metal was almost at
the edge of the spout. Then, upon request of the operator, the
table would incline to the calculated angle for which a
J. Desmeules et al.
quantity of metal equal to the weight of the sow was
transferred from the crucible.
This control method proved to be relatively accurate
(taking into account the limitations due to the shape of
the dross layer and the initial errors caused by not taking
into account the spout height variation). However, the
cycle time was excessive because the metal flow was too
low.
Automation and Optimization of Sow Casting in Alouette
Fig. 7 Inclination required to cast a sow, as a function of the starting angle
Then, based upon observation of the operator’s best
practices, a modified sequence was designed.
For each starting angle, low flow and high flow inclina-
tion angles are determined using experimentally developed
correction factors that are applied to the “delta angle”
required to transfer the correct amount of metal. The high
flow angle is an inclination angle that is maintained for only
a few seconds in order to accelerate the metal transfer. The
initial inclination set point corresponds to the low flow
angle. Upon detection of metal in the mould (approx.
10 mm), the table then reaches the high flow angle until the
mould is full.
When the mould if full, the table tilts back to the final
angle (reduced by a small angle to avoid metal dripping from
the spout). This final angle becomes the new starting angle
for the next sow. If the operator cancel the sequence for any
reason, it is possible for him to teach the system a new
starting position at the beginning of the next cycle.
Results
The system has been operating in semi-automatic mode
since Q2 2016. Since then, no metal spills, overfillings or
safety incidents were observed.
The cycle time for the pouring operation is 25 s, which is
similar to the cycle time observed with experienced
operators. Since the process is automated, there is no vari-
ation to the cycle time as observed with less experienced
operators.
1059
The rejection rates caused by insufficient or excessive
weight were reduced from 0.43 to 0% as compared to the
average manual operations during the tests.
The standard deviation with the semi-automatic mode is
reduced to 20 kg. This result should be improved with the
implementation of the improved customized level sensors
and with the combination of reduced pouring times and
better accuracy, the casting machines will be sufficient for
the continuous increase of the metal production.
Increase of the sow caster productivity will eventually
have to be monitored with regards to heat load in the
building. The original nameplate capacity of the sow casters
was predicted on a basis of a much lesser tonnage per year
when designing the buildings.
Conclusion
Despite being challenging due to the use of a mix of open
loop and closed loop control strategies, implementation of
the automation of sow casting was successful. While keep-
ing low cycle times (and even allowing reduction of global
cycle times due to lower rejection rates and standardization
of operations from one operator to another), the system will
allow for reduced standard deviation of the sow weights,
permitting the increase of the target sow weight and thus
sow caster productivity without significant capital expendi-
ture. The next step will be the implementation of improved
level sensors to make the process robust despite the amount
of turbulence in the mould during metal pouring.
1060
Acknowledgements The authors would like to acknowledge Alu-
minerie Alouette for the permission to publish the results of the project.
A special thanks to the operator teams for their support during the
implementation of the automated system. We would also like to thank
Claude Lajoie from the automation department for his dedication and
hard work during the whole project.
J. Desmeules et al.
References
1. T. Plikas, et al. Casthouse design for the production of air-cooled,
low profile aluminium sows. Light Metals. 759–764 (2010)
2. London Metals Exchange, Rules and Regulations
 Radio Frequency Identification (RFID)
Technology for the Aluminum Industry

Valérie Langelier, Guillaume Parenteau, Martin Lysight,

and Maryse Beaudry

Abstract
The current trend in all industries is to maximize operation time while lowering production
costs. To achieve this goal, manual tasks, such as data monitoring, are being transferred to
automated systems and carried out by them. Radio Frequency Identification (RFID)
technology is one of these alternatives, in which electromagnetic fields are used to
automatically identify and track objects. The present paper will elaborate on the possible
RFID applications for the aluminum industry using examples from a project currently being
executed at the Alcoa Deschambault and Baie-Comeau smelters. The implementation of an
RFID system in a metal environment and the major factors that need to be considered
during the design will be described. This paper will also describe the field tests performed
by the Casthouse and Potroom sectors and the methods used to improve metal time
management and personnel safety.

Keywords
RFID Aluminum smelter UHF

Introduction Crucible traceability and the transmission of the metals

Alcoa Deschambault and Baie-Comeau smelters plan to
introduce RFID technology in metal management logistics to
improve their operation time. Until now, Kaizen workshops
are used to optimize work tasks and to increase the pro-
duction of aluminum. Even with the optimization of the
tasks, there is still manual work involved which in itself
causes a loss of time.
V. Langelier (&)
Hatch, 5, Place Ville Marie, Montréal, QC H3B 2G2, Canada
e-mail: vlangelier@hatch.ca
G. Parenteau
Epsilia, 462, Rue Des Forges, Trois-Rivières, QC G9A 2H5,
Canada
M. Lysight
Stantec, 1455, Rue Champlain, Trois-Rivières, QC G9A 5X4,
Canada
M. Beaudry
Alcoa, 1 Boul. Des Sources, Deschambault, QC G0A 1S0, Canada
characteristics are tasks that can easily be replaced by an
automated detection system.
Crucible traceability is accomplished by different
operators by means of a radio. The transmission of metal
characteristics such as weight, pot number, and chemical
composition is handled manually on paper. The metal
information is written, attached to the crucible, delivered to
the Casthouse and finally manually entered into the plant’s
process information system.
Crucibles are weighed and poured into one of the three
different furnaces in two possible ways. Metal can be
delivered into the furnace using a siphon or poured by tilting
the crucible with a crane. In each step, the information has to
be entered into the information system (weigh, crucible
number, chemical composition, metal pouring method, fur-
nace number). These repetitive tasks create a loss in time.
It is well known that manual operations requires constant
interaction between workers and mobile equipment and as a
result it is inherently dangerous.

© The Minerals, Metals & Materials Society 2017 1061

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_128
1062
Opportunities
The main reasons to install a RFID system is to improve the
transmission of the metals characteristics and the crucibles
traceability. The resulting factors are the reduction of man
hours, operating costs and the optimization of metal pro-
duction; all the while, improving plant safety by reducing the
interaction between workers and mobile equipment.
Challenges
The main challenges of integrating a new technology into a
brownfield smelter are overcoming various interferences that
are present in a smelter and the achievement of an optimal
distance between tags and antennas.
RFID Technology Description
RFID, radio frequency identification, is a technology
composed of tags, antennas, readers and a processing data
system. It is basically an exchange of data over a wireless
network. The reading and writing of the data passes through
a chip connected to an antenna which receives radio fre-
quency signals from a read-write device called a reader,
encoder or interrogator. As illustrated in Fig. 1, the data
exchange is carried-out automatically using an electromag-
netic or electrostatic signal in the radio frequency portion of
the spectrum. The tags receive a signal through an antenna
and respond by transmitting stored data, which may include
numbers, dates, time and temperatures. The reader receives
the signal via its antenna, decodes the information and
transfers the data to a computer via Wi-Fi or wired
communication.
Fig. 1 RFID technology
V. Langelier et al.
There are two main tag categories: passive and active.
A comparison on their characteristics can be found in Table 1.
Passive tags are the most commonly used given that they
are low in cost and quite durable. These tags are also small in
size and low in weight because they don’t require an internal
battery. Nevertheless, the lack of an internal battery means
that passive tags have limited memory and operational dis-
tance. Additionally, passive tags may have some perfor-
mance difficulties in environments where large amounts of
interference such as the presence of metals, liquids and other
radio frequencies are present.
Active tags on the other hand require an internal battery
or power source for continuous data transmission. These tags
have a longer operational distance, a higher cost and they
require a continuous replacement of batteries.
In addition to the differences listed above, passive and
active tags operate at different frequencies.
Passive tags operate at three main frequencies. There is
Low Frequency (LF, 125 or 134 kHz), High Frequency (HF,
13.56 MHz) and Ultra-High Frequency (UHF, 915 MHz).
The frequency range determines the read range, application
options and infrastructure material. A comparison on their
characteristics can be found in Table 2.
Low Frequency is cheaper and is able to penetrate
non-metallic material because of its long wavelength. Low
Frequency has a short range, about 1–50 cm. This frequency
is typically used for animal tracking.
High Frequency has a medium wavelength. This fre-
quency is very popular for electronic payments like Paypass
and for the Near Field Communication (NFC).
Ultra-High Frequency (UHF) has a short but high energy
wavelength which provides a better range and a faster data
transmission. UHF is typically used with asset tracking and
race timing. In general, higher frequencies will provides
short but high energy wavelengths and, consequently, long
read ranges. However, the higher the frequency, the more
interference it will likely have with metal or water.
Active tags operate at two main frequencies: 433 and
915 MHz. Users generally prefer to operate with the
433 MHz because its longer wavelength helps to avoid
interferences.
RFID System Design
Why Choose RFID Instead of Barcode?
The three main reasons why a company would use RFID
instead of a barcode first and foremost because it allows for
automatic detection without any human intervention. Sec-
ondly, companies look toward RFID rather than a barcode
because of its ability to have very strong credentials. In fact,
crucible identification by a barcode method is virtually
Radio Frequency Identification (RFID) Technology … 1063

Table 1 Active and passive tags comparison

Passive Active
Power No power Battery
Read range Up to 30 m Up to 100 m
Data storage 128 bits (read-write) 128 Kbits (read-write)
Size Small (as credit card) Depends on application
Life Up to 10 years 3–8 years
Cost 0.10–5$ 20–100$
Industry applications Real-time location tracking in a high speed environment File tracking, supply chain management, smart label

Table 2 Passive tag frequencies comparison

LF (125 or 134 kHz) HF (13.56 MHz) UHF (915 MHz)
Capacity 64 bits reading only to Reading-writing tags with 512 bits of Reading-writing tags with 32 bits of memory
2 Kbits reading-writing memory (max: 8 Kbits with partition) (max: 4 Kbits with partition of 128 bits)
Transmission Below 1 Kbits/s 25 Kbits/s 28 Kbits/s
Read range 0–0.5 m 0.01–1 m 5–30 m
Reading Single or multiple Single or multiple Single, multiple and multi directional
mode
Limit Insensible to Less sensitive to electromagnetic Sensitive to electromagnetic disturbances and
electromagnetic disturbances other UHF
disturbances

unthinkable. On the other hand, the robust solution that
RFID tags offer is a plus. An imaging system can accumulate
dust on the lenses and therefore not read the information
properly. Finally, the third criterion that sets RFID’s apart is
their capacity to write information dynamically on the chips
memory.
Standards and Norms
During the design process, it is important to look at the
different standards and norms design.
RFID systems are standardized by their functionality,
operating frequency and communication protocol. This
standardization of the communication protocol is part of the
JTC1 committee, which includes the ISO (International
Organization for Standardization) and IEC (International
Electro technical Commission).
In Canada, there is also norm RSS-210 which specifies what
frequency can be legally used. This avoids having the risk of
using the same frequency of another application such as the one
used in a flight control tower. In Europe and USA they also
have specific RFID bandwidths. USA bandwidths are specified
in the norm FCC part 15, and are similar to those in Canada.
Alcoa Deschambault RFID Project Description
The Deschambault project consisted in installing an RFID
system in the Casthouse which included tags on the cru-
cibles, a laser position reader on the crucibles’ crane and
electronic interfaces on the tapping beams.
The electronic interface (iPad) on the tapping beams
located at the Potrooms allows operators to register the
operating data directly into the information system via
Wi-Fi. The use of paper is eliminated.
The crucible tags transmit the crucible number
information.
Antennas are installed in the Casthouse next to the
existing three scales as shown on Fig. 2 and next to and on
top of each of the three furnaces as shown on Fig. 3.
The RFID system tracks crucibles at each of these different
locations.
Antennas next to the scales are linked directly to the
existing operation system to allow the information system
to associate the crucible weight with the crucible number.
The antennas next to the three furnaces will then track the
crucibles that are siphoned. Antennas on top of the furnaces
will track the crucibles when the metal is poured using the
crane.
1064
Fig. 2 Antenna position at the
scales Antenna 3
Scale 3
Fig. 3 Antenna position at the
furnace
Alcoa Deschambault RFID Testing with Epsilia
To validate the RFID system performance in a smelter
environment, tests were performed with the help of Epsilia, a
RFID specialist firm from Quebec, Canada. These tests
allowed the verification of interferences produced by the
molten metal, the smelter’s environment and other frequency
noise.
The tests consisted in installing different types of tags on
the crucibles and verifying the signal intensity and reception
at different antenna and tag locations.
UHF passive tags technology was recommended by
Epsilia. The main reason was that passive tags have a lower
maintenance cost due to no battery requirement. Further-
more, the Ultra-High frequency range, data transmission and
memory are high enough for the application. Therefore, the
tests were performed using the UHF passive tags
technology.
V. Langelier et al.
Antenna 1
Scale 2 Scale 1
Antenna 2
Furnace
Side Antenna
Top Antenna
Four different tags suggested by Epsilia were tested. The
tags have different characteristics such as heat resistance and
range. The types tested were: Confidex Ironside, Xerafy
Micro, Troi Armored 300 and Omni-ID Dura 1500 as listed
in the Table 3.
The project used the reader Zebra FX9500 and the
antenna Zebra AN400 for the test. This equipment was also
recommended by Epsilia (Fig. 4).
The first series of tests were performed close to the
Casthouse scales. It appeared that the proximity of the
readers required to cover all the desired positions generated
an interference. For this reason, it was concluded that all
readers have to be activated one at a time by means of a
trigger. In the end, different triggers for each application
were used.
A trigger type was determined for each application. For
the scale, the trigger was the weight stabilization. For the
readers beside the furnaces, the trigger was the siphon
Radio Frequency Identification (RFID) Technology … 1065

Table 3 Different tags type

Tags Specifications Pictures
Confidex Medium range, medium heat resistivity

Ironside High range, low heat resistivity

Xerafy Micro Low range, high heat resistivity

Troi Armored 300c Low range, very high heat resistivity

Fig. 4 Reader and antenna used for the test

activation. For the readers on top of the furnaces, the
selection of a trigger was more challenging because the
pouring of metal with a crane is a mechanical operation.
Therefore, an electrical action had to be added in order to
determine the activation time of the antennas. A laser posi-
tion reader installed on the crane was added to the project
scope for this reason. The trigger is the location of the crane
at its pouring position during 10 s.
The position study of the antennas and readers confirmed
the number of the tags required for each crucible. The main
challenge was to obtain good tag detection while mechani-
cally protecting the antennas from mobile equipment, over-
head crane spreader beam and surrounding heat.
The scale system requires two tag positions on the cru-
cible. As shown in Fig. 2, the antenna had to be installed at
two different positions from the crucible. Therefore, as
observed in Fig. 5, the first tag is identified at position 1
while the second can be found at position 2.
To reach the detection of the antenna at the side of the
furnaces, the furnace system has a tag located at position 3.
Thus, the RFID system at ADQ has a total of 3 tags per
crucible.
Having the multiple tags on the crucibles caused the
antennas to detect more than one tag at a given time. To
resolve this problem a program was developed to segment the
different tag signals considering only the strongest signal.
1066 V. Langelier et al.

Tag 1

Tag 3
Tag 2

Fig. 5 Tags on a crucible

Furthermore, it appeared that the crucibles and the molten The tests consisted of installing readers and an antenna on
metal are a frequency barrier. This facilitated the determi- the crucible spreader beam at the strongest magnetic field
nation of the antenna position so as to optimize the seg- location (Fig. 6).
mentation of the tag signal. The greatest concerns were the signal reception, the
The distance between the tags and antenna (range) was readers’ resistance within a magnetic field for a prolonged
also measured. It was found that for the scales and the period of time and the mechanical resistance of the RFID
siphon positions the antenna and tags had an acceptable
range (close in distance). The metal pouring with crane
position was challenging, because the crucible is in constant
movement and the distance is therefore greater. However,
tests showed that the antennas are able to receive a tag’s
signal, including crucible movement, up to a 7 m distance.
Each tag was tested and analyzed at each position of the
RFID system. Tag position was validated by the number of
detections during 5 s, the maximum power reception and the
interferences between the other tags. The preferred tag was
the Confidex Ironside, due to its temperature resistance,
range and size footprint.
Another item that was analyzed is the optimal mechanical
support for the tags. The support has to have a good
mechanical and heat resistivity. A prototype was made using a
bent steel plate and Teflon; this prototype gave good results
because of its insulation air gap and was upheld as the solution.
Other tests were made by the Reduction team to verify
if an RFID system could work within a magnetic field. Fig. 6 Crucible spreader beam
Radio Frequency Identification (RFID) Technology …
devices when they are installed on heavy duty equipment
susceptible to collisions.
To overcome the mechanical collisions, the readers were
installed inside the lateral posts of the crucible spreader
beam. This position also created a sort of faraday cage effect,
which offers protection from the magnetic field. Some
readers were also installed but not turned on to verify their
mechanical resistance. After a month they were found to be
intact and operational.
A successful signal reception test was then performed
where the smelters strongest magnetic field was present.
Consequently, the use of RFID systems in the Potrooms was
found to be feasible.
Baie-Comeau RFID Project Description
The Baie-Comeau project consists on having crucible
traceability in the smelter. The project includes a system
which can detect crucible location and identification number
throughout the entire plant. The entire crucible route can be
detected and their path can be followed using the existing
operating system.
To do that, the project includes an intelligent crucible
transporter, an intelligent crucible crane and a crucible
detection system at the maintenance department.
To better understand the RFID project at Baie Comeau,
each point of the crucible route is described below.
First, the crucible is picked by the intelligent transporter
at the maintenance department to be filled with metal at the
reduction sector. This intelligent transporter is able to detect
the identification number and location of each crucible. To
do this, the transporter has two antennas, one to detect the
crucible’s number and another to detect the crucible’s
location. Therefore, a tag is installed on the crucible for its
identification number and other tags are installed on the floor
at various locations for detection of crucible location.
Therefore, when the crucible is picked up at the mainte-
nance department and transported to the reduction sector
parking lot, the crucible position and identification number
can be transferred into the operation system.
At the reduction area, the intelligent crane picks up the
crucible to be filled with aluminum from the pots. This crane
is also able to identify the crucible number using its own
antenna. After the crucible is filled with molten aluminum,
the crane then transports the crucible to the Casthouse
parking for further processing.
Before the metal is cast, the crucible is transported to the
skimmers, sow caster or TAC. All of these locations have
antennas which allow for crucible detection at every loca-
tion. After casting, the crucible is then transported to the
maintenance department, where it will either wait at the
parking lot or wait to be cleaned. Both of these locations are
1067
equipped with tags embedded in the concrete floor for
location detection.
As mentioned above, tags installed inside the concrete
floor are required, so that they can be protected from
mechanical collisions. However, testing of this installation
has not been conducted yet. The tests will be performed to
verify feasibility and to determine the depths (25, 50 or
75 mm).
One of the main challenges for the project is the seg-
mentation of the multiple tag detection. The program
developed by Deschambault will be reused, but it has to be
tested at the Baie-Comeau smelter. The RFID system oper-
ation inside the concrete floor and within a magnetic field is
another challenge because the magnetic field is stronger on
the floor and the concrete can create an additional interfer-
ence. Another challenge is the validation of the interference
under the crucible transporter. The metal plate of the trans-
porter can create frequency reflection and the metal can act
as a mirror for the frequency.
The Baie-Comeau project has many challenges that still
need to be resolved. Tests to resolve the pending questions
have not been performed at the moment, but they are plan-
ned to take place in spring 2017.
RFID System Implementation Guidelines
The RFID system does not require a complicated construc-
tion and installation strategy simply because the equipment
is small and light. However, some installation guidelines
have to be followed to ensure proper commissioning.
Antennas need mechanical protection from heavy
equipment or vehicles. Tags require mechanical protection
from heat and heavy equipment, but before investing in
heavy protection the cost of the tags has to be considered,
given that it might be cheaper to purchase an additional tag.
Readers have to be installed in dust resistant cabinets
(NEMA 4) and should be able to transmit the signal via
Wi-Fi or wired communication. Depending on the demand, a
communication cable may need to be installed. The RFID
system also needs a PLC which processes, manages and
acquires all the data. For the Deschambault project, testing
was done using an Allen-Bradley PLC. Triggers for the
antenna require some communication devices such as relay,
I/O, modules and a feeding block.
It should also be mentioned that the implementation and
commissioning of an RFID system requires elaborate pro-
gramming. For this reason, the full commitment from the
programming team is essential. At Deschambault, the pro-
gramming was performed by plant personnel, given that the
information is going directly into the Alcoa system. The
programming included the RFID system data acquisition and
processing, PLC, triggers, operation pages, operator
1068
interfaces and commissioning. The Deschambault plant’s
commitment facilitated the integration of this new technol-
ogy into the smelter.
Conclusion
From the Alcoa projects and testing, it was concluded that
for an aluminum smelter the preferred RFID technology is
the passive UHF technology. All the tests with this tech-
nology were successful at each location and system. Fur-
thermore, the system was developed by the Alcoa team
meaning that the system is not a black box and it permits
modifications.
The need of triggers was an important finding identified
during the testing. It is therefore important that during the
design phase the installation of triggers is considered when
V. Langelier et al.
there is a large number of readers since multiple readers
create a signal interference.
In conclusion, a RFID project’s success requires the use
of the right type of technology for the appropriate applica-
tion, the correct positioning of the tags and antennas with
respect to operations, the commitment of the programming
and operation teams since the project’s core is related to the
RFID devices programming and PLC. Additionally,
pro-actively managing the system’s testing and the envi-
ronmental interferences as well as the involvement and
alignment of all stakeholders is necessary to ensure that this
new technology is implemented successfully.
Acknowledgements Technical acknowledgements to Claude Roch-
ette, Alcoa Electrical, and Patrick Barbieri, Hatch Mechanical for their
support and involvement.
 Semi Finished Products Traceability
Improvement with Laser Marking

J.F. Desmeules, B. Côté, and J.D. Dufour

Abstract
Parts traceability is becoming more and more important in many industries. Among others,
automotive, military, aeronautics and medical industries have strict rules on parts
traceability. Different marking technologies can be used to meet these requirements.
Durability and reliability of the marking is very important. Also important is the automation
of the marking process to avoid any human error in the procedure. Improved traceability is
possible with lasers as compared to stickers and ink jet marking. A powerful, quick acting
laser is now available but safety of the installation in an existing process is essential and it is
one of the main design criteria. A successful integration of an equipment providing laser,
ink jet and micro-percussion in an existing production line was made while complying to
all safety and cycle time requirements.

Keywords
Traceability Laser Safety

Introduction an existing rolling slab sawing line at Alcoa Baie-Comeau,

Laser marking is proven to be an advantageous technology
for improved parts traceability. It is already used in many
industries for parts marking but it is still in the early stages of
deployment for the primary and secondary aluminium
industry. The main reasons for this was the lack of avail-
ability of marking equipment with sufficient power to mark
areas large enough to be read at reasonable distances for
large parts such as rolling slabs or sows. The workplace
safety aspects of using such powerful lasers is also of
concern. Finally, proper positioning of the equipment with
regards to the parts to be marked is also critical for the
efficiency of the marking process. A powerful laser marking
system is now available and have been successfully imple-
mented in cast houses.
An equipment combining laser, ink jet and
micro-percussion marking was developed to be installed in
J.F. Desmeules (&)
B. Côté
J.D. Dufour
Dynamic Concept, 2400 Alexis-Le-Trotteur, Jonquiere, QC G7X
0J7, Canada
e-mail: jfd@dynamic-concept.ca
Canada, in replacement for manual marking and labeling.
This application posed many challenges due to interference
with existing equipment as well as variable positioning of
the parts to be marked. The resulting equipment allows
combination of the various marking technologies.
Available Traceability Technologies
There are many technologies available for parts marking. In
the smelter or large cast house where the products are
semi-finished parts such as rolling slabs or sows, the
requirements are quite different than that of other industries
such as automotive or aerospace. It is important to know, as
a minimum, the alloy and weight of the ingot. Some cus-
tomers will also require identification of the producer and
batch number, and the producers will also want to put some
trade mark on their products. Large rolling slabs or sows
must be clearly identified from a good distance for proper
identification in a warehouse or storage yard. The metal can

© The Minerals, Metals & Materials Society 2017 1069

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_129
1070
be stored outside for years so good durability and resistance
to elements is required.
Manual Marking
Manual marking is still used in many plants. Manual painting
with stencils or identification with punches can provide a
very durable identification. However, this is labor intensive
and the risks of errors are omnipresent (Figs. 1, 2, 3 and 4).
Some plants also mark the heads of rolling slab using
code bars pre-printed on aluminium plates that are dropped
on the ingot heads at the end of the cast before it is solidified.
Although very durable, there is still the need to match the
codes manually and it is a manual operation that can present
some risks. There is a possibility that this step is forgotten
depending on the workload of the operators. The positioning
of the labels is also variable and this can cause problems
with automated label reading systems.
Fig. 1 Manual marking with
stencils
Fig. 2 Picture of manual
aluminium plates identification at
the end of casting
J.F. Desmeules et al.
It is also worth noting that manual marking of very large
parts pose a risk due to the possible pedestrian/vehicle
interference.
Stickers
Sticker marking can be automated. It has the advantage of
being limitless in terms of sizes and marking possibility.
Cycle time is usually not a concern. However, it requires
proper positioning of the ingot with regards to the marking
equipment and it requires a flat and clean surface for proper
adhesion. When marking rolling slab, this can be a concern
since there may be oil or cutting fluid residue on the surface.
Hot marking is also possible for sows. Since sows are
often very hot when demoulded from sow casters, stickers
with heat sensitive adhesives can be used. However, the
temperature must be within certain limits otherwise the label
will not adhere to the metal if it is too cold and it can burn or
detach if it is too hot.
Semi Finished Products Traceability Improvement … 1071

Fig. 3 Picture of ink jet

marking. The upper line on the
picture is the marking made with
automated ink jet. The picture
was taken during the
commissioning, hence the various
markings

Fig. 4 Picture of
micro-percussion stamping

One of the main concerns with stickers is also the high Durability of the marking can be a source of concern for
operating cost because of the consumables. products exposed to weather for long periods or for alloys
Problems can arise with the thermal treatment of certain that will be heat treated.
alloys, where the labels can either burn or detach.

Micro Percussion

Ink Jet Marking
Ink jet marking allows marking of very large characters on
the sides of rolling slab, which is an advantage for quick
identification from a distance. One other advantage is that it
is less sensitive to surface defects than stickers, at least for
large characters where surface defects will not affect
readability.
Ink jet marking, as for stickers, can be affected by the
presence of oil and cutting fluid residues on the surface of
the ingots. It requires some maintenance due to the use of
inks and solvents, but the cost of the consumables is rea-
sonable. The marking operation itself can be synchronized
with conveyor movement or made using a movable head.
The process has some sensitivity to the distance between the
head and the surface to be marked.
Micro percussion marking has the advantages of being very
durable since the surface is engraved. It is possible to mark
characters and even 2D codes such as Datamatrix (but not 1D
barcodes). However, the engraving is usually relatively small
and the contrast is low from the viewer’s standpoint. It is
generally used in conjunction with other methods such as
stickers and ink jet marking to provide a permanent engrav-
ing while the other marking will offer the convenience of
providing more direct information such as alloy and weight.
Stamping
Stamping of serial codes is possible using automated
marking system is also possible. This method has a very
short cycle time which is good for billet marking. However
1072 J.F. Desmeules et al.

Fig. 5 Picture of manual

stamping of a slab head

the amount of information that can be stamped is limited to a

few characters and no 2D codes can be stamped (Fig. 5).
Automated coding with serial code indexation is possi-
ble, but complete changeover of the information requires
tooling setup.

Laser Marking

Laser marking is relatively new to the primary aluminium

industry. Recent advances in the technology allowed for large
format, high contrast and durable markings [1] (Fig. 6).
The advantages of the laser marking is that complex
images and data can be “printed” directly on the surface. It is
possible to reproduce images and logos. The contrast can be
high as long as the proper parameters are set in the laser
controller. Complex information can be engraved on the
part, regardless of the surface finish and cleanliness. The
marking is durable, even with long exposure to atmospheric
conditions. Fig. 6 Picture of an actual laser label
The marking system can be programmed to adapt to the
part temperature. Slightly longer cycle times are to be
expected for colder parts. Parts up to 400 °C can be marked Challenges Related to Laser Marking
with high contrast.
Laser marking can pose some challenges for implementation
in a smelter or other large cast house. The main challenges
Summary Table are cycle time and safety.

Technology Cap. cost Op. cost Marking Durability Cycle time Surface Position
complexity sensitivity sensitivity
Manual marking – $$$ – – +++ – –
Stickers $$ $$ +++ – + ++ +
Ink jet $$ $$ +++ – ++ ++ ++
Micro $ $ ++ +++ ++ + +
percussion
Stamping $ $ + +++ + + +
Laser $$ $ +++ +++ + to +++ – ++
Semi Finished Products Traceability Improvement …
Cycle Times
Cycle time is a function of the size of the marking and the
power of the laser. When studying the implementation of a
laser for an existing application, first of all the available
cycle time must be evaluated. Rolling slab marking systems
typically have long “marking windows” available, while
billet marking can be in the order of magnitude of a few
seconds post-cutting.
When marking with a laser, to get a good contrast it is
advisable to “clean” the area surrounding the marking, that
is, to produce a tag where the black (that is, more of a dark
grey tone) areas will stand clear as compared to the sur-
roundings. The white “pixels” require less energy whereas
the black “pixels”. Thus, the more black areas the mark
contains, the longer the cycle time required [1].
When a laser marking system is installed to replace an
existing sticker marking system, it is often advisable to
redesign the marking pattern to optimize the cycle time.
It is possible to reproduce marking patterns similar to
stamping with cycle times around 5 s as shown on the fol-
lowing picture.
Safety
High power laser marking systems, capable of engraving
metal, can obviously pose a safety threat if installed and
operated inappropriately. Moreover, these lasers typically
operates at or around 1064 nm, which is not in the visible
range. This wavelength is between 400 and 1400 nm, the
most dangerous spectral range for retina damage. Therefore,
exposure to the beam to may not cause pain or a blinking
reflex. However, permanent damage can occur.
The direct laser beam can cause injuries up to a distance
of 100 m under certain conditions. This distance depends on
many parameters, including the laser power, the focal dis-
tance, the diameter of the beam and the Maximum Permis-
sible Exposure (MPE). For example, the MPE for the
Laserax Q-Switched laser at 1064 nm wavelength is
0.005 W/cm2.
The first direct reflections from the surface to be marked
are to be considered as dangerous as the direct beam for
safeguarding purposes. In fact, they are certainly less dan-
gerous since some of the energy is absorbed by the material,
but as it is difficult to evaluate how much is absorbed by the
material (especially for pure aluminium), it is safer to con-
sider that none is absorbed for safe distance calculations.
Second reflections from a black, diffusing surface such as
anodized aluminium are also harmful for the eye in a radius
within a certain distance around the intersection point.
1073
This also depends on many parameters, including the laser
power, MPE, the fraction of reflected energy and the angle
of reflection. Conservative evaluation with worst case values
gives a safe distance of 1 m. The following figure explains
schematically the configuration of the dangerous zones
(Figs. 7 and 8).
The typical installation is located within an enclosed area
with interlocked doors. The laser system can be energized
only when the area is free. However it is not always possible
or practical, so good safeguarding practices include detection
to ensure that the part to be marked is at the correct place and
that there is no possibility for the laser beam to “shoot”
outside the part. When the conditions are fulfilled, the laser
is “enabled” to mark.
Provision must be made to contain, from the intersection
point of the part to be marked, reflections in any direction.
For example, the surface may appear flat, but
micro-asperities, saw marks and flashings can cause the laser
beam to be diverted in any direction. Panels made of black
anodized aluminium or other diffusing media (plastics and
rubbers to be avoided since the laser could eventually
damage them) must be placed around the part to be marked
so that the hemisphere of possible reflections are absorbed.
The location of any surrounding guarding must prevent any
body part to be closer that 1 m from the diffusing surface.
A good practice is to enclose the laser source into some
kind of “tunnel” that will come close to the surface to be
marked so that most reflections will be captured inside the
tunnel, leaving only a gap to cover.
It is to be noted that an inflatable seal or brushes pressed
against the surface to contain the reflections cannot be
considered as a reliable safety device, since the integrity
cannot be monitored and a reflected beam could theoretically
pass through a scratch or between two asperities. Total
surrounding of the surface by rigid panels is a good way to
ensure a 100% safe operation.
Fig. 7 Picture of high speed laser lettering on billet
1074
Fig. 8 Typical safeguarding configuration
Brownfield Integration of a Multiple Marking
System
The Project
The overall project, which took place in a Canadian smelter,
consisted in the modernization of the ingot saw for a fully
automated process comprising a combination of ink jet,
micro-percussion and laser marking. The whole marking
process had to take place while the slabs were on an accu-
mulation table. Many different sizes of slabs had to be marked,
with ink jet marking on two lines on both longitudinal sides of
the slabs, and laser and pin marking on the heads. The heads
were as cast, meaning that the surface was not exactly flat due
to solidification recess that is variable from one size to another
and various imperfections caused by the removal of the skim
dams and combo bags at the end of the casting process.
All marking information was supplied to the marking
equipment via the plant software and network so the
equipment was fully automated (Figs. 9, 10, 11 and 12).
Ink Jet Marking
One of the challenges with ink jet marking was that the slabs
had different width and length. Moreover, the position on the
J.F. Desmeules et al.
conveyor could be different from one slab to another and the
alignment could not be guaranteed.
Since either side had to be marked with two lines of text,
a versatile solution had to be developed. 3D movement was
required, with an indexing system capable of moving the
marking system from one side to the other. The movement
along the slabs was assured by a rail with a servodrive and
timing belt. Horizontal and vertical movements were assured
using a servo-driven multi-axis system, itself mounted on a
rotary slewing ring for transferring from one side to the
other.
The Diagraph inkjet system marking head was equipped
with a rotary encoder so that marking was possible during
acceleration and deceleration without the need for real-time
synchronization with the translation axis speed. In order to
adapt to different widths and compensate for misalignment
of the slab, pressure was applied to the marking head
assembly (equipped with polymer wheels) by the horizontal
axis of the multi-axis system using open-loop torque control
on the servo-motor of the pressure axis drive. The marking
head was thus always in contact with a slight pressure on the
slab side, ensuring an optimal marking distance for every
condition.
Very low ambient temperature during the winter required
the use of acetone-based ink. This ink stays fluid at very low
temperature and no heating of the head is required.
Semi Finished Products Traceability Improvement … 1075

Fig. 9 Marking equipment

during shop testing

Fig. 10 Ink jet marking system

on multi-axis positioning system

Micro-percussion Marking
A Telesys marking system was used for the
micro-percussion marking. Location of the marking on the
ingot head is always the same, however the surface is not
always at a consistent orientation due to differences from
size to size. A swivel mounting system had to be designed to
accommodate for various surface inclinations and limited
pin travel.
This marking system was used as a redundancy for the
other systems.
Laser Implementation and Positioning
Challenges
A Laserax LXQ-100 system was selected for this applica-
tion. It is a 1064 nm, 100 W laser marking system.
1076
In order to ensure an optimal marking distance, the
positioning system locates the laser in two steps. The first
step consists in locating the marking laser enclosure to a
preset distance using the measurement from a laser distance
transmitter and a servo-driven positioner. This step fulfill 2
objectives: (1) To compensate for the variable position of the
ingot heads (due to different lengths) and (2) to position the
laser safety protections.
As for micro-percussion marking, since the laser focus
“sweet spot” is approximately ±3 mm from the ideal plane,
a 2-axis swivel mount laser supporting head was designed.
The supporting head is thus pressed against the ingot head to
ensure consistent distance between the laser and the surface,
using a pneumatic cylinder for the final approach.
Detection systems were put in place to ensure that the
laser would mark only in presence of an ingot.
Since the marking operation generates some fumes and
dust, an aspiration system was integrated to the supporting
head to keep the surroundings clean during the marking
Fig. 11 Picture of micro-percussion head
Fig. 12 Picture of laser marking
system enclosure during shop
commissioning
J.F. Desmeules et al.
operation. If no aspiration system is used, the laser beam can
dissipate upon contact with the dust particles, losing effi-
ciency, and dust can deposit on the laser lens which creates
further problems. With good aspiration, reliable perfor-
mances are attained. A camera then automatically proceed to
a reading of the mark to validate the operation and detect any
problem.
The laser model used was one with fixed focus, however
it is also possible to use a new version (that was not available
yet at the beginning of the project). This new model (Laserax
LXQ3DV-100) incorporates a 3D scanning camera so that
each pixel is at the right focus, providing optimal contrast on
uneven surfaces. The camera can also automatically validate
the result.
Laser Safeguarding Challenges
As described above, on of the major concerns when inte-
grating a laser marking system is the safeguarding. Care
must also be taken so that the system can safely be
commissioned.
In that case, the equipment is totally enclosed in an
exclusion zone so no human is allowed within the area
during operations.
The laser is only enabled to be activated when a slab is
detected in the correct position and the marking head is
correctly pressed against the slab. Flat black painted panels
are then automatically positioned around the area to be
marked to intercept any reflection. All laser guarding and
enabling instrumentation is use and monitored according to
machinery safeguarding best practices.
The safeguarding was studied to avoid any direct reflec-
tion outside the protected area.
During the commissioning, it is required to observe the
behaviour of the equipment. Since the laser is a Class 4 at
Semi Finished Products Traceability Improvement …
1064 nm, short duration exposure of the skin outside the
focal point is not harmful but eye exposure can cause
immediate damages. Special protective glasses were worn by
the field engineers.
Conclusions
A polyvalent slab marking system allows to clearly mark
multiple sizes of slabs. Ink jet marking provides large let-
tering for quick identification of the products in the storage
area while laser marking allows for a high contrast marking
with bar code, logos and lettering providing complete
information and automated reading systems capability.
Micro percussion engraving system allows for redundancy.
The laser marking is very durable regardless of exposure to
atmospheric conditions or heat treatments and the equipment
1077
provides low cost operation (no consumables) and reliable
identification of the products. This provides a very reliable
traceability solution for the cast house products at a rea-
sonable cost.
It is possible to install such systems in existing production
lines, provided that proper analysis is made for a safe
installation of the laser marking system.
Acknowledgements The authors would like to thank Xavier God-
maire and Alex Fraser for their contribution and Alcoa for the per-
mission to publish pictures.
References
1. A. Fraser et al., Important considerations for laser marking an
identifier on aluminum, in Light Metals 2016 (2016), pp. 261–264
 Structural Integrity Assessment of Pressurized
Ladles for Aluminum Smelting

Maher Al-Dojayli, Pouya Zangeneh, Alexandre Lamoureux,

Daniel Richard, Pierre-Louis Allaire, and Hamid Ghorbani

Abstract
Pressurized ladles, being closed, minimize aluminum dross due to oxidization and conserve
energy required for ladle preheating. Design of pressurized ladles is not addressed by ladle
design standards such as AISE Technical Report No. 9. This paper presents a
design-by-analysis methodology for structural integrity assessment of pressurized ladles
using finite element analysis and guidelines of ASME Boiler and Pressure Vessel Code.
Transient temperatures in the ladle shell during preheating and aluminum
charging/discharging are estimated and validated against site measurement data. Thermal
loads are then combined with gravity loads (ladle self-weight and molten metal charge) and
ladle internal pressure at different pressurization, lifting, and metal pouring stages. The
resultant stresses and deformations in the ladle are compared with the ASME allowable
limits against plastic collapse, thermal ratcheting and fatigue failures. This paper
demonstrates the robustness of design-by-analysis methodology for integrity assessment
of ladles under non-standard conditions.

Keywords

Pressurized ladles Aluminum smelting Structural integrity Design-by-analysis Heat
transfer Ratcheting Fatigue

Introduction dross as well as conserve energy required for pre-heating.

Effort is being made to minimize aluminum oxidation losses
in the form of dross generated during the operating cycle of
ladles and the discharging process. The use of pressurized
ladles is an example of such techniques, which can reduce
M. Al-Dojayli (&)
P. Zangeneh
H. Ghorbani
Hatch Ltd, 2800 Speakman Drive, Mississauga, on, L5K 2R7,
Canada
e-mail: maher.al-dojayli@hatch.com
A. Lamoureux
Hatch Ltd, 5 Place Ville Marie, Bureau 1400, Montréal,
QC H3B 2G2, Canada
D. Richard
Hatch Ltd, 322 Industrial Ave, Kitimat, BC V8C 2E9, Canada
P.-L. Allaire
Hatch Ltd, 5555 rue Pierre-Thibault, Bécancour, QC G9H 2T7,
Canada
Conventional non-pressurized ladle design commonly uses
the guidelines given in Association of Iron and Steel Engi-
neers (AISE) Technical Report No. 9 [1]. These design
guidelines are mainly based on design-by-rule methodology
and typical ladle loading, and do not account for internal
pressure loading in pressurized ladles. In addition, ladle
thermal profile and cycles are different in pressurized ladles
compared to those in conventional ladles. Failure to properly
account for cyclic loading in ladle design may lead to
damage such as ladle shell cracking or rupture as shown in
Fig. 1.
This paper presents a design-by-analysis methodology,
based on the guidelines of ASME Boiler and Pressure Vessel
Code (ASME BPVC II-Part D and ASME BPVC VIII-Div. 2)
[2, 3], for structural integrity assessment of pressurized ladles.
This approach can be used as a stand-alone structural integrity

© The Minerals, Metals & Materials Society 2017 1079

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_130
1080
Fig. 1 Cyclic cracking failures in industrial ladles
assessment or in combination with the guidelines of AISE
Technical Report No. 9. Finite element analysis (FEA) is
utilized to estimate the temperature and thermo-mechanical
stresses in the ladle. These stresses are compared with the
allowable limits in ASME BPVC against global and local
plastic collapse, cyclic ratcheting and fatigue failures.
A summary of this procedure is, outlined in Fig. 2, and may
be used for new ladle design as well as campaign life esti-
mation and extension of existing ladles.
Load Cases and Load Combinations
In this paper, an example ladle is investigated with a max-
imum capacity of 11.5 tons of molten aluminum. The ladle
internal operating pressure varies from a minimum of (−10)
psig during charging and maximum of 10 psig during dis-
charging. Each ladle operation cycle consists of charging the
ladle (over three equally charging durations and capacities),
transit to the cast-house, Treatment of Aluminum in Crucible
(TAC) operation, seated transportation, discharging, transit
to the pot-room and standby. This cycle results in nine Load
M. Al-Dojayli et al.
Combinations (LC), as shown in Table 1. In order to eval-
uate the ladle design, detailed thermo-mechanical analyses
and ASME code checking are needed for each load
combination.
Finite Element Model
Finite element analysis (FEA), using commercial FEA
software ANSYS v.15 [4], is used for the example ladle heat
transfer and thermo-mechanical stress analysis. This ladle is
made of ASTM A36 plain carbon steel material. Appropriate
meshing schemes are developed for the ladle geometry in
such a way to capture membrane, bending and local stresses,
as shown in Fig. 3.
Transient Thermal Analyses
Pressurized ladles undergo several heating stages during a
single operating cycle, including preheating, charging,
standby and discharging. Transient thermal analysis is
Structural Integrity Assessment of Pressurized … 1081

Fig. 2 Structural integrity

assessment procedure for
pressurized ladles

Table 1 Pressurized ladle load cases and combinations

Load combination (LC)
1 2 3 4 5 6 7 8 9
Load Case Support condition Lifted Lifted Lifted Lifted Seated Lifted Lifted/tilted Seated Seated
Capacity Empty Empty Full Full Full Full 25% Empty Empty
Temperature low low high high high high high High low
Internal pressure [psig] 0 −10 −10 0 0 10 5 0 0

therefore performed to estimate the range of temperatures
experienced by the ladle during one operating cycle. Infrared
thermography was used to validate the predictions of FEA
model both before and after the TAC operation.
Ladle operating cycles vary in duration, depending on
process requirements in terms of charging and standby. Two
extreme cycle durations are statistically identified, resulting
in high ladle temperature (high temperature cycle) and low
ladle temperature (low temperature cycle), as shown in
Table 2. These process durations are used in the FEA tran-
sient thermal model to estimate the ladle skin temperatures.
The thermal boundary conditions considered in the
analyses include the added mass and energy of the molten
aluminum, thermal conduction from the molten aluminum to
the ladle refractory, radiation within the inner surfaces of the
ladle, radiation from the free surface of molten aluminum,
1082 M. Al-Dojayli et al.

Fig. 3 Finite element model of ladle

Table 2 Pressurized ladle Process LC sequence Process duration [minutes]

operation
High Low Calibration
temperature temperature cycle
Cycle Cycle
Charging + inter-charging LC1, LC2, 3*(LC3, LC4) 11.7  3 2.5  3 5.8  3
(three times) (with incremental load)
Standby & transit to cast LC5, LC4, LC5 80.0 16.0 50.0
House & standby for TAC
TAC LC5 6.0 6.0 6.0
Standby & transit to furnace LC5 5.0 5.0 5.0
Discharging LC6, LC7 1.0 1.0 1.0
Standby & transit to pot room LC8, LC9, LC1, LC9 16.0 302.3 86.0
Total 143.1 337.8 165.3

and convection and radiation heat transfer of the ladle out-
side surfaces to the plant. For each thermal cycle, three
consecutive cycles are repeated to achieve steady-state
maximum and minimum ladle skin temperatures. Figure 4
shows the temperature development of a selected point on
the ladle steel shell versus time for the corresponding high
and low temperature cycles calculated in the FEA model.
In order to calibrate/validate the developed FEA thermal
model, a validation ladle was sent through the process with
the cycle information (calibration cycle) given in Table 2.
The measured temperature values are compared with the
predicted temperatures by the FEA model and found to be in
good agreement, with a thermography focused temperature
point of 169 °C compared to 164 °C predicted by FEA, as
shown in Fig. 5. The measured maximum temperature;
however, shows higher value than the predicted temperature
by FEA. This is believed to be due to the fact that the
infrared thermography measurements were performed on a
validation ladle on site, which might have gone through a
previous high temperature cycle, while FEA results are
based on repeated calibration cycles.
Stress Analyses
The highest and lowest temperature profiles are used to
calculate the thermal stresses in the ladle. Thermal loads are
combined with mechanical loads due to ladle self-weight
(steel and refractory), molten aluminum weight, internal
pressure and lifting/seating for the structural integrity
assessment of the pressurized ladle.
LC6 was found to be the most critical thermo-mechanical
load combination for this ladle, see Table 1, when the ladle
is full, lifted from the trunnion, under 10 psi internal pressure
Structural Integrity Assessment of Pressurized … 1083

Fig. 4 Temperature predictions of the selected point on the ladle steel shell

Fig. 5 Measured versus calculated temperatures in the ladle during standby in cast house

and at high temperature. Consequently, only the stress
results for LC6 are presented in the rest of this paper to
maintain the brevity of the manuscript.
Assessment Against Plastic Collapse
and Local Failure
According to ASME BPVC VIII Division 2, the sum of
bending and membrane stresses due to mechanical loads for
local primary and secondary stresses must be less than 1.5 S
and 3 S, respectively, with S being the allowable basic stress
for the material at the operating temperature [2]. Local pri-
mary stresses are mechanical membrane and bending
equivalent (von-Mises) stresses derived from internal
pressure, external loads and discontinuity effects [3]. Sec-
ondary stresses are equivalent stresses induced by thermal
expansion and displacement controlled loadings [3]. The
algebraic sum of the principal stresses is also required to be
less than 4S to meet local failure criteria, where:
S ¼ 114½MPa;
Temperature ¼ 40  350½ C for ASTM A36
These conditions are met for all of the nine load combi-
nations (mechanical loads only) for both plastic collapse and
local failure. Figure 6 shows the equivalent (von Mises)
stress distribution in the ladle steel shell from LC6, due to
mechanical loading only. Stresses of up to 152 MPa are
estimated for the ladle bottom, with the maximum local
1084
Fig. 6 Von-Mises stresses due to only mechanical loading in LC6
stress of 324 MPa at the bottom weld of the ladle hook
attachment.
Maximum primary stress: 150 MPa \ 114  1:5 ¼
270 MPa
Maximum secondary stress: 324 MPa \ 114  3 ¼
342 MPa.
Assessment Against Cyclic Ratcheting Failure
According to ASME BPVC VIII Division 2, the combina-
tion of linearized local primary membrane stresses, primary
bending stresses, and secondary stresses, should be less than
SPS , which is defined as the maximum of three times S, the
M. Al-Dojayli et al.
allowable stress, or two times Sy, the yield stress at the ladle
operating temperature.


SPS ¼ Max 3S; 2Sy ¼ Maxð3  114; 2  210Þ ¼ 420 MPa
Thermal stresses are calculated for both high and low
temperature cycles. The results show that thermal stresses
are substantially higher than the mechanical stresses and
govern the cyclic ratcheting assessment. Figure 7 shows the
equivalent stress distribution in the ladle steel shell due to
the combined thermal and mechanical loading for load
combination LC6, which produces the highest temperatures
and corresponding highest stresses in the ladle.
Structural Integrity Assessment of Pressurized … 1085

For the majority of the ladle steel shell, the combined (441 MPa) above the cyclic ratcheting criterion. For this
thermal and mechanical stresses are well below SPS . Only a point, the total linearized thermal stress Q, is 417 MPa and
small and localized region, located at the upper weld line the mechanical membrane stress Pm , is 22 MPa.
above the trunnion (Fig. 7), shows an equivalent stress

Fig. 7 Von-Mises stresses due to both thermal and mechanical loadings in LC6

Fig. 8 Fatigue sensitive areas in ladle

1086 M. Al-Dojayli et al.

ASME BPVC VIII Div.2 requires a supplementary cyclic
ratcheting criterion to be met for any point with stresses
exceeding SPS as follows:
 
Pm 22
X¼ ¼ ¼ 0:105
Sy 210
 
1 210
SQ ¼ Sy ¼ ¼ 2000 MPa
X 0:105
Q  SQ ! 417 \ 2000 MPa ! Pass
In summary, the ladle passes the ASME BPVC VIII
Division 2 protection criteria against ratcheting for all nine
thermo-mechanical load combinations listed in Table 1.
Assessment Against Fatigue Failure
Five of the highly stressed areas and the trunnion are
assessed against fatigue failure, using the guidelines of the
ASME BPVC VIII Div 2. Based on the average number of
operations and load cases per each of the ladle cycles given
in Table 2, fatigue life is estimated at six critical locations.
Figure 8 shows all the identified fatigue-sensitive areas,
using the operational information of the ladle. Certain
locations, such as the trunnion and bottom of the ladle,
experience sub-cycles in each operation cycle, particularly
when the ladle is seated/lifted, pressurized/non-pressurized
more than once. These sub-cycles are accounted for using
the Rainflow cycle counting.
The highlighted areas (2, 4 and 5) identify the regions for
which fatigue life is significantly reduced as a result of
pressurizing the ladle. In order to estimate the fatigue life in
the ladle shell, the through thickness linearized membrane
and bending stresses are considered at the peak stress
regions, produced by gross and local structural discontinu-
ities, in combination with the use of the structural stress
based approach in assessing the fatigue life [3]. These
stresses are calculated for all the nine load combinations,
given in Table 1, with the ladle operation sub-cycles in
Table 2. Fatigue life is estimated at these locations for each
sub-cycle, assuming grinded welds, then the total fatigue life
is calculated using Miner’s rule, see Table 3.
With the current ladle design and existence of the upper
ring stiffness, the fatigue life of the upper regions of the
ladle, areas (1 and 3), are not strongly sensitive to the
pressurizing effect. Rather, they are mainly impacted by the
ladle thermal cycles. It is clearly shown that ladle pressur-
ization is significant in reducing the fatigue life by an order
of magnitude in the ladle bottom regions, areas (2, 4 and 5).
This indicates that the current design of the example ladle
requires scheduled inspection for cracks, unless design
modifications are made in these regions. These concerns are
not captured by conventional ladle design procedures such
as AIST Technical Report No. 9.
These fatigue calculations are performed for a new ladle
and are intended to provide a framework for estimating the
remaining life of the ladle and establish a good measure to
perform inspections for fatigue cracks, repairs, and design
modification if required.
Trunnion Analysis
Fatigue life calculation for the trunnion is conducted based
on a highly refined sub-model. Figure 9 shows the equiva-
lent (von-Mises) stress distribution in the trunnion due to the
combined thermal and mechanical loading, including the
non-linear through thickness stresses (peak stresses) pro-
duced by gross and local structural discontinuities. This
model captures the behavior of the bolted connections of the
trunnion to the shell. This sub-model indicates that the
trunnion stresses are not sensitive to the ladle pressurizing
effect.

Table 3 Summary of estimated Area# Location Fatigue life (ladle cycles)

fatigue cycles in ladle with and
without pressurization With Without
pressurization pressurization
1 Upper corners of trunnion plates weld line to the 2600 3000
shell
2 Mid stiffeners of the ladle floor 284,000 5,000,000
3 Top weld of the belly belt stiffener to the shell 6500 7000
4 Shell and bottom plate weld line 14,600 33,000
5 Bottom weld of the tilting hook to the ladle 2400 5800
6 Trunnion 30,400
Structural Integrity Assessment of Pressurized …
Fig. 9 Von-Mises thermo-mechanical stresses (LC6) in trunnion with and without internal pressure
Conclusions
A general design-by-analysis procedure for structural
integrity assessment of pressurized ladles is presented in this
paper. Transient thermal and mechanical stresses were
estimated using finite element analysis and compared
against the allowable in ASME BPVC VIII Division 2 for
plastic collapse, local failures, cyclic ratcheting and fatigue
failures.
It is found that the pressurization significantly reduces the
ladle fatigue life, especially in the ladle bottom regions, such
as ladle bottom plate at the tilting hook, ladle wall to floor,
and ladle bottom plate weld lines. This is due to the com-
bined effect of internal pressure and higher ladle tempera-
ture, as a result of lower heat losses. Such insight into the
ladle integrity and campaign life may not be achieved using
1087
design-by-rule provisions of conventional ladle design
standards, such as AISE Technical Report No. 9.
The presented methodology is general and can be used in
design and design optimization of non-conventional ladles
as well as troubleshooting and campaign life extension of
existing ladles.
References
1. Specifications for Design and Use of Ladles, AISE Technical
Report No. 9, Association of Iron and Steel Engineers, Pittsburgh,
USA, 1991
2. ASME Boiler and Pressure Vessel Code, Section II, Part D, 2015
3. ASME Boiler and Pressure Vessel Code, Section VIII, Division 2,
2015
4. ANSYS Mechanical APDL Theory Reference, Release 15, 2013
 Has Recent Advances in Direct Chill Casting
Made Us Less Safe?

Alex W. Lowery

Abstract
The frequency and severity of molten metal explosions in our industry has increased over
the past decade. This paper considers if recent technology advances in direct chill casting
processes resulted in our industry downplaying this hazard. Through analysis of past
research studies, molten metal incident reporting data and review of the recent explosion
that destroyed the Noranda Aluminium cast house. The causes of molten metal explosions
are considered and explored. I argue that recent molten metal explosions could have been
prevented if the past research studies’ conclusions were adopted as best practices.

Keywords
Molten metal Explosions

Introduction Reporting System. This program, administered by the Alu-

Whenever two liquids with widely different temperatures
come into contact, an explosion can result. This explosion is
purely a physical phenomenon. There is an additional con-
cern with aluminium because it is a very reactive chemical
element that has a strong chemical attraction for oxygen.
Aluminum is almost always attached with Oxygen in nature.
Just as aluminium requires a large amount of energy to break
the aluminium-oxygen bonds and produce metallic alu-
minium in a reduction cell, that energy will be released if the
aluminium is able to recombine with the oxygen from either
water or air. The energy released of one half kilogram of
aluminium fully reacted with oxygen is equivalent to deto-
nating 1.4 kg of trinitrotoluene (TNT).
2Al þ 3H2 O ¼ Al2 O3 þ H2 þ Energy
There are three distinctly different types of explosions
that can occur when molten aluminium comes in contact
with water as defined by the Molten Metal Incident
A.W. Lowery (&)
Wise Chem LLC, P.O. Box 633, New Albany, OH 43054, USA
e-mail: ALEX.LOWERY@WISECHEM.NET
minium Association since 1985, is credited for bringing
awareness to this hazard. In that system the different
explosions are defined as Force 1, Force 2, and Force 3,
which are categorized as follows:
Force 1 explosions, also referred to as “steam explosions”
or “pops”, occur when molten metal traps water that
quickly turns to steam. These explosions are characterized
by metal thrown a short distance, usually up to about 4.5 m
and often less than 4.5 kg, with minimal to no property
damage.
Force 2 explosions are violent steam explosions. As with
Force 1 explosions, water is trapped and instantaneously
turned to steam. But in this case, the water is trapped by the
molten metal and pressure builds to the point that consid-
erably more metal is thrown a great distance of 4.5–6 m,
often to the roof of the plant. There may be some accom-
panying equipment damage.
Force 3 explosions are catastrophic events arising from
reaction of molten metal with oxygen from water, air or both.
They are characterized by considerable property damage and
metal dispersed more than 15 m away. Often the metal has
disappeared and what remains is a white powder—aluminium
oxide. An example of a Force 3 explosion is shown in
Picture 1.

© The Minerals, Metals & Materials Society 2017 1089

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_131
1090
Picture 1 Force 3 explosion
The explosion locations vary from melting, casting,
charging, etc. Most explosions reported over the 25 years
have occurred in casting operations.
Past Research Studies
Hess and Brondyke
Paul D. Hess and Kenneth J. Brondyke’s 1969 Metal Pro-
gress article, “Causes of Molten Aluminum-Water Explo-
sions” [2] expanded on the foundation that George Long laid
a decade earlier. Through a series of tests, they concluded
that they knew the mechanism involved in the explosions.
They proposed “efficient ways” to prevent explosions on the
different substrates on that molten metal could come into
contact. Substrates such as rust and bare concrete (lime)
were repeatedly tested and found that they “greatly increased
the likelihood and violence of the explosions.” In subsequent
studies, Hess and Brondyke would focus on the minimum
area of exposed rust that could generate a molten metal
explosion. The researchers were the first to utilize high speed
video to record the explosions. Recording 700–1000 frames
per second showed three types of explosions. These findings
are the basis of the Aluminium Association’s molten metal
explosion classification system used today.
The researchers incorporated thermocouples to “study the
influence of temperatures on explosions.” Results showed
that metal with an original temperature of 632 °C that the
temperature at the bottom of the water container would rise
instantaneously to 760–982 °C within 0.25 s after an
explosion. In several tests, the water temperature rose from
20 to 693 °C in 0.06 s and then quickly (0.25 s) went off the
scale (760 °C).
A.W. Lowery
While experimenting with elevating metal temperatures
(above 982 °C), the molten metal detonated “before it was
poured, indicating that a chemical reaction had taken place”.
When testing a water container with a rusted surface, a flash
proceeded the explosion. They surmised that the flash, the
dispersal of large quantities of aluminum oxide particles
over the area, and the fact that the maximum temperatures
within the container were above that of the incoming metal
clearly indicated that the most violent explosions involve a
chemical reaction.
The three mechanisms Hess and Brondyke listed are the
basis of today’s Force 1, Force 2, and Force 3 molten metal
explosion classification system. They put forth that catas-
trophic explosions (Force 3 classification) that destroyed the
water container and were accompanied by a flash were
associated with a thermite reaction. This was the exact
opposite of George Long’s belief that a thermite reaction
played “a minor part” in the most severe explosion. They
concluded their paper by proposing two ways to prevent
explosions. The first is by having sufficient depth of water
and second by applying a protective coating on exposed
surfaces. Today’s best industry practice toward safety of
having a minimum 3 feet of water above the bottom of the
casting pit or debris was developed by Hess and Brondyke.
Absent from their Metal Progress publication was
research that Hess and Brondyke performed in 1968 inves-
tigating the “maximum size of bare spot” in the protective
coating surface exposing the bare substrate underneath. They
determined that “any bare spot larger than 2” × 2” on steel
or concrete surfaces in casting operations represents an
explosive hazard and should be patched immediately.” Many
fail to acknowledge this important contribution from Hess
and Brondyke resulting in explosions that could easily be
prevented with proper maintenance.
Has Recent Advances in Direct Chill Casting Made Us Less Safe?
Hess and Miller
Paul Hess and Ron Miller, Alcoa Technical Center
researchers headed an Aluminum Association sponsored
research project in 1980 [3]. The project was “undertaken to
extend the margin of safety in casting operations by
improving the engineering solutions to the inherently haz-
ardous casting operations where molten aluminum and water
are often in close proximity.” More than 500 explosion tests
were performed in this study. Previous studies by Hess and
Brondyke resulted in the widespread use of Tarset, a cat-
alyzed coal tar epoxy. Complaints of Tarset arose, overtime,
regarding difficulty of application on wet surfaces, mainte-
nance, repair and premature failures. In addition, the black
color of Tarset had the unintended consequence of
camouflaging damage that molten metal exposure left
making it difficult to visually see exposed bare substrate.
This study evaluated other coatings that had properties
including, but not limited to; ease of application, short
drying time, ease of repair, durability. [Some coatings were
added to the list because some member companies were
already using them (e.g., Wise Chem E-212-F).] The white
colored Wise Chem E-212-F was tested over 55 times
resulting in zero explosions. Wise Chem was quickly
adopted throughout the industry because it could be applied
on concrete, steel, and stainless steel substrates.
Water containers were constructed out of a variety of
substrates during the testing (e.g., plywood, tar impregnated
brick, concrete, etc.). When George Long tested stainless
steel water containers no explosions occurred. However
Hess and Miller observed “moderate” explosions on stain-
less steel substrates. This caused the researchers to make the
unusually forceful statement “that bare stainless steel should
not be used”. This recommendation seems to have been
forgotten in our industry now. Some believe bare stainless
substrates are safe while bare concrete and steel are dan-
gerous in close proximity to molten metal. Hess and Miller
and numerous other researchers have proven time and time
again that bare concrete, bare steel and bare stainless steel
can all generate explosions with molten metal. It is common
place now to see bare stainless steel in close proximity to
molten metal in cast houses. Several vertical casting pits
have been constructed over the past few years out of stain-
less steel. Each and every one of those stainless casting pits
that was recently built was eventually coated with Wise
Chem E-212-F or Wise Chem E-115 (Fig. 1).
Another coating, Rustoleum 769, was added to the testing
because some member companies were applying it in their
casthouses. Hess and Miller’s testing showed that Rus-
toleum 769 “did not prevent explosions”. “During impact
testing, pan coated with Rustoleum 769, exploded before the
mechanical impact could be delivered.” Previous research
studies had obtained an explosion by setting off a small
1091
explosive charge inside a mixture of molten aluminum and
water in a Tarset coated water container. Hess and Miller
wondered if a purely mechanical [impact] could initiate an
explosion under otherwise protected conditions (e.g., use of
Tarset). Tarset and Wise Chem E-212-F passed the
mechanical impact test because an explosion did not occur.
Hess and Miller’s study was able to confirm the results of
previous studies and produced new findings that are still
pertinent today. Our industry should heed their findings
including especially that “explosions occur with stainless
steel containers”, and “that purely mechanical impact caused
explosions in pans coated with Rustoleum 769”.
Taleyarkhan and Kim
Rusi Taleyarkhan and Seokho Kim U.S. Department of
Energy’s Oak Ridge National Laboratory (ORNL), partici-
pated in another Aluminum Association study in 1997
evaluating protective coatings [4]. The ORNL researchers
developed a unique experimental apparatus called the Steam
Explosion Triggering Studies (SETS) facility (Fig. 2).
In this facility, molten aluminum never comes into con-
tact with water in a tank so there is no danger of a steam
explosion. However, the facility accurately simulated heat
transfer from molten aluminum moving over submerged
surfaces using tungsten as a replacement interface material.
This technology was able to produce test results quicker than
the Aluminum Associations previous studies that involved
molten metal. The SETS facility corroborated Hess and
Miller’s results that explosions can be generated from
stainless steel substrates. Taleyarkhan and Kim reported that
molten metal coming into contact with bare stainless steel
was “very explosive”.
The researchers also tested the amount of gases released
upon pyrolysis from the protective coatings upon contact
with hot metal. It was found that certain organic coatings
that gave off significant non-condensable gases during attack
by hot metals also gave assistance in avoiding explosive
shocks. Wise Chem E-115 was found to “retain the highest
gas generation potential” in the study. Taleyarkhan and
Kim’s testing proved once again that the maximum area of
bare substrate in a protective coating that would generate an
explosion was 5 cm by 5 cm.
Direct Chill Casting Advancements
Forty years ago direct chill casting equipment consisted of
cables and motors to raise and lower the casting table.
During the beginning of casting many workers were required
to stand atop the casting table. These workers were in danger
of injury or death if an explosion occurred. Direct chill
1092 A.W. Lowery

Fig. 1 Stainless steel vertical casting pit built in 2012 coated with Wise Chem E-115

Fig. 2 Steam explosion triggering studies (SETS) facility

casting equipment manufacturers design progressed over-
time to where workers are now not required to be on or near
the casting table during the beginning of the cast. This
development may have the largest effect in preventing
workers from injuries and fatalities. Unfortunately, there
may be an unintended consequence where workers either
disregard or fail to follow their safety training.
Most incidents occur when a worker fails to follow
training, skip steps, or makes assumptions. These failures are
minimized but not eliminated with the use of PLCs (program
Has Recent Advances in Direct Chill Casting Made Us Less Safe?
200
180
160
140
120
100
80
60
40
20
0
Fig. 3 Incidents by year
logic controllers) at casting stations. The hazard with PLCs
is that some workers may rely solely on what the computer
screen is showing versus without confirming with their eyes.
The problem may be made worse when workers have never
experienced an explosion. A lack of experience results in
workers having a false safety belief. False safety beliefs can
begin when a lack of knowledge transforms into a habit or a
practice. Overtime those practices are assumed to be safe. It
is only after an incident resulting in an injury or death that
the practice is found to actually be a hazard. Training should
include videos of actual molten metal explosions and past
notable incidents should be discussed. Only by acknowl-
edging our industry’s history of molten metal explosions can
one fully accept the hazard potential. Through that accep-
tance of that potential hazard workers are reminded of the
importance of following their training, to never skip steps
and to never make assumptions (Fig. 3).
Noranda Explosion
At 12:30 PM on August 4, 2015 a holding furnace in the cast
house of Noranda Aluminium in New Madrid, Missouri
suffered a lining failure resulting in the unexpected release of
ninety thousand pounds of molten metal onto the factory
floor. The aluminium company believes molten metal flowed
across the plant floor to the casting pit and entered the
casting pit exhaust vent. There molten aluminium chemi-
cally reacted with the water in the bare steel pipe resulting in
a series of explosions. A small fire was limited to the
combustibles in the area. The series of explosions culmi-
1093
nated with a Force 3 explosion completely destroying the
casthouse that produced 100,000 metric tons of extrusion
billet annually in sizes of 150, 170, 200, 220, 250, 300 cm
diameter in two vertical casting stations. The magnitude of
the explosions was so great it generated a small earthquake
that radiated out from the factory for over 18 km. The
casthouse currently produces no billet.
This explosion was the largest explosion to occur in our
industry in North America in 40 years. Until an explosion
destroyed another casthouse in June 2016. No information
regarding the cause(s) of this most recent explosion has yet
to be released by the aluminium company at this time.
Conclusions
The history of our industry cannot be discussed without
mentioning the hazard of molten metal explosions. Our
industry would not have achieved its current level without
the research conducted on this hazard over the past 65 years.
The researchers cited in this publication along with a mul-
titude of others should be acknowledged for their contribu-
tions to making our industry safety. It is impossible to
calculate the number of injuries and lives saved by our
industry incorporating past research findings. We commend
the direct chill casting equipment manufacturers for placing
an importance on worker safety with every design. Never-
theless, with the recent technological advancements workers
should be trained on what could occur if they fail to follow
their training, skip steps or make assumptions.
References
1. S.G Epstein, Causes and prevention of molten aluminium water
explosion, in Light Metals 1991 (1991)
2. G. Long, Explosions of molten aluminium and water—cause and
prevention, in Metal Progress (1957), pp. 107–112
3. R.P. Taleyarkhan, V. Georgevich, L. Nelson, Fundamental exper-
imentation and theoretical modelling for prevention of molten metal
explosion in casting pits, in Light Metal Age 1997 (1997)
4. D.D. Leon, R.T. Richter, T.L. Levendusky, Investigation of
coatings which prevent molten aluminum/water explosions, in
Light Metals 2001 (2001)
5. Guidelines for Handling Molten Aluminium, 3rd edn
6. D. Jone, Email Interview (2013, October 11)
7. D. Sale, Email Interview (2013, October 9)
8. C. Emes, Email Interview (2013, October 14)
 Part XXV
Cast Shop Technology: Recycling
and Sustainability Joint Session
 Tramp Element Accumulation and Its Effects
on Secondary Phase Particles

Samuel R. Wagstaff, Robert B. Wagstaff, and Antoine Allanore

Abstract
Increased demand for wrought aluminum products has put pressure on suppliers to increase
the amount of recycled material used in the production stream. While this has financial and
ecological benefits, even single-source scrap streams never exhibit the composition profile
of the original product. The corresponding accumulation of so-called “tramp” elements
such as iron, chromium, and vanadium can have an impact on the secondary phase
intermetallic particles formed during Direct-Chill (DC) casting. In order to better
understand the influence of increased concentrations of certain tramp elements, an
AA3104 ingot has been cast with an increased level of iron compared to the standard. The
secondary phase particles have been analyzed as a function of position using a deep-etch
technique and compared to grain size and macrosegregation profiles.

Keywords
DC casting Intermetallic formation Recycling Tramp elements

Introduction recycle material streams. In the case of aluminum products,

The recycling of aluminum is known to have numerous
economic and environmental benefits. Compared to other
high production volume materials, aluminum has one of the
largest energy differences between primary and secondary
production: 186 MJ/kg for primary compared to 10–20 MJ/kg
for secondary [1]. With financial and energy savings in
mind, many producers now have targets for use of secondary
materials. However, there is never a 100% compositional
return on recycled products, and the accumulation of
impurities in material streams is a significant barrier to any
of these goals [2].
A growing number of studies indicate that the accumu-
lation of unwanted elements is a growing problem in all
S.R. Wagstaff
A. Allanore
Massachusetts Institute of Technology, 77 Massachusetts Ave,
Cambridge, MA 02139, USA
R.B. Wagstaff (&)
Novelis Solatens Technology Center, 16004 E. Euclid Ave,
Spokane Valley, WA 99016, USA
e-mail: bob.wagstaff@novelis.adityabirla.com
the list of problematic elements is fairly significant includ-
ing: Si, Mg, Ni, Zn, Pb, Cr, Fe, Cu, V, and Mn [3–9]. The
reuse and recycling of metals is a metallurgical decision
governed by the fundamental laws of thermodynamics, one
of which being that the separation of unwanted elements has
a given energetic cost. With no evident and simple ther-
modynamic approach to separate tramp elements at low
concentration, melt practitioners must identify strategies
throughout production in order to minimize their effects.
Of particular interest to the entire aluminum industry is
the impact of increased iron content on the performance of
wrought products during thermo-mechanical processing.
Due to its low solid solubility, iron is almost found uni-
formly at grain boundaries forming complex intermetallic
compounds which aid in subsequent recrystallization pro-
cesses (see appendix for a high level review of the ther-
modynamics of competitive nucleation/precipitation). The
particular compound to be found is tightly controlled by
compositional windows. Operating near the boundaries of
these windows can lead to compounds which adversely
affect downstream performance.

© The Minerals, Metals & Materials Society 2017 1097

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_132
1098
One alloy particularly sensitive to type of intermetallic
formed is AA3104, currently used in can body stock. The
as-cast structure of AA3104 consists of a cellular dendritic
aluminum matrix with stringers of intermetallic phases along
the cell boundaries, remnants of the last segregated melt to
finally solidify. The main features defining the cast structure
are: (1) the cell size and intermetallic particle size, (2) the
degree of solute supersaturation, and (3) the morphology of
the intermetallics. Due to the thickness of Direct-Chill
(DC) cast ingots, the freezing rate varies from the edge to the
center [10–12]. As the freezing rate increases, the dendrite
cell size decreases and the stringers become thinner and
envelop cell boundaries more completely. In contrast, at
slower freezing rates cell size increases and intermetallics
become larger and more sparsely surround the cell
boundaries.
The intermetallic phases that form in AA3104 consist of
two major species: orthorhombic Al6(Fe,Mn) and cubic
a-Al12(Fe,Mn)3Si (as well as a metastable b variant). The
relative amounts of these phases are determined by com-
position as well as solidification rate [11–14]. In DC prod-
ucts, approximately 85% correspond to the Al6(Fe,Mn)
phase, with the balance being a-Al12(Fe,Mn)3Si. Under
these casting conditions 25–30% of the manganese precipi-
tates out of solution as intermetallic particles, while the
remainder remains in solid solution [13]. The effect of iron is
very pronounced in AA3104. Even small additions of iron
greatly augment the number of constituent particles, which
promotes manganese precipitation and inhibits the formation
of metastable ternary phases (AlxMnyFez) [15]. Instead of
promoting a ternary phase, iron substitutes for manganese in
Al6Mn. During homogenization manganese enters Al6(Fe,
Mn) until the phase reaches its maximum stability at
Al6(Fe0.5,Mn0.5). Any remaining iron will be forced into
another compound which may not perform ideally under
thermo-mechanical processing.
In order to better understand the effect of tramp element
accumulation in DC cast AA3104 ingots the present research
has been launched. This investigation focuses on a set of two
full size rolling slab ingots produced using standard tech-
niques. One ingot is comprised of primary-sourced material,
while the other is a recycle-based product. By leveraging the
knowledge gained during the course of these experiments,
one could gain insight into potential solutions to deleterious
intermetallic formation.
Table 1 Composition of ingots investigated consisting of a melt prepared with primary material and a melt prepared with predominantly recycled
material
Si Fe Cu Mn Mg
Primary 0.1767 0.433 0.1865 0.8425 1.0247
Recycle 0.26 0.58 0.18 0.9 1.16
S.R. Wagstaff et al.
Experimental Procedure
These experiments were performed on full scale DC casting
machines in order to facilitate further thermo-mechanical
processing and can processing trials. Two ingots were pre-
pared in a commercial gas burner furnace, one using primary
material, and one using predominantly recycled material.
Care was taken such that the recycled ingot chemistry did
not exceed the specifications for AA3104. The chemical
analysis was performed using an Optical-Emission Spec-
trometer, whose results are presented in Table 1.
The molten alloys were degassed with a rotary degasser
bubbling argon, and then filtered with a ceramic foam filter.
The melt was inoculated with 5 ppm 3/1 TiB grain refining
rod (based on B addition). Casting was performed with a
600  1750 mm WAGSTAFF LHCTM mold at a casting
speed of 65 mm/min. A standard combination (distribution)
bag was used for these trials.
Following casting, one inch thick slices were taken from
the ingot at 1800 mm of cast length. Composition analyses
were performed using an Olympus Alloy Plus XRF analyzer
from the centerline of the ingot to the edge, every 12.5 mm
according to the scheme presented in Fig. 1 (From A to E).
A 25 mm core drill was used to remove samples from the
ingot slices from the points indicated in Fig. 1. The samples
were polished using standard metallographic techniques and
then an optical microscope was used to observe the as-cast
microstructure. Images were taken of these microstructures,
and an image processing software was used to analyze the
size and density of the intermetallic species present. These
same samples were then analyzed using an SEM EDS
technique in order to spot check compositions of the
observed intermetallic species. Following EDS measure-
ments, the samples were “deep etched” using a hydrochloric
acid solution to a depth of 40 lm, and images were taken
with an SEM.
The remainder of the ingots were post continuously
(tandem) hot rolled with equivalent temperatures according
to standard mill practice for AA3104. Samples were taken
from the sheet 100 m from the end of the sheet (corre-
sponding to 80 cm from the head of the ingot) and 580 mm
from the edge (corresponding to locations in Fig. 1) and
analyzed using EBSD for recrystallization. The remainder of
the sheet was processed into beverage cans to observe pro-
duction performance.
Ni Cr Zn Ti Bi Pb
0 0.007 0.0131 0.013 0 0.0007
0.006 0.0107 0.01 0.0252 0.0032 0.0027
Tramp Element Accumulation and Its Effects on Secondary Phase Particles
Fig. 1 Schematic representation of sample locations taken from the
two test ingots. XRF analyses were performed every 12.5 mm from
point A to point E. The circles represent core-drill sample locations
removed for metallographic analysis
Fig. 2 Iron concentration for the two ingots as a function of distance
from the ingot center, as represented in Fig. 1
Results
Figure 2 is a plot of the iron concentration for the primary
and recycle based ingots as a function of distance from the
ingot centerline (see Fig. 1). We can see that the general
forms of the concentration (macrosegregation) curves are
nearly parallel, only offset by, perhaps, 0.15%. As is com-
mon in most eutectic formers, there is a depletion at the
centerline [16, 17]. This depletion is followed by a zone of
enrichment at approximately 100 mm from the ingot cen-
terline. The remainder of the ingot (approximately 100 mm
to edge) is around the average iron composition reported in
Table 1.
Figure 3 are plots of the population size of intermetallics
sorted by size. Each of the sample locations from Fig. 1 are
represented by a unique color and marker in the upper two
plots. In looking at these two plots we can see that the size
range and population are nearly identical. We only were able
1099
to find minute differences in curves corresponding to posi-
tions A and B, which represent the center of the ingot and
approximately 75 mm from the ingot center. These curves
have been represented in the two lower figures, A on the left
and B on the right. We can see from position A that the
recycled ingot has a population of intermetallics that is
generally smaller than the primary ingot (seen as a rotation
of the recycle curve relative to the primary). In position B,
there seems to be a distinct lack of intermetallics smaller
than 20 lm for the primary case as compared to the recycled
case.
Figure 4 are SEM images taken from positions A and B
for both the recycled and primary case. We can see by
comparing positions A and B (both cases) that position A is
exemplified by much finer intermetallics that surround
nearly the entire grain. Position B on the other hand has
much larger intermetallics that only partially surround each
grain. As we compare recycled to primary material, we can
see that the recycled material has a much larger number of
small constituent particles. The primary material on the other
hand, exhibits the typical “Chinese Script” morphology and
appears to be much larger. EDS techniques were used on
these samples as well in order to identify constituent phases.
Overall there were two primary families of phases present,
Al–Fe–Mn and Al–Fe–Mn–Si. Since the stoichiometry of
each phase can vary slightly, there is little to be seen in terms
of compositional trends. However, we were able to see that
the Al–Fe–Mn–Si phase has a much blockier microstructure
than the Al–Fe–Mn phase, which appears much more as
stringers or as chinese script.
Figure 5 are deep etched samples from positions A, B,
and C for the primary and recycled cases. The scale bar for
position A has been increased in order to give a better view
of a single constituent phase. The remainder of the images
have all been scaled identically. From these samples there
seems to be little difference morphologically between recy-
cled and primary cases. While we have already discussed
apparent size images, the intermetallic morphologies all
seem to be corrugated sheets, needles, and spears. It is
important to note that these are 3-dimensional views of the
intermetallic particles. The samples from Fig. 4 are
2-Dimensional images formed by taking slices from the
3-Dimensional form. Thus, it can be very difficult to extract
the full shape of a constituent particle from a simple
2-Dimensional SEM image.
Figure 6 are EBSD maps of the post-rolled material. The
samples are taken from 2.3 mm thick sheet (left to right
dimension). The rolling direction is parallel to the long axis
of the page. The sample taken corresponds to the full
reduction of the ingot cross section in Fig. 1 (600 mm axis
becomes 2.3 mm). Thus, the maps represent from the left
1100 S.R. Wagstaff et al.

Fig. 3 Population of intermetallics as sorted by size for each of the positions described in Fig. 1. The intermetallic size was analyzed by an
imaging processing software, and converted to an equivalent diameter

Fig. 4 SEM images of positions A and B along with EDS analyses for
recycled and primary cases

edge to the center positions E–A on Fig. 1, and then the

mirror A′–E′ from the center to the right edge. EBSD is used
to analyze crystallographic orientations. By probing the Fig. 5 Deep etch samples from positions A, B, and C illustrating the
entire surface, one can generate a map of the grain size and 3-D microstructure of the constituent phases. Note that Sample A has a
orientations of a sample. From Fig. 6 we can get an idea of scale bar of 50 lm, while Samples B and C have scale bars of 100 lm
Tramp Element Accumulation and Its Effects on Secondary Phase Particles
the degree of recrystallization of these samples at this point
in the processing. We can see that the two images seem to be
nearly identical in form and appearance. An observation we
were able to make is that there seems to be a slightly
increased number of elongated grains in the center of the
primary sample as compared to the recycled sample. No
numerical analyses were performed to determine if this is
statistically relevant.
The remainder of the sheets from these trials were used to
make beverage cans using a typical drawing process at the
Novelis Kennesaw Can line. No difference could be seen in
overall run ability of the two products with respect to earing
or self-lubrication of the iron intermetallics (tear offs).
Discussion
The primary motivation of this study was to examine the
effect of increasing recycle content on can body stock ingots.
Perhaps the most telling feature of this addition was the stark
difference in iron composition across the thickness of the
ingot (Fig. 2). It has been previously demonstrated that even
slight additions of iron will increase the number of con-
stituent particles due to the decreased solid solubility of iron
[15]. We have been able to confirm this in Fig. 3, as the
number of intermetallics seems to increase as their average
size decreases notably in position A. We can observe this
visually in the SEM images from Fig. 4. While this larger
number of fine intermetallics may have little bearing on the
cast product, the increased number of particles will change
recrystallization kinetics. As particle-stimulated-nucleation
(PSN) becomes more dominant, there should be an increase
in driving force for recrystallization. This effect can be
observed in Fig. 6, where the primary material actually
exhibited more oblong grains than the recycled material,
Fig. 6 EBSD maps of the primary and recycled material taken post
rolling, 100 m from the end of the sheet (80 cm from head of ingot).
The entire thickness of the sheet (2.3 mm) is represented from left to
right. From the left edge to the center represents positions E–A in
Fig. 1. From the center to the right edge corresponds to the mirror
A′–E′. The rolling direction is towards the top of the page in this
orientation
1101
indicative of a lesser degree of recrystallization. These two
samples were rolled under identical thermo mechanical
conditions, thus the increased number of constituent parti-
cles seems to have had a beneficial effect.
Conclusion
We have performed a set of experiments in order to inves-
tigate the effects of increasing recycle content on the
microstructure and performance of a can body stock alloy
(AA3104). The increased degree of iron from the recycled
material seems to have refined the constituent particle
microstructure especially in the ingot center. This increase in
particle number and decrease in particle size has had a direct
positive impact on the recrystallization kinetics of this alloy
(via PSN). While these results do seem to be positive, we
attempted to remain within the composition limits for
AA3104. Additional trials should be performed as chemis-
tries for other tramp elements (V, Cr, Ni, etc.) also reach the
limits for the alloy. As these elements tend to behave simi-
larly to iron, one could anticipate similar behavior, but the
effects may not always be synergistic.
Appendix
Thermodynamics of competitive nucleation
The driving force for the onset of precipitation ðDa Þ of a
phase (a) from a liquid with composition X0L is schematically
represented below in Fig. 7.
Fig. 7 Illustration of the driving force of precipitation of a binary
phase a from a supersaturated liquid solution
1102 S.R. Wagstaff et al.

From this figure, Da can be written as:

 L

 @G
a 
Da ¼ GL X0L þ X  X0L  Ga
@X XL
L
0

This equation can also be rewritten the following way:

 L  
a

L @G
a 
D ¼ G X0 þ
L
X  X L
0  G L L
Xeq
@X L X L
 L  0

@G a
 X  X L
@X L XeqL eq

   
@GL
If we expand @X L X L and GL Xeq
L
using a truncated
0

Taylor’s series, this equation then becomes:

!

 @ 2 L
G  
Da ¼ X a  X0L x x X L
0  X L
Fig. 8 An example of how the driving force of precipitation depends
ð@X L Þ2 XL
eq
on the initial melt composition
0

As we can see, at low supersaturations, the driving force

Da linearly depends on the supersaturation X0L  Xeq L
, the
difference between the initial composition of the liquid and
stoichiometric phase X a  Xeq L
, and on the curvature of the
concentration dependence of the molar Gibb’s free energy of
 2 L
@ G
the liquid phase ð@X L Þ2 L
.
X0
If we generalize these results to a system of K compo-
nents, we get:
2 / L 3
X2;0  X2;eq
 
6 .. 7
Da ¼ X2/  X2;eq
L
; . . .; XK/  XK;eq
L
xHx4 . 5
XK/  XK;eq
L

where H is the Hessian of the molar Gibbs energy.

Recalling that the precipitation of a phase is only possible
where Da [ 0, there are some concentration regions where
this condition is satisfied, and can be defined. We call these
regions “nucleability regions” or “nucleability fields”, and
they cannot span over the entire concentration field. Figure 8 Fig. 9 Driving forces for the onset of precipitation of two competing
phases
is a representation of the nucleability region for our pre-
cipitated phase (a).
In the nucleability regions of (a) between ðXeq L
Þ1 and In the case now where two stoichiometric phases have the
ðXeq
L
Þ2 , the driving forces for precipitation are positive and chance to precipitate from the melt (Fig. 9), the following
(a) can be nucleated. equation can be written:
Tramp Element Accumulation and Its Effects on Secondary Phase Particles 1103

2. Z.-K. Liu, Effect of Impurities on Alloys (I.T. Program. Energy

Efficiency and Renewable Energy, US Department of Energy,
Washington, DC, 2003)
3. J.-Y. Kim, S.-J. Kim, I.-K. Song, J.-H. Han, Aging characteristics
of recycled ACSR wires for distribution lines. Electrical insulation
conference and electrical manufacturing & coil winding confer-
ence (1997)
4. C. Viklund-White, N. Menad, Impurity Accumulation as a
Consequence of Increased Scrap Recycling (Minerals and Metals
Recycling Research Centre, MiMeR Lulea University of Technol-
ogy, Stockholm, Sweden 1999), p. 35
5. A. Gesing, J Mater 56, 18–27 (2004)
6. U. Lundqvist, B. Andersson, M. Axsater, P. Forsberg, K. Heikkila,
U. Jonson et al., Design for Recycling in the Transport Sector—
Future Scenarios and Challenges (Chalmers University of Tech-
nology, Goteberg University, Goteborg, Sweden, 2004)
7. S.K. Das, Light Metals (TMS, 2006), pp. 911–916
Fig. 10 Illustration of how phase formation depends on the initial 8. A. Gesing, H. Harbeck, Particle sorting of light-metal alloys and
composition of the melt expanded use of manufacturing scrap in automotive, marine, and
aerospace markets. in Global symposium on recycling, waste
treatment, and clean technology (REWAS) (2008)
9. G. Gaustad, E. Olivetti, R. Kirchain, J. Ind. Ecol. 14, 286–308
Dba ¼ Db  Da (2010)
"  L #

L @G
b  b
10. H.D. Merchant, T.Z. Kattamis, Homogenization and Annealing of
¼ G X0 þ
L
X  X0  G
L Aluminum and Copper Alloys (TMS, Warrendale, PA, 1988),
@X L XL pp. 1–52
"  L
0
# 11. S.X. Ding, B. Ren, J.G. Morris, ed. by J.J. Jonas, T.R. Bieler, K.

 @G
 J. Bowman. Advances in Hot Deformation Textures and
 GL X0L þ X a  X0L  Ga
@X L X L Microstructures (1994), pp. 281–288
 L 0 12. R.G. Kamat, JOM 48, 34–38 (1996)
@G
b  13. L. Chen, J.G. Morris, S.K. Das, ed. by H.D. Mercant et al.
¼ X  X  ðGb  Ga Þ
a
@X L X L Continuous Casting of Non-Ferrous Metals and Alloys (TMS,
0 Warrendale, PA, 1989), pp. 269–284
14. L.F. Mondolfo, Aluminum Alloys, Structure and Properties
Figure 10 shows the variation of driving forces for pre- (Butterworth & Co ltd, London, 1976)
cipitation of (a) and (b) by changing the composition. It is 15. J.J. Theler, P. Furrer, Aluminum 8, 511–521 (1974)
worthy of note how the initial melt composition affects the 16. D.G. Eskin, Physical Metallurgy of Direct-Chill Casting of
driving forces for precipitation of these phases. It can be Aluminum Alloys (CRC Press, Boca Raton, 2008)
17. S.R. Wagstaff, A. Allanore, Light Metals (TMS, 2015), pp. 977–982
seen that by increasing the supersaturation of the melt, the
likelihood of the formation of (b) is increased.

References

1. J.A.S. Green, Aluminum Recycling and Processing for Energy

Conservation and Sustainability (Materials Park, OH, ASM
International, 2007)
 Dross Formation Mechanisms of Thermally
Pre-Treated Used Beverage Can Scrap Bales
with Different Density

J. Steglich, R. Dittrich, G. Rombach, M. Rosefort, B. Friedrich,

and A. Pichat

Abstract
Used beverage can scrap (UBC) bales can be remelted in state of the art multi-chamber
furnaces. Following the recycling of baled UBC scrap in multi-chamber furnaces, a
laboratory scale process route was developed for thermal pre-treatment and submerged
melting of the scrap. In the present work, UBC scrap types with different densities and level
of contamination are compared. The scrap types were thermally pre-treated in different
atmospheres up to 823 K (550 °C) and subsequently melted by submerging in a salt-free
laboratory process. Melting was performed in pure aluminum at 1023 K (750 °C) under
protective argon atmosphere to exclude the influence of thermolysis gases and atmosphere.
The impact of remaining organic contamination and oxidation products after thermal
pre-treatment on dross formation were described. Results of SEM EDX analysis, as well as
thermochemical calculations, were used to explain reactions between solid scrap and the
liquid aluminium melt to improve recycling efficiency.

Keywords
Dross formation UBC Thermal pre-treatment Submerged melting

Introduction found that the pre-treatment can decrease or even increase

This study investigates the impact of thermal pre-treatment
on dross formation of used beverage can scrap (UBC).
During re-melting of thermally pre-treated UBC scrap, it was
J. Steglich (&)
M. Rosefort
TRIMET Aluminium SE, Aluminiumallee 1,
45356 Essen, Germany
e-mail: jan.steglich@trimet.de
R. Dittrich
B. Friedrich
IME Process Metallurgy and Metal Recycling, RWTH Aachen
University, Intzestr. 3, 52056 Aachen, Germany
G. Rombach
Hydro Aluminium Rolled Products GmbH,
Georg-Von-Boeselager-Str. 21, 53117 Bonn, Germany
A. Pichat
Parc Economique Centr’alp, Constellium Technology Center,
38341 Voreppe, France
the amount of dross formation, compared to the un-treated
scrap material. This phenomenon is investigated here by
combined pre-treatment and submerged melting experiments
in laboratory scale.
Two UBC scrap bale qualities with densities of 0.45 and
0.91 t/m3 were used as raw material. These bales have dif-
ferent levels of contamination, depending of the scrap purity
before compacting. The influences of thermal pre-treatment
and submerged melting on dross formation are investigated
with both scrap types. These process steps are commonly
performed and may be combined into one furnace process.
The twin-chamber furnace and shaft furnace are two state of
the art examples for a combined furnace processes [1]. One
goal of this investigation is to describe the impact of organic
residue, formed by heating in oxygen containing atmosphere
(thermolysis) versus heating in inert-gas atmosphere
(pyrolysis).

© The Minerals, Metals & Materials Society 2017 1105

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_133
1106 J. Steglich et al.

Literature Survey on Can Coating Reaction Epoxy Polymer Degradation During Thermal
Products by Thermal Pre-treatment Pre-treatment

In order to describe reaction mechanisms between coating
residue of UBC scrap and the liquid melt, a description of
this residue is needed. This literature survey focuses on
organic coating residue after thermal pre-treatment.
Structure of Thermosetting Can Coating
Waterborne epoxy, polyester and acrylic polymer resins are
widely used as beverage can coatings [2–4]. Additionally,
phenolic, polyamide and formaldehyde resins are used as
crosslinking agents or hardeners for epoxy based coatings
[2]. Although a wide variety of coatings and coating mix-
tures are in use, they are all thermosetting polymers cross-
linked into a three-dimensional structure [2, 3, 5].
Bisphenol-a-diglycidylether (BADGE) based epoxy resins
are examples for commonly used coating in the can industry.
The curing temperature of waterborne resins is in the range
of 423–473 K, depending of the resin-cure system and time
[2, 3, 6]. In curing, crosslinks are formed and the liquid resin
is transformed into a glass-like thermoset. Thermosetting
polymers have short sub-chains without rotational freedom
and do not become elastic with increasing temperature like
thermoplastic resins [5].
When the curing temperature of a thermosetting polymer is
exceeded, the cross-linked polymer network starts to
degrade at the crosslink bonds [5, 7]. The scission of
crosslinks leads to reduced crosslink length, resulting a
coating with reduced elasticity and hardness [4, 5, 7].
Figure 2 shows the thermogravimetric analysis
(TGA) results of two epoxy based can coatings by [4, 7, 8].
The presence of oxygen in the atmosphere determines the
decomposition mechanism and how much char is formed.
The analysis of [4, 7] are performed with BADGE based
epoxy cured with an amine hardener. In investigations of [8],
a mixture of BADGE epoxy and phenol-formaldehyde
(novolac) resin of ratio 2:1 was used.
Figure 1 shows that polymer degradation in inert gas
leads to higher residual char mass, compared to degradation
in air or oxygen. Even after heating beyond the liquidus
temperature of aluminum, char yields of pure BADGE
epoxy were 6.3–7.6% of the initial weight in N2, compared
to 0.1–0.2% heated in air at 1153 K [4]. Whereas [9] reports
1.5 wt% residual char after pyrolysis of pure BADGE
epoxy heated in N2 up to 1073 K.
The solid char residue can be described as an amorphous
structure with low crystalline content, featuring porosity and
crevices [7, 9, 10]. The char residue of amine cured

Fig. 1 Comparison of
100
thermogravimetric analysis and
90
temperature depending residual
masses of two different epoxy
80
Residual mass in%

70 Epoxy-Novolac, 30 K/min, He [9]

coatings in O2, air, He and N2
atmospheres at different heating 60 BADGE-Epoxy, 20 K/min, N2 [5]
rates according to [4, 7, 8] 50 BADGE-Epoxy, 25 K/min, N2 [4]
40
Epoxy-Novolac, 30 K/min, O2 [9]
30
20 BADGE-Epoxy, 20 K/min, Air [5]
10
0
0 200 400 600 800 1000 1200 1400
Temperature in K

Fig. 2 Detail from UBC material

cross sections A (left side) and B
(right side)

1 cm 1 cm
Dross Formation Mechanisms of Thermally Pre-Treated … 1107

BADGE epoxy resin was analyzed by [10], after heating to
1073 K in N2 flow for a TGA analysis. The results are
84 wt%C, 11 wt%O and 2 wt%N, without traces of sulfur
and phosphor. The char residue has a high thermal stability
and a low thermal conductivity [10]. Thermal conductivity
of epoxy/carbon laminates are measured by [7] to be
8–12 W/mK measured in plane with the laminate and
0.17 W/mK of its solid char, compared to 0.23 W/mK of
pure epoxy resin [7].
Experimental Procedure
To investigate the impact of thermal pre-treatment and
compacting on dross formation by baled UBC scrap, two
scrap types have been characterized, thermally pre-treated,
and melted by submerging in pure aluminum melt at labo-
ratory scale.
UBC Material Characterization and Thermal
Pre-treatment
Figure 2 shows a cross section details from UBC material
A and B. The differences in porosity and contamination are
visible. The can sheets are commonly made of EN AW-3104
(AlMn1Mg1Cu) and EN AW-5182 (AlMg4.5Mn0.4) alloy.
The two UBC scrap qualities were cut into slices of about
300 mm by 150 mm and 50 mm thickness for thermal
pre-treatment. Pre-treatment was performed in an air tight
steel cylinder with inner diameter of 260 mm and a height of
445 mm, heated by external resistance heating. To maintain
a controlled atmosphere, the scrap was loaded before start of
the heating cycle and removed after cooling down. There-
fore, a heating ramp with a plateau at the target holding
temperature was achieved. The experiments were performed
at atmospheric pressure with pure argon, argon with 4 vol.%
O2 and air. Table 2 shows parameters of the thermal
pre-treatment. The process temperature and atmosphere
represent possible industry conditions.
The temperature distribution in the compacted UBC sli-
ces during pre-treatment is assumed to be constant, due to
50 mm thin samples, a low heating rate and use of only one
slice per experiment.

Two different commercially available UBC bale qualities are
used for the experiments. Table 1 gives an overview of
physical bale properties before thermal pre-treatment. UBC
material A is a very clean scrap, with a volatile organic
content of 2.8 ± 0.3 wt%, showing only minimal other
impurities than can coating. The volatile organic content was
measured as glowing loss by glowing for 4 h in 773 K hot
air on basis of [11]. UBC material B has higher levels of
contamination, which are described in Table 1 and shown in
Fig. 2.
Submerged Melting in Laboratory Scale
Following the process route of a twin-chamber process, the
pre-treated scrap is melted by submerging into liquid metal,
to investigate the dross formation reactions occurring at the
liquid metal/solid scrap interface. Therefore, a laboratory
scale setup was built to ensure a protective argon atmosphere
above the melt during dross formation and to keep the
skimming procedure for dross constant. The setup is shown
in Fig. 3.

Table 1 Physical UBC scrap Property Unit UBC A UBC B Method of analysis
bale properties before thermal
pre-treatment Major impurities – Coating Coating, plastic, iron, copper Visual
3
Density kg/m 450 910 Weighing
Volatile organic content wt% 2.8 ± 0.3 8.4 ± 4.0 Glowing loss
Moisture content wt% 0.9 ± 0.7 1.7 ± 1.1 Drying
Porosity % 83 66 Calculated

Table 2 Experiment parameters Experiment Atmosphere at Gas Heating Cooling Holding Holding
of thermal pre-treatment in 1 atm flow in ramp in ramp in temperature time in
laboratory scale steel cylinder l/min K/min K/min in K min
Argon Argon 10 5 2–3 823 ± 5 30 ± 5
Argon + 4O2 Argon + 4 vol. 10 5 2–3 823 ± 5 30 ± 5
% O2
Air 823 K Air 10 5 2–3 823 ± 5 30 ± 5
Air 723 K Air 10 5 2–3 723 ± 5 30 ± 5
Raw Only pre-dried raw UBC material
1108
Fig. 3 Schematic laboratory scale setup for dross formation experi-
ments by submerged melting of UBC in argon inert gas
For each experiment, 1000 ± 5 g of Al 99.9 metal were
molten in a SiO–Al2O3 crucible. When the metal reached
1023 ± 5 K, a thin pristine dross layer was skimmed off,
and 100 ± 1 g UBC scrap were attached by aluminum-wire
to a sample carrier tool. The sample was placed in the steel
cylinder with argon atmosphere and the lid was closed.
A purge time of two minutes achieved an O2 concentration
below 100 ppm in the atmosphere. All pre-treated UBC
samples were submerged in 5–10 s into the melt. After
5 min reaction time, the carrier tool was exchanged against a
skimming tool (shown in Fig. 3) and the dross layer was
visually inspected to ensure complete melting of the scrap,
otherwise stirred manually once. An additional 30 min
reaction time in argon atmosphere were maintained. Finally,
the dross was skimmed, cooled in argon, weight and ana-
lyzed. The experiments were performed three times for each
condition with new metal heals.
Dross formation is calculated, as usual in the industry [1],
in relation to the scrap input mass, according to Eq. 1.
The non-metallic particle (NMP) content is measured by
remelting under salt flux and calculated by Eq. 2:
dross mass
Dross in % ¼  100 ð1Þ
dry scrap mass
dross mass  recovered metal mass
NMP in % ¼  100
dross mass
ð2Þ
For analysis, the non-metallic-particle content of the
skimmed dross was measured by remelting under salt flux
(equimolar NaCl:KCl flux with 5 wt% added cryolite) in a
scrap to salt ratio of 1:2 at 1023 K. After the salt was liquid,
the dross was added and molten for 40–50 min under
repeated stirring. Carbon and oxygen concentrations in the
UBC material were measured by the total combustion
method with a Leco TC600 and Leco TOS800. The samples
were taken as drilling swarf spot samples from each material
by nine spot samples for each UBC scrap material. As a
J. Steglich et al.
result, a total of 90 carbon and oxygen samples of UBC
scrap were analyzed. With this scrap material, 30 dross
formation experiments have been performed.
Results and Discussion
The total carbon and oxygen content remaining on the can
sheets is used to rate the success of organic removal while
preventing oxidation of the material. Afterwards, the dross
structures are analyzed for reaction products and set into
context with the dross formation masses.
Influence of Thermal Pre-treatment on Carbon
and Oxygen Content of Baled UBC Scrap
Figure 4 shows a significant difference in carbon and oxygen
content of UBC material A and B after thermal
pre-treatment. There is a strong reduction of carbon and
oxygen of UBC material A under all thermolysis (substoi-
chiometric oxygen in atmosphere) and pyrolysis (absence of
oxygen) conditions used. For UBC A, pyrolysis with argon
at 823 K leads to the highest concentration of C and O
remaining on the scrap. In contrast, thermolysis in air at
823 K, leads to the highest removal of C (0.04 wt% left) and
less O than in the raw material. Oxygen concentration is
decreased as well, due to the presence of oxygen in volatiles.
On the other hand, C and O removal of material B was
not as significant. A comparison of sample B Raw with the
remaining B series samples shows a reduction of carbon
content. The lowest remaining carbon concentration of UBC
material B was also achieved by thermolysis in air at 823 K,
but the highest oxidation as well. The thermolysed samples
show higher concentrations of oxygen than the raw material.
Even though an increase in reactor temperature or off gas
temperature during thermal pre-treatment was not measured,
an exothermic reaction of the plastic content could have
raised the temperature in the bale locally, resulting in oxi-
dation. This is supported by the lower O concentration of
material thermolysed at 723 K in air. Humidity in material B
was also higher, which can initiate earlier oxidation [12].
Temperature dependent oxidation reactions and kinetics are
described in studies of [12, 13].
The main difference of the can sheet is shown in Fig. 5,
as taper-section of AlMn1Mg1Cu can sheet after pyrolysis
(sample A Argon) by an optical microscope image. A con-
tinuous coating residue layer was observed. The image is
overexposed to highlight the can coating. No residual coat-
ing layer was visible on the thermolysed sample A Air
823 K.
Pyrolysis lead to the transformation of can coating to a
1–3 µm thick char layer on can body sheets and 3–4 µm
Dross Formation Mechanisms of Thermally Pre-Treated … 1109

Fig. 4 Carbon and oxygen

concentration in compacted UBC
material A and B, taken as spot
samples by drilling from one slice
for each type after thermal
pre-treatment

Influence of Scrap Bale Density

and Pre-treatment on Dross Formation

The skimmed dross was cooled, weight, and remelted under

Fig. 5 Polished taper sections as optical microscopic image of can
body sheets after pyrolysis and heating by 5 K/min to 823 K in argon
thick layer on can ends and. The thermolysis samples of
scrap A and B show almost complete removal of the coating
on can ends and sheet, with scattered pits and pores, indi-
cating starting oxidation, but no severe oxidation products
by break-away oxidation. These features are also identified
by SEM EDX analysis in the solidified dross samples after
submerged melting.
salt. The results of generated dross mass and
non-metallic-particle (NMP) content are shown in Fig. 6.
The dross formation masses are higher than in industry
processes, due to effect of laboratory scale and skimming
procedure. Material A shows a significantly reduction of
dross formation by thermolysis at 823 K, as expected by the
low C and O concentrations.
Submerged melting of pyrolysed UBC A produced more
dross compared to untreated material, due to the adhering
char residue on the can sheets. The effect is explained in
detail in Sect. “Influence of Thermal Pre-treatment on Dross
Structure and Reactions”.
For material B the results show no significant difference
in dross formation after thermal pre-treatment. The major
differences in material A and B are the higher density and
level of contamination of scrap B. This can be explained by

Fig. 6 Dross formation mass and

NMP content of dross generated
by three experiments with 100 g
of each UBC scrap type, sorted by
formed dross mass
1110 J. Steglich et al.

the higher level of organic residue on the scrap of UBC Activities of O2 are based on the partial pressure of 4 vol.%
material B, indicated by C and O levels (Fig. 4). O2 at atmospheric pressure, all other adducts are set to 1.
By incomplete removal of organic residue, it is concluded
that the higher density impeded the organic removal as 1=2Mg þ Al þ O2 ¼ 1=2Al2 MgO4
ð3Þ
gaseous pyrolysis/thermolysis products through smaller DG723=823K ¼ 970=945 kJ=mol
tortuous pores. Therefore, a higher compaction rate seems
not beneficial, if organics have to be removed as gaseous 2 Mg þ O2 ¼ 2 MgO DG723=823K ¼ 986=955kJ=mol
products. These results are not contrary to findings of [14, ð4Þ
15], using washed and pre-dried aluminum swarf with usual
volatile content below 0.2 wt%. 4=3Al þ O2 ¼ 2=3 Al2 O3
ð5Þ
DG723=823K ¼ 946=922 kJ=mol

Influence of Thermal Pre-treatment on Dross
Structure and Reactions
Cross sections of dross samples were ground, polished and
investigated by optical microscopy followed by SEM EDX
analysis. For the SEM EDX analysis, the samples were
additionally ion-polished in vacuum, to exclude carbon
contamination. Figure 7 shows the SEM image of dross
sample A Raw in BSE mode. Dark regions have lower
atomic number, bright regions higher.
Figure 7 shows bright regions of pure aluminum (spec-
trum 1) used as metal heal in the experiment, which sur-
rounds an aluminum-oxide “bi-film” [16] (spectrum 4). The
bi-film originates from the can sheet alloy, as the presence of
Mg indicates. The bi-film is present on the can sheets as
natural oxide or by oxidation during pre-treatment according
to reaction 3–5. All ΔG values of the following reactions
were calculated with the reaction module of FactSage Ver-
sion 7.0 [17] at the indicated temperature. The activities of
alloying elements are calculated with the Equilib module,
based on a 3:1 mixture of can body to can end alloy.
Spectrum 4 shows C and S present in the oxide film,
indicating organic residue. C could be present atomic or as
Al4C3 from reaction 8 during dross formation. Spectrum 2
shows similar elements, but O and C in much higher con-
centration in a larger region with a defined shape. Using
5 kV voltage for EDX analysis, the interaction volume has a
diameter smaller than 1 µm. Therefore, all elements can be
present in the area of particle (2). Reactions 6–8 yield
products that can be present simultaneously.
4=3Al þ 2=3MgO þ O2 ¼ 2=3Al2 MgO4
ð6Þ
DG1023K ¼ 896 kJ=mol
2 Mg þ O2 ¼ 2 MgO DG1023K ¼ 885 kJ=mol ð7Þ
4=3Al þ C ¼ 1=3 Al4 C3 DG1023K ¼ 150 kJ=mol ð8Þ
Region (3) with spectrum 3 shows a porous, foam-like
structure with internal porosity and high amounts of O, Mg
and C. The porous structure implies the involvement of
reactive gases as described in reactions 3–7 or the solid
oxidation of magnesium according to

Fig. 7 SEM image of dross sample a raw with according EDX spectra on the right
Dross Formation Mechanisms of Thermally Pre-Treated … 1111

4=3cAl2 O3 þ Mg ¼ 2=3Al þ Al2 O4 Mg
ð9Þ
G1023K ¼ 52 kJ=mol
MgO þ cAl2 O3 ¼ Al2 MgO4 DG1023K ¼ 44 kJ=mol
ð10Þ
Sample A Argon is analyzed in Fig. 8. Unfortunately, the
ion-polishing deposited aluminum material in the porosity of
the dross. Nevertheless, the pyrolysed can coating residue is
visible in the dross matrix after 30 min at 1023 K, stirred in
a 10 kHz induction furnace and forced submerged melting.
Figure 8 shows pyrolysed char residue of can coating
with defined shape, featuring sharp edges at the cracks,
indicating a brittle material, as described in Sect. “Epoxy
Polymer Degradation During Thermal Pre-treatment”. White
TiO2 pigments are passivated in the coating layer, which can
be reduced by aluminum if the char has cracked. Region 1
shows Mg, Si and O present together, which can be formed a
local enrichment in Mg and Si, as by dissolving Mg2Si
phases, which are present in 5000 series alloy systems [16],
according to Eq. 11. This phase oxidation has to be verified
in future work.
Mg2 Si þ O2 ¼ 2 MgO þ Si
ð11Þ
DG823=1023K ¼ 917=866 kJ=mol
In sample A Argon, pores have formed directly at the
pyrolysed coating. The low wetting of aluminum and carbon
[16] promotes the separation of aluminum matrix and the
oxide films, resulting in porosity in between the bi-films.
[16]. Without wetting, coalescence of entrapped aluminum is
impeded.
This observation is confirmed by Fig. 9, showing metal
penetrating through oxide films in the polished cross section
of sample A Air 823 K. The folded oxide films have started
to fragmentize by penetrating metal during dross formation.
The fragmentation is necessary to promote coalescence of
the liquid metal. The oxide films coagulate with other oxi-
des, as refractory or the dross layer on the liquid metal.
Deduction of Dross Formation Mechanisms
and Summary
Following the twin-chamber process organically contami-
nated used beverage can (UBC) scrap bales have been
thermally pre-treated and melted by submerging in Al99.9 in
laboratory scale. Thermal pre-treatment was performed
under argon atmosphere (pyrolysis) and oxygen containing
atmospheres (thermolysis) in air at 723 and 823 K at
atmospheric pressure.

Fig. 8 SEM image of dross

sample A Argon after
ion-polishing with enlarged
section on the right side. The dark
char residue is visible with white
pigments incorporated

Fig. 9 Light optical image of

polished cross section from
sample A Air 823 K. Oxide film
residues of can sheets are visible
in the aluminum matrix
1112
Fig. 10 Proposed dross
formation mechanisms of coated
can sheet with and without
thermal pre-treatment based on
microscopic- and SEM
EDX-results
The UBC material with a density of 450 kg/m3 and a
volatile organic content of 2.8 ± 0.3 wt% responded with
significant difference in organic removal to the thermal
pre-treatment. The lowest dross formation and oxidation of
the material were achieved by thermolysis with argon + 4
vol.% O2 at 823 K (Fig. 6), a heating ramp of 5 K/min and
30 ± 5 min at target temperature. Under the assumption that
closed porosity in an idealized bale of clean sheets is filled
with oxygen containing air, this bale would generate com-
parable amounts of dross. Pyrolysis under pure argon and
equivalent heating conditions increased the dross formation
in comparison to the untreated material. This is caused by
pyrolysed coating char residue, adhering to the metal sheets,
even after forced submerging and a reaction time of
30 ± 5 min at 1023 K in a stirred laboratory induction
furnace. Consequently, the pyrolysis process leads to rein-
forced composite “bi-films” [16] supporting their structure.
The described dross formation mechanisms are summarized
in Fig. 10.
In contrast, the UBC B with a higher density of
910 kg/m3 and high volatile organic content of 8.4 ± 4.0%
does show an increased oxygen content after thermolysis.
The oxidation is possibly caused by locally exothermic
reactions of the plastic content and moisture in the scrap. In
combination with the smaller pores, which impede gas
transport out of the bale structure, the removal of organic
contamination was not successful. Therefore, thermal
pre-treatment of this UBC material shows no significant
reduction of dross formation.
In future work, the reaction kinetics of different carbon
qualities, as for example the amorphous residue of can
coating should be investigated at different temperatures. This
investigation should explain the conditions necessary to
induce carbide formation.
J. Steglich et al.
Acknowledgements The research leading to these results has been
carried out within the framework of the AMAP (Advanced Metals And
Processes) research cluster at RWTH Aachen University, Germany. We
like to thank Aleris Rolled Products Germany GmbH, Constellium,
Hydro Aluminium Rolled Products GmbH and Trimet Aluminium SE
for financial support of this research. Furthermore, the Bachelor Thesis
of student Fabio Rühl is gratefully acknowledged.
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Verlag GmbH, München, 2011), pp. 409–444
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of epoxy adhesives incorporating the influence of post-curing
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polymer and its effect on fire retardancy, thermal degradation and
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14–22 (2015)
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nation of Ignition Loss (2002)
12. D. Stevens et al., Oxidation of AlMg in dry and humid
atmospheres, Light Metals (2011)
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13. S.A. Impey, The mechanism of dross formation on aluminium and
aluminium-magnesium alloys. Ph.D. Thesis, Cranfield institute of
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1113
16. J. Campbell, Complete Casting Handbook (Oxford, Elsevier Ltd.,
1998), pp. 3–103
17. W. Bale et al., FactSage 7.0 (Thermfact Ltd, GTT–Technologies,
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18. T. Ahamad, S. Alshehri, Thermal degradation and evolved gas
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(2013)
 Influence of Coating and De-Coating
on the Coalescence of Aluminium Drops in Salt

Stefano Capuzzi, Anne Kvithyld, Giulio Timelli, Arne Nordmark,

and Thorvald Abel Engh

Abstract
In a rotary furnace for aluminium recycling and dross treatment, a salt flux is added which
protects against oxidation and captures non-metallic impurities. Furthermore, the salt has to
promote the coalescence of the metal drops in the dross. This work investigates the
coalescence of molten aluminium for different types of scrap. One hundred discs were
stamped from aluminium alloy sheets with and without coating. They were melted, covered
in NaCl–KCl–Na3AlF6 molten salt, in an induction furnace at 790 °C. The solidified
aluminum droplets were extracted by leaching the salt with water. The fraction of coalesced
drops and the average diameter were determined to evaluate the coalescence efficiency. The
effect of various de-coating temperatures was studied. The results show that the coalescence
is negatively affected by coating. Long holding times has no effect. Complete coalescence
off all discs are achieved with uncoated scrap. The drops coalesce if the temperature of the
combustion reaction for the coating is attained.

Keywords
Aluminium recycling Coalescence De-coating

Introduction anodization to increase the resistance to corrosion of the

aluminium and for aesthetic reasons [1]. Coatings are
During aluminium recycling, the surface of the scrap is a applied for the same reasons [2] and the coats lead to more
source of various impurities. An oxide layer always covers inclusions during the remelting of the aluminium scrap,
the surface of the aluminium scrap due to the high affinity of lowering its quality. Also aluminium metal reacts with
aluminium to oxygen. This oxide layer can be modified by impurities, which increases the metal loss [3]. In industry,
the charging sequence plays an important role in reducing
S. Capuzzi (&)
G. Timelli the metal loss: it is important to rapidly submerge the scrap
Department of Management and Engineering, under the molten salt to prevent burn-off and high oxidation
University of Padova, 36100 Vicenza, Italy
[4].
e-mail: capuzzi@gest.unipd.it
Pre-processes to reduce the presence of non-metallic
G. Timelli
coats on the scrap surface are therefore necessary. Various
e-mail: timelli@gest.unipd.it
techniques are proposed to de-coat the Al scrap [5, 6].
A. Kvithyld
A. Nordmark
However, the conventional thermal process in rotary kilns is
SINTEF, Trondheim, 7465, Norway
e-mail: Anne.Kvithyld@sintef.no the most frequently used strategy. The aim of the thermal
de-coating process is to combust all the organic material
A. Nordmark
e-mail: Arne.Nordmark@sintef.no without oxidizing the metal [7]. A significant portion of the
combustion gas products is returned to the kiln, creating a
T.A. Engh
NTNU, 7465 Trondheim, Norway recirculation loop. De-coating removes the organic fraction
e-mail: thorvald.engh@material.ntnu.no of the layers that cover the scrap, but oxides and other

© The Minerals, Metals & Materials Society 2017 1115

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_134
1116
impurities remain and affect the scrap. Therefore, it is nec-
essary to remove oxides and impurities present in the
charged scrap and to protect the molten bath from oxidation.
These two goals are achieved by the addition of salts, i.e.
fluxing. An equimolar mixture of sodium and potassium
chlorides is usually used due to the low cost and the low
melting point [8]. The salt, however, entraps molten metal.
The oxides collected in the salt increase its viscosity and
density, slowing metal/salt separation. As a result, a
non-negligible portion of metal is lost in the salt in form of
aluminum drops. The ability of the salt to enhance the
coalescence of these drops becomes a key factor in metal
recovery.
Sodium and potassium chlorides do not promote the
recovery of the metal drops, and in general chlorides, like
MgCl2 or CaCl2, seem not to encourage coalescence [9]. The
addition of fluorides is suggested to be the most effective.
Various fluorides salts have been tested and classified in four
categories regarding the coalescence ability: from poor,
when no fluorides were added, to excellent in case of NaF,
KF, LiF and Na3AlF6 addition [10, 11]. The composition
and the quality of the scrap are important issues. The pres-
ence of Mg negatively affects coalescence by forming a
stronger oxide layer [12, 13], while non-metallic compounds
(NMCs) slow the recovery due to a higher viscosity of the
salt [14].
The aim of this paper is to study coalescence of the
aluminium drops for different scrap surface conditions.
Experimental Procedure
The scrap was stamped out from AA3000 coil (Table 1)
with and without coating in the form of discs with a radius
equal to 4 mm and a height of 0.5 mm.
The coated coils presented various protective layers. The
coat was different on the front and the back side of the coils.
The surfaces of the uncoated and coated discs, as well as the
thickness of the various coats, have been investigated by
Scanning Electron Microscope (SEM).
The thermal de-coating treatments were performed in an
electric resistance furnace at 400, 500 and 600 °C, with a
heating rate 10 °C/min. The treatment at the highest tem-
perature, i.e. 600 °C, is the only one that reached the com-
bustion temperature of the coat. The coils were placed
obliquely. The slanting orientation of the coils is intended to
avoid contact of the surfaces with the furnace walls. The
back side was the upper side for all the treatments.
Table 1 Chemical composition Alloy Si Fe Cu
of the experimental alloy (wt%)
AA3000 0.53 0.58 0.20
S. Capuzzi et al.
The coalescence tests were carried out at 790 °C in an
electric induction furnace.
A flux composed of an equimolar mixture of NaCl–KCl
with the addition of 5% in weight of Na3AlF6 salts was used
in all the tests. The amount of the salt was 4 times the
amount of scrap. One hundred discs were charged to the
molten flux. After the experiment, the crucible was cooled in
air. The salt was leached with water, and the solidified drops
were dried and sieved.
A Matlab code was developed to evaluate the drop
morphology in terms of roundness and aspect radio and to
calculate the area and the equivalent diameter of the pro-
jection of the drops. A drop from a single disc has a diameter
equal to 3.6 mm therefore only the particles whose equiva-
lent diameter was greater than 3.6 mm, here called spherical
drops, were considered for the coalescence efficiency. Two
features were considered to evaluate the coalescence: the
average diameter of the spherical drops and the ratio of the
number of spherical drops to the number of all the drops.
A coalescence factor (CF) was defined as follows:
CF ¼ d  Nb =Nd ð1Þ
Here ḏ is the average diameter of the spherical drops, Nb is
the number of the spherical drops and Nd is the number of all
the drops.
Each de-coating heating condition was studied for a
holding time of 8 min and repeated three times.
The influence of holding time was also considered,
however only for the coated discs. In particular, tests were
performed for 8, 15 and 60 min.
Results
Characterisation
The surfaces of the coated and uncoated discs are completely
different. Firstly, the thickness of the oxide layer on the
coated discs (Fig. 1a) is approximately 10 times greater than
uncoated ones (Fig. 1b), due to an anodization process
applied before the coating.
In addition, two different coatings cover the coated discs.
The priming coating is the same for both sides, a thickness
ranging from 4 to 5 lm was measured. The second layer
differs depending on the side. The front size appears black
and it is 5 lm thinner than the back side that is covered by a
gray pigment. The total thicknesses of the layers are 20 and
25 lm, respectively (Fig. 2).
Mn Mg Cr Ni Pb Zn Ti
0.68 0.34 0.02 0.01 0.01 0.23 0.02
Influence of Coating and De-Coating … 1117

Fig. 1 Scanning electron

microscope micrographs of the
oxides that cover the (a) uncoated
and the (b) coated discs. The
thicknesses of the oxide layers are
measured

Fig. 2 Scanning electron

microscope micrographs of and
the coating layers on the (a) front
side and on the (b) back side of
the coated discs. The thicknesses
of the coating layers are measured

The evolution of the coating layers in response to the
de-coating treatments is shown in Fig. 3. In both cases, the
thickness of the painted layers decreases even at the lowest
temperature.
A greater effect was obtained on the front side. The
thickness of the coat on this side decreased from 20 lm to
less than 5 lm after a de-coating treatment at 400 °C
(Fig. 3a). The reduction in thickness was more evident upon
increasing the temperature (Fig. 3b) and at the highest
temperature, i.e. 600 °C, only the oxide layer is visible
(Fig. 3c).
On the front side, de-coating affects both painted layers,
while the initial primary coating does not significantly
change on the back side. Here, the thickness reduction of the
coat is similar for all the de-coating temperatures (Fig. 3 c, e,
f) and a covering layer is still present even if the coil was
heated at 600 °C (Fig. 3f). The thermal de-coating process
can remove only the organic compounds present in the coats,
so the different results for the two sides can be related to a
different inorganic fraction in the paints.
Figure 4 summarizes the trends in thickness reduction of
the coats for the two sides and the total coat, i.e. the sum of
the two coats. The coat that covers the coil decreases with
increasing thermal de-coating temperature. A layer of about
10 lm persists also at the highest temperature, but the car-
bon fraction is removed.
Furthermore, it must be taken into account that layer
present after the de-coting treatment was not firmly attached
to the metal and a stamping process easily removes it
decreasing even more the amount of impurities charged.
A mechanical removal of the de-coated layer is likely to
happen also during industrial processes in which scrap is
treated in rotary kilns and then moved to storage.
Effect of De-coating
The discs used for the experiments are reported in Fig. 5 to
show the initial conditions.
Figure 6 shows representative drops obtained from
melting the coated discs not thermally treated as well as after
the de-coating treatment. The results obtained from melting
the untreated coated discs (Fig. 6a) and those de-coated at
400 °C (Fig. 6b) are similar: at few drops coalescence and
1118 S. Capuzzi et al.

Fig. 3 Scanning electron microscope micrographs of the coating layers on the (top) front side and on the (bottom) back side after the different
de-coating treatments: a, d 400 °C, b, e 500 °C and c, f 600 °C. The thicknesses of the coating layers are measured

some oxidized discs are present. No disc is oxidized if they

Fig. 4 Evolution of the coating thickness at different de-coating
temperatures
were de-coated at 500 °C and most of them coalesced into
bigger drops (Fig. 6c). At the highest temperature, 600 °C,
all the drops coalesced forming a big drop (Fig. 6d). This is
also seen by the recovered drop of the uncoated discs
(Fig. 6e).
Figure 7 shows the percentage of spherical drops, aver-
age diameter, and CF obtained for all the tested conditions.
The fraction of spherical drops is lower than 1 for the coated
discs and those de-coated at 400 °C, meaning that the scrap
burn off took place. A fraction of spherical drops equal to 1
with a null standard deviation were achieved in the other
experimental condition, i.e. discs de-coated at 500 and
600 °C and uncoated discs. In fact, in all the tests no discs
burned in these experimental conditions.
The low average diameter obtained with coated discs and
those de-coated at 400 °C highlights that the coat prevents
drops coalescence. The uncoated discs reached the highest
average diameter with no standard deviation as one big drop
result in all the replicates. Only a fraction of the discs
de-coated at 500 and at 600 °C coalesced. Therefore the
average diameter is lower compared to uncoated discs.
Influence of Coating and De-Coating … 1119

Fig. 5 Hundred discs before the

experiment cut of the a coated
and b uncoated coil

Fig. 6 Drops obtained melting the discs after different de-coating temperature: a no treatment b 400 °C c 500 °C and d 600 °C and e recovered
drops of uncoated discs

Better results were achieved with a de-coating at 600 than at
500 °C.
The CF is useful in ranking the response at the different
surface condition of the scrap considering both the burn-off
rate and the number of coalesced drops. As mentioned
before, the uncoated discs reached the highest CF. The high
efficiency of the de-coating at 500 and 600 °C is evident.
Effect of Holding Time
The influence of the holding time was tested at 8, 16 and
60 min (Fig. 8) from melting the coated scrap with no
de-coating treatments in the same experimental conditions.
No more coalescence of the drops is achieved by
increasing the holding time. This suggests that coalescence
1120 S. Capuzzi et al.

Fig. 7 Coalescence of the drops

in terms of a fraction of spherical
drops, b average diameter and
c CF for the various types of
scrap

Fig. 8 No coalescence drops obtained melting and for non-treated coated discs at various holding times: a 8 b 16 and c 60 min at 790 °C
Influence of Coating and De-Coating …
takes place during the melting of the discs when they change
morphology and break the oxide layer.
Conclusions
The effects of the surface coating and the de-coating treat-
ment on aluminium drop coalescence in the salt during the
re-melting of AA3000 scrap were investigated. Coalescence
of Al drops in salt is measured. The following conclusions
can be drawn.
• The coat that covers the scrap surface can hinder the
coalescence of the aluminium drops in the molten salt,
preventing their recovery.
• A temperature of de-coating equal to 400 °C is too low
and does not help the drops to coalesce.
• The drop coalescence increases if the combustion reac-
tion temperature is reached in the de-coating treatment.
Acknowledgements The authors acknowledge finical support from
Erasmus, facilities of SFI Metal Production and Hydro Aluminium for
providing materials. We would particularly like to thank Erik Vullum
(SINTEF) for its support with the SEM micrographs and Eva Maria
Gumbmann at Hydro for fruitful discussions.
References
1. I. Tsangaraki-Kaplanoglou et al., Effect of alloy types on the
electrolytic coloring process of aluminum. Surf. Coat. Technol.
200, 3969–3979 (2006)
1121
2. A.A. Tracton, Coatings Technology Handbook (CRC Press Taylor
& Francis Group, 2006)
3. D. Dispinar, A. Kvithyld, A. Nordmark, Quality Assessment of
Recycled Aluminium, Light Metals 2011 (TMS: The Minerals,
Metals & Materials Society, 2011), pp. 731–735
4. G. Girard et al., Furnace operation: “a gold mine in your
casthouse”. Mater. Sci. Forum 630, 77–84 (2010)
5. M.A. Rabah, Preparation of aluminium-magnesium alloys and
some valuable salts from used beverage cans. Waste Manag. 23,
173–182 (2003)
6. N. Li, K. Qiu, Study on Delacquer used beverage cans by vacuum
pyrolysis for recycle. Environ. Sci. Technol. 47, 11734–11738
(2013)
7. A. Kvithyld et al., Recycling light metals: optimal thermal
de-coating. JOM 60, 47–51 (2008)
8. P.N. Crepeau, M.L. Fenyes, L.J. Jeanneret, Solid fluxing practices
for aluminum melting. Mod. Cast. 28–30 (1992)
9. R.D. Peterson, Effect of Salt Flux Additives on Aluminum Droplets
Coalescence, Second International Symposium-Recycling of
Metals and Engineered Materials (TMS: The Minerals, Metals
& Materials Society, 1990), pp. 69–84
10. R.R. Roy, Y. Sahai, Coalescence behaviour of aluminum alloy
drops in molten salts. Mater. Trans. 38, 995–1003 (1997)
11. A. Sydykov, B. Friedrich, A. Arnold, Impact of Parameter
Changes on the Aluminum Recovery in a Rotary Kiln, Light Metals
2002 (TMS: The Minerals, Metals & Materials Society, 2002),
pp. 1045–1052
12. Y.-S. Kim et al., Effects of salt flux and alloying elements on the
coalescence behaviour of aluminum droplets. J. Korea Foundry
Soc. 20, 39–45 (2000)
13. S. Besson et al., Improving coalescence in al-recycling by salt
optimization, in European Metallurgical Conference 2011 (Dus-
seldorf, 2011), pp. 1–16
14. M. Thoraval, B. Friedrich, Metal entrapment in slag during the
aluminium recycling process in Tilting rotary furnace, in European
Metallurgical Conference 2015 (Dusseldorf, 2015), pp. 359–367
 The Scale-Up of High Shear Processing
for the Purification of Recycled Molten Scrap
Aluminium Alloy: Key Features of Fluid Flow

Mingming Tong, Jayesh B. Patel, Ian Stone, Zhongyun Fan,

and David J. Browne

Abstract
In order to remove impurities in scrap aluminum alloys, hence increasing their value, a
laboratory-scale high shear processing (HSP) unit for mixing the molten alloy was
developed, which makes it possible to remove iron-based contaminants using physical
conditioning, at relatively low cost. In order to make this technology applicable in the
industrial environment, we are now investigating the scale-up of HSP by using computer
simulation. The computational research quantitatively predicts a variety of key features of
fluid flow, which determine the feasibility of the scale-up. These include the mass flow rate
through the mixing head, the effective agitation of the melt in the bulk crucible, and the
shear rate that can be achieved. Based on the configuration of HSP that we review in this
paper, we predict that it is feasible to achieve a factor of four scale-up in the volume of
liquid alloy treated.

Keywords
High shear processing Materials purification Aluminium alloy Materials recycling

Introduction
Significant reductions in energy, and environment costs can be
achieved by manufacturing high performance aluminium alloy
using recycled aluminium instead of the primary aluminium
that is produced from bauxite ores. Because scrap aluminium
is normally contaminated by harmful elements e.g. iron, at
relatively high level, a key challenge to the recycling process is
the purification of recycled materials. Physically conditioning
molten scrap aluminium by using high shear processing
(HSP) was recently found to be a promising technology for
M. Tong
D.J. Browne (&)
School of Mechanical and Materials Engineering,
University College Dublin, Dublin, Ireland
e-mail: david.browne@ucd.ie
M. Tong
Mechanical Engineering, College of Engineering and Informatics,
NUI Galway, Galway, Ireland
e-mail: mingming.tong@nuigalway.ie
J.B. Patel
I. Stone
Z. Fan
BCAST, Brunel University, London, UK
this type of purification [1]. It was found that HSP can frag-
ment solid oxide films and clusters in the molten aluminium
alloy into individual fine oxide particles, which act as potent
sites for the nucleation of Fe-rich intermetallic phases. The
solidified intermetallic particles can subsequently be removed
by a downstream sedimentation process, and hence recycled
aluminium alloy is purified by removing the harmful elements.
The original design of the high shear mixer is shown in
Fig. 1. It consists of closely coupled stator and rotor, which
are coaxial and separated by a very small gap. The impeller
of the rotor, which is connected to a long shaft, has four flat
blades. The stator is a tube, which has a series of circular
holes in the wall near its end. The outer diameter of the stator
is 42 mm, and there are 72 holes of 2.5 mm diameter in the
stator which are aligned along four rows. The impeller speed
is conventionally 5000 rpm.
Initial experimental and computational research showed
this mixer to be capable of successfully shearing molten
aluminium alloy in a cylindrical crucible of 300 mm diam-
eter and 300 mm depth, accounting for about 50 kg of liquid
metal. In order to investigate the feasibility of the scale-up of

© The Minerals, Metals & Materials Society 2017 1123

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_135
1124 M. Tong et al.

Fig. 1 Geometry of the original

high shear mixer

the HSP, computational simulation was employed in recent
research. In this paper, we label the former HSP trials, using
the original 42 mm diameter mixer, as the baseline case.
In the case study of the scale-up of the HSP, the design of
the high shear mixer is adjusted. The outer diameter of the new
mixer is 80 mm and there are 280 radial holes of 2.5 mm
diameter in the wall near the end of the stator, aligned along
seven rows. The diameter of the new mixer is almost twice that
of the baseline mixer. The rotor of the new mixer runs at a
speed of 2000 rpm and the mixing head is 150 mm below the
free surface of liquid metal. The crucible that is employed in
the scale-up case of HSP is 650 mm in diameter and 650 mm
deep. In the computation, the crucible is filled with liquid
AA6060 aluminium alloy to a depth of 550 mm. The total
mass of liquid metal in this scale-up case is around 493 kg.
Compared with the former case of HSP using the 42 mm
diameter mixer, this accounts for a factor of nearly ten scale-up
in terms of the mass of the liquid metal.
0.4 and 15 mm. Sliding mesh is employed in order to take into
account the rotational movement of the impeller and its influ-
ence on the fluid flow. The overall governing equations are
solved with the SIMPLE method [5], in order to find the tran-
sient solution of the target problem. The size of the time step is
5  10−4 s. The computation was implemented by using the
FLUENT module of ANSYS.
Mass Flow Rate
The predicted temporal evolution of the mass flow rate of
liquid metal through the different rows of holes in the wall of
the stator is illustrated in Fig. 2. While the flow rate through

Simulation Results

The overall fluid flow problem is mathematically formulated

with the conservation equations of mass and momentum, in 3D
Cartesian coordinates. The turbulence feature of fluid flow is
taken into account by using the realizable k-e model [2] with
enhanced wall treatment [3]. The interface between the liquid
metal and air is implicitly captured by the volume of fluid
method [4]. The overall simulation domain is discretized with
tetrahedral mesh of adaptive resolution, in order to resolve the
geometric features of different sizes at different places in the Fig. 2 Predicted temporal evolution of the mass flow rate through the
computational domain. The mesh size varies between around holes at the side of the stator
The Scale-Up of High Shear Processing …
the rows of holes near the bottom of the mixing head (e.g.
Row 1–4 counting from the bottom of the mixing head
upwards) is comparatively low, the mass flow rate through
the top rows of the holes (row 5–7) is comparatively high. At
the steady state, the total mass flow rate through all the holes
in the wall of the stator is around 3.1 kg/s. Because the fluid
flow reaches its steady state after 2 s of shearing, we analyse
the respective features of fluid flow at this time of 2 s in the
rest of this paper.
The area integrated absolute value of mass flux of the melt
crossing a circular cross-section of the crucible is illustrated in
Fig. 3, which characterises the effective vertical mass flow rate
Fig. 3 Profile of the effective vertical mass flow rate along the depth of
the crucible at 2 s of shearing
Fig. 4 Contour of the melt
velocity in a plane through the
rotor shaft at 2 s of shearing
1125
of liquid metal in the crucible along its depth. In this figure, it
can be found that the effective vertical mass flow rate has a
maximum value at around 50 mm below the bottom of the
mixing head. Within the range of above the top of the mixing
head by 50 mm and below the bottom of the mixing head by
200 mm, the effective vertical mass flow rate is above
3.1 kg/s. The effective vertical mass flow rate mathematically
formulates the significance of the vertical agitation of the
liquid metal in the crucible. As only the vertical agitation of
liquid metal has the capability of redistributing the liquid metal
in the depth of the crucible to go through the mixing head and
get effectively sheared, this rate can be used to characterise the
effective agitation of liquid metal in the overall crucible.
Because the mixing head can only treat the liquid metal at a
rate of 3.11 kg/s (shown in Fig. 1), the liquid metal that is
within the range of 200–500 mm deep in the crucible can be
effectively redistributed through the mixing head and sheared.
The liquid metal that sits at the bottom 200 mm of the crucible
or at the top 50 mm relative to the free surface is not effectively
redistributed through the mixing and sheared. This means that
approximately 269 kg liquid metal can be effectively processed
at the mass flow rate of the order of 3 kg/s in this crucible.
Radial Agitation of the Liquid Metal
The effective vertical mass flow rate only quantifies the
vertical component of melt flow, averaged across the
diameter of the crucible. When sampling the contour of melt
velocity along a plane through the rotor shaft as shown in
Fig. 4, it can be seen that the magnitude of melt velocity is
1126
Fig. 5 Contour of melt velocity
of 1 cm/s at 2 s of shearing
Fig. 6 Vector of melt velocity at
2 s of shearing
relatively high in the close vicinity of the mixing head and it
decays rapidly away from the mixing head. The liquid metal
near the wall or bottom of the crucible is relatively stagnant.
The radial profile of the velocity of the melt is very
nonuniform. If we define the value of melt velocity of 1 cm/s
to be the threshold value that defines the volume of well
agitated melt, we can get the geometry of effective agitation
as shown in Fig. 5.
M. Tong et al.
The diameter of this volume is around 450 mm and it
extends from the free surface of liquid metal continuously
downwards by around 400 mm. This means that this 80 mm
diameter mixer can effectively agitate the whole liquid metal
in a 450 mm diameter and 400 mm deep volume when
running at an impeller speed of 2000 rpm.
The vectors shown in Fig. 6 demonstrate the tangential
velocity of the liquid metal at a plane through the rotor shaft
The Scale-Up of High Shear Processing …
Fig. 7 Streamline of the liquid
metal at 2 s of shearing
at 2 s of shearing. It can be seen that there is a very localised
strong recirculation of liquid metal near the bottom of the
mixing head. Such recirculation entrains the outshooting
melt jets immediately back into the mixing head through the
large opening at its bottom. This strong and localized melt
recirculation makes the liquid metal in the far field difficult
to agitate effectively. Above the mixing, however, the melt
jets shooting out through the holes in the wall of the stator
are acting as a highly energetic barrier, impeding the liquid
metal above the mixing head from flowing into it at all.
The streamlines shown in Fig. 7 can help our under-
standing of the overall flow pattern of the liquid metal in the
crucible. Within the range of 100 mm above and below the
mixing head, there is a very strong recirculation of the melt
in the far field of the crucible, along which the liquid metal
flows along the radial and circumferential direction simul-
taneously. Below this region, there is a counter rotating
recirculation of the liquid metal, along which the liquid
metal flows at relatively low velocity.
Shear Rate
As shown in Fig. 8, the turbulence eddy dissipation rate is
highly nonuniform along the depth (a) and diameter (b) of
the crucible. The characteristic shear rate can be calculated
by using the square root of the turbulence eddy dissipation
rate divided by the kinematic viscosity of the melt as:
1127
rffiffiffi
e
r= : ð1Þ
m
At the time of 2 s of shearing, the maximum shear rate in
the whole crucible is 6.56  105/s.
Discussion and Conclusion
According to calculations using CFD modelling, in the
scale-up case of the HSP treatment of molten aluminium
alloy, we predict achievement of a mass flow rate of around
3.1 kg/s through the mixing head. This value is less than the
corresponding value (10.3 kg/s) of the baseline case (when
formerly using the 42 mm diameter mixer). The key reason
is that we sheared at 5000 rpm in the baseline case and
sheared at 2000 rpm in the scale-up case. However, it was
found that a relatively larger volume of liquid metal is
effectively agitated in the scale-up case. Specifically, within
the range of 300 mm in depth, about the mixing head, the
effective vertical mass flow rate across the diameter of the
crucible can match the mass flow rate through the holes at
the side of the stator (Fig. 2). It is reasonable to conclude
that the 80 mm mixer can effectively agitate and shear the
whole bulk liquid metal in a crucible of 450 mm diameter
and 300 mm deep. This accounts for around 129 kg of
AA6060 alloy.
While the scale-up case has a lower value of mass flow
rate through the mixing head, its maximum value of shear
1128 M. Tong et al.

Fig. 8 Contour of the turbulence

eddy dissipation rate at a plane
along the rotor shaft (a) and at a
plane that is normal to the rotor
shaft and sectioning a row of the
holes in the wall of the stator
(b) at 2 s of shearing

rate (6.56  105/s) is higher than that of the baseline case
(1.95  105/s). This is probably because the larger size
mixing head has larger space for the turbulence of fluid flow
to develop. While using either the baseline case or scale-up
case setup of HSP, the high shear rate only exists in the close
vicinity of the mixing head and the liquid metal is only
strongly agitated within a distance of a few centimetres
above and below the mixing head.
The overall conclusion is that the scale-up case can be
expected to effectively treat the liquid metal in a 450 mm
diameter and 300 mm deep crucible (holding around 129 kg
aluminium alloy) within the time order of a minute, using the
80 mm diameter mixer running at 2000 rpm. Compared with
the baseline case of HSP, this accounts for the scale-up of
around factor of three. Because only a moderate rotor speed
of 2000 rpm was employed in the computation, and the mass
The Scale-Up of High Shear Processing …
flow rate through the mixing head was found to be strongly
and positively dependent on the impeller speed by our recent
research, it is reasonable to estimate that the 80 mm mixer
has the potential to be effectively applied in the four time
scale-up of HSP (i.e. treating 200 kg liquid metal at a time
running at 5000 rpm or so) instead of three time scale in
reality. If an even high factor of scale-up of HSP is to be
achieved, besides using an even larger size mixer in diam-
eter, adjusting the length of the stator below the bottom of
the mixing head is an option. The extension of the length of
the stator can dramatically enlarge the volume of well agi-
tated liquid metal without needing a higher power motor to
drive the rotor.
Acknowledgements This work is financially supported by the Euro-
pean Commission FP7 project “High shear processing of recycled
aluminium scrap for manufacturing high performance aluminium
alloys”; Grant Number 603577.
1129
References
1. M. Tong, S. Jagarlapudi, J. Patel, I. Stone, Z. Fan, D.J. Browne,
Computational prediction of the refinement of oxide agglomerates
in a physical conditioning process for molten aluminium alloy. IOP
Conf. Ser: Mat. Sci. Eng. 84, 012092 (2015)
2. T.H. Shih, W.W. Liou, A. Shabbir, Z. Yang, J. Zhu, A new
eddy-viscosity model for high reynolds number turbulent flows—
model development and validation. Comput. Fluids 24, 227–238
(1995)
3. ANSYS® Academic Research, Release 17.0, Help System. Turbu-
lence. ANSYS, Inc.
4. C.W. Hirt, B.D. Nichols, Volume of fluid (VOF) method for the
dynamics of free boundaries. J. Comput. Phys. 39, 201–225 (1981)
5. S.V. Patanker, D.B. Spalding, A calculation procedure for heat,
mass and momentum transfer in three-dimensional parabolic flows.
Int. J. Heat Mass Transf. 15, 1787–1806 (1972)
 Centrifugal Casting of Al–Si Scrap

Aya Assem, Shimaa El-Haddad, and Iman El Mahallawi

Abstract
Recycling is a sustainability strategy that enables environmental savings as well as energy
and cost reduction. Sustainability and reduced energy consumption requirements demand
that Al–Si alloys are recycled by re-melting. Industries that use cast Al–Si alloys are
increasing, leading to more consumption of these alloys that in turn leads to more
scrap. Unfortunately, when cast Al–Si alloys are recycled, detrimental microstructures
combined with reduction in the mechanical properties occur. In this work, the limitations of
recycling of cast Al–Si scrap are discussed. To overcome some of these limitations,
centrifugal casting was adopted and the effect of the centrifugal speed was investigated. The
microstructure of Al–Si alloys with high recycled content produced by centrifugal casting
using different parameters was studied. The independent variables are the centrifugal speed
and scrap material mix. The microstructure of the recycled cast Al–Si alloys was observed
to improve by centrifugal casting, resulting a graded microstructure from inner to outer
surface of the casting. The centrifugal separation is shown to be a promising method for
controlling the Fe-rich enormous structures and the porosity present in the recycled Al–Si
alloys.

Keywords
Al scrap Centrifugal casting Microstructure

Introduction
Recycling is a sustainability strategy that is gaining inter-
national interest in order to achieve environmental savings as
well as energy and cost reduction. Al–Si cast alloys are
A. Assem
Faculty of Engineering, Mechanical Engineering Department,
The British University in Egypt, El Shorouk, Egypt
e-mail: Aya116242@bue.edu.eg
S. El-Haddad
Central Metallurgical Research and Development Institute
(CMRDI), Helwan, Egypt
I. El Mahallawi (&)
Faculty of Engineering, Metallurgical Engineering Department,
Cairo University, Giza, Egypt
e-mail: saiman@eng1.cu.edu.eg; ielmahallawi@bue.edu.eg
among the highly used Al alloys in some industries [1]. The
range of products made from these alloys in the automotive
industry results in accumulation of Al–Si scrap that could be
recycled.
Recycling of metal parts is usually done by re-melting
and casting into ingots or by pouring the molten metal into
large thermal containers and keeping it in the liquid state [2].
The cost of the ingots produced from scrap Al alloys is much
less than that produced from primary Al, therefore, many Al
castings are fabricated from recycled scrap [3]. According to
Kim and Im in March 2013, half of the production of Al
alloys in the European Union (EU-25) originated from
recycled materials [2].
Production using primary Al demands a great deal of
energy, which will be significantly reduced if the Al–Si
alloys are re-melted to provide this material. More than 90%
of the required energy for production of Al alloys may be

© The Minerals, Metals & Materials Society 2017 1131

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_136
1132
saved upon re-melting [5], as re-melting only requires up to
5% of the actual energy needed for the initial production [2].
However, re-melting Al alloys is a challenging task due
to the imperfections found in recycled alloys by re-melting.
Iron impurities provide a great challenge, as they affect
negatively the mechanical properties of the recycled
material, especially when combined with silicon [6].
Moreover, an accumulation of the impurities occurs grad-
ually due to the repetitive usage of the scrap. Fe is among
the most important harmful impurities for these alloys,
taking into consideration that iron removal is harder when
there is less amount of iron content [2–7]. Several inves-
tigations have reported the presence of enormous inter-
metallic precipitates in recycled Al–Si alloys. High
porosity in cast recycled Al alloys is another challenge [4].
The chemical properties of the recycled material are also
impaired.
Therefore, the aim of this work is to study, the recycling
limitations of the recycled Al–Si scrap. Centrifugal casting is
suggested in this work as an alternative one-step economical
casting method for recycled Al scrap.
Experimental Methods and Approach
Sample Preparation
This study investigated the effects brought about by using
centrifugal casting instead of gravity pouring methods on the
microstructure of cast-recycled material. We investigated the
effect of varying parameters on the microstructure of prod-
ucts made from recycled scrap. The investigated parameters
Fig. 1 Schematic diagram of the rod specimen
Table 1 Chemical composition AL-01 Al-global calibration
of the scrap
Average of 2 sparks
Si Fe Cu
X 10.2 >2.25 1.79
Sn Ti V Co
X 0.0434 0.0325 0.0076
A. Assem et al.
are the speed of rotation (from 300 to 500 rpm) and the
material composition. Figure 1 shows a schematic illustration
of the rod-type sample produced in this work. Table 1 shows
the composition of the scrap material used for this study. In
addition to the scrap, A413 Al–Si and A390 Al–Si were used
in this study. Three groups of material were prepared, one
group consisting of 100% scrap and two groups consisting of
50% scrap and 50% of each alloy. Eight grams from each
alloy were used, in case of single material. Four grams from
each material were used in case of mixed material.
Machines and Equipment
Figure 2 shows the Ultra Flex centrifugal casting machine
used for this work. The machine operates under vacuum.
The mould was prepared using a rubber silicon former and
an investment powder (SHERATITAN-EASY) with
SHERALIQUID and SHERALIQUID EXTRA added to the
powder and mixed together with specific amounts until fully
homogenous (Fig. 3a), the mix was left in the former for
24 h until it dried (Fig. 3b).
The mould was then preheated up to 700 °C in a
de-waxing oven before the centrifugal process. After that,
the material to be recycled and the mould were placed in the
centrifugal casting machine as in Fig. 4, then the machine
was prepared with the desire setup to recycle the sample
using centrifugal casting. Figure 5 shows one of the samples
produced.
All the manufactured samples were prepared by grinding
and polishing to be examined by the optical microscope as
well as SEM with EDX analysis. The prepared samples were
divided into three main sections, inner, middle and outer
surfaces of the cast samples to study the gradient.
Results and Discussion
Alloy Made from 100% Scrap
Figure 6 illustrates the micrographs for all the samples
obtained from one single material in this work.
It can be observed from the previous comparison that, the
intermetallics size differed from inner to outer more in the
11/2/15 13:36
Mn Mg Zn Ni Cr Pb
0.150 0.146 3.71 0.056 0.0243 0.123
Al
0.00256 61.19
Centrifugal Casting of Al–Si Scrap 1133

material made from scrap rather than the other alloys while the cast scrap. The EDX analysis indicates the presence of iron
silicon particles distribution was more affected by centrifugal intermetallics and b-Al5FeSi (point 1) [2]. Point 2 is a Cu-rich
force in the Al–Si alloys. At 300 rpm a reduction in length of phase [3] with Zn particles as inclusions according to the EDX
intermetallics particles from 400 to 100 µm was observed analysis. Primary eutectic Si particles are also observed in
(Fig. 7). With increasing speed, relatively smaller inter- point 3. The EDX analysis is shown in Table 2
metallics were produced with lower porosity. SEM was used
to identify the intermetallics and the different structures in the
produced samples. While, EDX was used in order to identify
the chemical composition of some specific spots on the SEM
to identify the structures. Figure 7 shows the SEM micro-
graphs of the intermetallic phases observed in the centrifugal

Fig. 4 The mould connected with the crucible in the machine

Fig. 2 The ultra flex vacuum centrifugal casting machine Fig. 5 One of the produced samples

Fig. 3 a The homogenous mould mix. b Then mould after it dried

1134 A. Assem et al.

Fig. 6 Microstructure of produced single material rods at different rpm

Centrifugal Casting of Al–Si Scrap 1135

50% Scrap–50% Alloy Material Composition

This composition consists of scrap as the main component in

addition to A413 or A390 Al–Si alloy. In this experiment,
the rotational speed was fixed at 400 rpm while the material
composition was varied. The results are shown in Fig. 8
showing the micrographs obtained from the optical micro-
scope for these samples.
Figure 9 shows a magnified SEM image of the 50%
scrap–50% A413 Al–Si sample at 400 rpm, from which the
change in the length of the Fe-intermetallic phases with
respect to the outer direction is observed. The EDX analysis
showed that many elements exist and precipitated in the
sample during the centrifugal casting. In addition, the den-
sity of the intermetallics such as points (1) and (2) inclusions
is less in the outer surface of the sample.

Fig. 7 a Material made from scrap microstructure at 300 rpm, b at
400 rpm, and c SEM at 400 rpm
Conclusion
• The point furthest from the centre of rotation shows
smaller silicon particles and smaller iron intermetallics,
and smaller needles form at the outer surface.

Table 2 The EDX analysis Atomic

Element Weight% % Net Int. Error%
EDX 1 in scrap microstructure
OK 1.55 3.07 11.93 16.83
AIK 56.39 66.41 1610.5 5.09
SiK 11.72 13.25 209.27 8.59
Fek 30.34 17.26 298.56 2.85
EEDX for spot 2 in scrap microstructure
OK 12.06 20.81 24.31 12.59
AIK 66.03 67.59 506.11 5.31
SiK 3.38 3.33 14.57 14.97
Fek 6.14 3.03 16.55 10.47
Znk 12.39 5.24 16.08 10.52
EDX for spot 3 in scrap microstructure
OK 15.03 24.35 102.85 10.45
AIK 68.2 65.53 2000.69 3.98
SiK 6.03 5.56 90.72 9.95
Fek 3.65 1.7 32.66 12.91
Cuk 4.03 1.64 21.35 14.58
Znk 3.07 1.22 13.37 18.55
1136
Fig. 8 Microstructure of 50%
scrap–50% alloy material com-
position samples at 400 rpm
Fig. 9 SEM of produced mixed
S+A413 at 400 rpm
• The length of the intermetallic particles decreases from
about 400 µm to less than 100 µm, with the rotational
speed of 300 rpm for the 100% scrap samples.
• Porosity density decreases with distance from the inner
surface and with higher speeds.
• Centrifugal casting produces new phases where it attracts
most of the composing elements to form new inter-
metallic phases and inclusions far from the outer surface.
• The addition of fresh alloys to the scrap did not result
improvement in the microstructure.
A. Assem et al.
References
1. C.G. Maricel, Mechanical and fatigue properties of functionally
graded aluminium silicon alloys, Ph.D. Thesis, Minho Escola de
Engenharia University, pp. 61–67, 2011
2. S.W. Kim, H.C. Cha, Removal of primary iron rich phase from
aluminum-silicon melt by centrifugal separation. Overseas Foundry
25(2), 112–117 (2013)
3. E. Fiorese, F. Bonollo, G. Timelli, New classification of defects and
imperfections for aluminum alloy castings. Int. J. Metalcast. 9(1),
55–66 (2015)
Centrifugal Casting of Al–Si Scrap
4. G. Mrówka Grazyna-Nowotnik, in Intermetallic Phases Examina-
tion in Cast AlSi5Cu1Mg and AlCu4Ni2Mg2. Recent Trends in
Processing and Degradation of Aluminium (Shanghai, InTech,
2011), pp. 20–40
5. E. Tillová, M. Chalupová, L. Hurtalová, in Evolution of Phases in a
Recycled Al-Si Cast. Scanning Electron Microscopy (InTech, 2012),
pp. 411–437
1137
6. A. Bjurenstedt, Imperfections in Recycled Aluminium-Silicon Cast
Alloys (Department of Materials and Manufacturing—School of
Engineering, Jönköping University, Jönköping, 2015)
7. J. Giblert Kaufman, E.L. Rooy, Aluminum Alloy Castings: Prop-
erties, Processes, and Applications (American Foundry Society,
USA, 2004)
 Improved Recyclability of Cast Al-Alloys
by Engineering b-Al9Fe2Si2 Phase

C.B. Basak and N. Hari Babu

Abstract
Castability and tensile properties of recycled cast Al–Si alloys are affected by the presence
of high iron content. The present study demonstrates a promising scope of better
recyclability by engineering the intermetallic b-phase that present in cast Al–6 wt%Si
model alloy systems with as high as 2 wt%Fe. Thermodynamic interplay between Si and
Fe concentration on the formation of the b-phase and the solidification behaviour of this
hypoeutectic Al–Si alloy has been explored. It has been demonstrated that suitable heat
treatment alters the morphology of the b-phase and simultaneous addition of Cu improves
the strength. Based on the experimental evidences, the mechanism behind the solid-state
morphological changes of beta phase has been proposed. Experimental results and
thermodynamic calculations suggest that Cu content of more than 2 wt% marginally
increases the yield of beta phase; however, at 4 wt%Cu the solid solution strengthening
improve the strength of solutionized alloy.

Keywords
Aluminium alloy Intermetallics Precipitation Thermodynamic modelling Scanning
electron microscopy

Introduction physical separation techniques are being employed in the

Primary production of aluminium from bauxite ore attracts
an energy expenditure of about 186 MJ/kg of metallic
aluminium; however, this expenditure could be reduced to
10–20 MJ/kg by recycling the discarded aluminium prod-
ucts or scraps [1, 2]. These figures emphasize not only the
economic importance but also the underlying environmental
benefits in the favour of recycling aluminium scraps.
Recyclable scrap may come from manufacturing industries,
automobile sector, beverage cans and from other miscella-
neous sources. Because of the diversified sources and
involvement of processing equipment the recycled
aluminium accumulates several metallic impurities, e.g. Si,
Mg, Ni, Zn, Pb, Cr, Fe, Cu, V, Mn to name a few. Different
C.B. Basak (&)
N. Hari Babu
BCAST, Brunel University London, Kingston Lane,
Uxbridge, Middlesex UB8 3PH, UK
e-mail: chandrabhanu.basak@brunel.ac.uk
industries today before melting the Al-scraps to minimize
the impurity pick up in the recycled aluminium products;
e.g. magnetic separation, air separation, heavy media sepa-
ration (using water based slurry) and colour sorting [3].
Despite employing such physical separation techniques, iron
pick up from the handling and processing equipment
remains inevitable. This residual iron impurity poses as the
major challenge for the recycled aluminium because of two
main reasons. Firstly, higher iron content usually associated
with less flowability and shrinkage porosities in the casting,
i.e. poor castability and secondly, it drastically reduces the
ductility due to the formation of intermetallic phases,
specifically the b-phase.
Al–Si alloys are usually considered as cast alloys and
have applications in automobile sectors. Higher iron content
in Al–Si alloy system causes formation of several inter-
metallic phases, e.g. hexagonal a-Al8Fe2Si (s5), monoclinic
b-Al9Fe2Si2 (s6), d-Al4Fe2Si (s11) etc. along with other

© The Minerals, Metals & Materials Society 2017 1139

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_137
1140
binary Al–Fe compounds (Al13Fe4, Al5Fe2 etc.); further
details on these intermetallic compounds are available in the
literature [4–7]. However, thermodynamic selection of
intermetallic phase formation is strongly dependent on the
concentration of both Fe and Si [8, 9].
The room temperature intermetallic phase in high Fe
containing Al–Si alloy is the so-called b-Al9Fe2Si2 phase,
also designated as b-Al5FeSi or s6 phase as reported in the
literature [4–9]. It is known that this inherently brittle
b-phase is formed as three-dimensionally interlinked thin
platelets with characteristic needle-like appearance [10, 11].
This interconnectivity of the b-phase along with its poor
thermal conductivity causes retention of isolated liquid metal
pool in the inter-dendritic cavities causing shrinkage
porosity in the final casting upon solidification [12]. Higher
Fe content in the Al–Si alloys also causes reduced fluidity of
the molten alloy causing inefficient and rather poor die filling
[13]. These factors together render poor castability in
high-Fe Al–Si alloys as mentioned earlier. On the other
hand, the sharp corners (and often incoherent interface) of
the b-phase act as stress raisers in the matrix causing severe
brittleness in the final casting; with a comparatively lower
strength and no more than about 3% ductility [9]. The only
apparent advantage of having higher Fe content (up to about
0.9 wt%Fe) is the avoidance of die sticking or soldering in
the die castable Al–Si–Fe alloys [10].
The most straightforward approach to counter the level of
iron impurity is to dilute the recycled aluminium using
primary aluminium, also known as “down cycling” [3].
A second approach is to hinder the formation of b-phase by
Mn addition, in case of moderate Fe level, by promoting the
formation of Al15(Fe, Mn)3Si2 phase having polygonal
morphology. Such change in morphology actually improves
the ductility of the castings. However, beyond about 1.2 wt
%Fe both needle like b-phase and polygonal Al15(Fe,
Mn)3Si2 phase appears which diminishes the positive effect
of Mn addition [12]. The question we address in this paper
is, if recycled Al-Si cast alloys can accommodate more than
1.2 wt%Fe concentration without Mn addition.
In Al–Si alloys almost all Fe contributes to the formation of
equilibrium b-phase (i.e. higher Fe causes more phase fraction
of b-phase) owing to its extremely low solid solubility in Al of
about 10 ppm [14]. Therefore, it makes sense, rather than
focusing on Fe, to focus on dealing with the b-phase. This
approach could offer an indirect way to deal with the high Fe
content in Al–Si alloys. Two different methodologies could be
proposed based on this philosophy; namely, gravitational
segregation of b-phase and alteration of morphology of the
b-phase; which has been discussed in details in the literature
[9]. It suffices here to state that the segregation of b-phase in
liquid alloy is possible owing to the difference in the density
between the b-phase and liquid-Al. However, we note that
segregation of b-phase changes the overall chemistry of the
C.B. Basak and N. Hari Babu
liquid alloy towards low iron as well as low silicon content;
whereas alteration of morphology of the b-phase targets to
keep the chemistry invariant and yet tries to improve the
mechanical properties. Segregation of b-phase can only take
place before the final casting is produced; whereas altering the
morphology of b-phase can be done in the final cast product
using suitable heat-treatment. Along the similar line of
thought, one could use filtration technique as well to separate
the b-phase from the molten liquid [15].
Experimental Procedure
Al–6 wt%Si–2 wt%Fe was chosen as the model alloy; for
the sake of brevity this alloy would be referred as 6Si alloy
or base alloy in the rest of the article. Also, 2 and 4 wt%Cu
was added to see the effect of Cu in the tensile strength of the
alloy under different heat treated condition. Al ingots, Al–
50 wt%Si, Al–45 wt%Fe and Al–40 wt%Cu master alloys
having commercial purity level were used for preparing the
alloy. A resistance furnace and boron nitride coated clay
bonded graphite crucible was used for preparing the alloy.
First Al ingot was melted and then Al–Si and Al–Fe master
alloy was added sequentially with stirring. A melt of about
1 kg was prepared at 800 °C with intermittent stirring of at
least 6 times with a total holding time of 2 h to ensure
chemical homogeneity. Commercially available degassing
tablet was used and the top oxide layer of the melt was
skimmed off. Finally, the melt at a temperature of 750 °C
was poured into a boron nitride coated mild steel rectangular
block preheated at 250 °C. An average cooling rate of about
4–5 °C/s was expected based on previous experiments and
existing literature [8]. A part of the melt also poured in a
60 mm dia. steel die for chemical analysis using glow dis-
charge optical emission spectroscopy (GD-OES). GD-OES
chemical analysis is provided at Table 1, which is averaged
over five analyses from five random locations.
For microstructural analysis, standard metallographic
practice was adopted where final polishing was carried out
using 0.25 lm colloidal silica. An aqueous solution of
10 wt%NaOH was used for chemical etching, whenever
required. A field emission scanning electron microscope
(FESEM) (having both secondary electron (SE) and back
scattered electron (BSE) detectors) equipped with energy
dispersive spectroscope (EDS) was used for microstructural
analysis. An x-ray diffractometer was equipped with
solid-state detector and operated at 1.6 kW Cu–Ka radiation.
Thermodynamic calculations were performed with CALcu-
lation of PHAse Diagram (CALPHAD) methodology using
PandaT software [16] and image analysis were carried out
using ImageJ software [17]. Tensile testing was carried out
in selected specimens with 25 mm gauge length in compli-
ance with ASTM B557-10 standard [18].
Improved Recyclability of Cast Al-Alloys … 1141

Results and Discussions

0.002
0.002
0.001
The calculated isopleth at 2 wt%Fe obtained from CAL-

Table 1 Typical chemical composition (in wt%) of 6Si and Cu added 6Si samples from GD-OES analysis, elements having concentration less than 0.001 wt% are not shown here
P
PHAD calculation is depicted in Fig. 1; where 6Si compo-
sition line is indicated. We note that though lever rule, in
general, can not be applied in such isopleth, nevertheless it is

0.004
0.009
0.009
helpful in determining the phases present at any given
Zn temperature and composition. Figure 2a shows solidification
profiles of the base alloy as per Scheil and equilibrium
solidification model. Figure 2b depicts the yield of b-phase
during solidification at different level of Cu as per Scheil
0.004
0.005
0.005
Mg

model; since most of the practical alloys follow Scheil model

during solidification [19]. It is interesting to note that the
calculated liquid phase fraction does not differ in an appre-
ciable way between the two solidification models for a given
0.005
0.007
0.008

alloy. The reason for such model invariant solidification is

Sn

due to the fact, as can be seen from Fig. 1, that the liquid
phase of the base alloy is in equilibrium with one of the
intermetallic phases; namely, a-phase and b-phase (at lower
0.006
0.005
0.005

temperature). Since, these intermetallic phases do not show

Ca

appreciable range of solute solubility for either Si or Fe.

Therefore, as solidification progresses only the fraction of
intermetallic phase (b or a-phase) increases without any
0.006
0.007
0.008

appreciable change in its composition; as exhibited by an

Ni

equilibrium model or Scheil model. Therefore, the corre-

sponding liquid phase fraction also remains model invariant
at any given temperature. Only small deviation occurs
0.006
0.007
0.006

between the two models due to the generation of pro-eutectic

Mn

Al having appreciable solubility of Si. Thus, such variation

is slightly more predominant where pro-eutectic Al is more,
i.e. for compositions away from the eutectic composition.
0.015

Figure 3a is the as-cast microstructure of 6Si samples (as

0.01
0.01
In

polished condition) in BSE mode where b-phase appears

brighter due to the presence of heavy element like Fe.
0.011
0.013
0.009
Ti
0.012
0.011
0.009

Temperature, oC
Ga
0.003
2.11
4.02
Cu
1.97
1.96
2.01
Fe

Composition, wt% Si
6.02
6.12
6.08

Fig. 1 Isopleth of Al–Fe–Si system sectioned at 2 wt%Fe, red dashed

Si

lines indicate 6 wt% and 10 wt%Si compositions

1142 C.B. Basak and N. Hari Babu

1.0 diffusion of the chemical species and thereby facilitating

(a) 12
faster change in the morphology of the b-phase. The

Elemental concentration in liquid, wt%

0.8 Liquid 10 microstructures of these samples are shown in Fig. 3c, d.
Phase fraction, mole/mole

Al
β−Al9Fe2Si2 Upon comparison with the as-cast sample (Fig. 3a) it
0.6 α−Al8Fe2Si 8
becomes rather clear that the platelets of b-phase get refined
6
by fragmentation. In fact, image analysis of 6Si sample
0.4 Si reveals that the average aspect ratio of b-phase platelets
4 reduces from 6.2 to 2.7 from the as-cast condition to the one
0.2
Fe
isothermally held at 572 °C for 24 h as shown in Fig. 3c, d.
2
Subsequent X-ray mapping clearly reveals that the
0.0 grey-shaded rounded particles, almost obscured in the
0
580 590 600 610 620 630 640 background (Al matrix), are nothing but Si particles; as
Temperature, oC evident from Fig. 4a, c. It is important to note that the Si
particles also tend to be spheroidized during heat-treatment as
0.050 (b) indicated in these micrographs. Therefore, it could be con-
0.045 sidered that the as-cast microstructures of 6Si alloy are
0.040 L <=> Al + Si + β
actually far from the equilibrium so long as the phase mor-
0.035 phology is concerned. Similarly, a 24 h of soaking was given
Phase fraction

0.030 to 2 wt% Cu and 4 wt%Cu samples at 520 °C instead of

0.025
0.020
0.015
0.010 0Cu
2Cu
0.005 4Cu
0.000
520 540 560
Temperature, oC
Fig. 2 a Simulation of solidification as per equilibrium model and
Scheil model for 6Si alloy (0Cu or base alloy). Solid line indicates
Scheil model of solidification whereas dashed line indicates lever rule
method (equilibrium model). Symbol+line (right hand axis) are for the
composition of the liquid phase. Note that liquid composition profile
does not change much from equilibrium model to Scheil model. b Yield
of b-phase as a function of temperature
Figure 3b is the as-cast microstructure with the addition of
4 wt%Cu with two noted features that are distinct from the
base alloy; i.e. presence of eutectic Al2Cu and absence of
Al–Si eutectic. No noted difference was found between
2 wt%Cu and 4 wt%Cu except the lower amount of Al2Cu
phase in the former.
Morphological Change of b-Phase
It is well known that solid-solid interfacial energy is always
higher than the solid-liquid interfacial energy. Therefore, it is
but natural to expect that the morphological change of the
b-phase can minimise the interfacial energy, with suitable
heat-treatment in solid-state. Accordingly, 6Si samples were
isothermally held at 572 °C for 24 h. The idea behind this
heat treatment is to go to a temperature as high as possible
near to the eutectic point (575.7 °C) to facilitate faster
580 °C; owing to the lower solidus temperature of Cu added
alloys. After this soaking treatment, microstructurally no
difference was observed than that of base alloys, except for a
small amount of Al2Cu formation in 4 wt%Cu alloy. This
indicates that most of the Cu goes into the solid solution.
It has also been thought to modify the morphology of the
580 600 620
b-phase of base alloy by heat-treating just above the eutectic
temperature, i.e. at 580 °C, but without inducing any segre-
gation. Accordingly, only 2 h of soaking was given to 6Si
samples at 580 °C. From Fig. 2a it could be seen that the
phase fractions of the liquid phase is about 38% at 580 °C for
6Si alloy; however, no visual shape change was observed in
6Si sample after the heat-treatment. Microstructures for 6Si
samples treated at 580 °C are presented in Fig. 3d. Based on
the obtained results the following observations can be made:
(i) Change in morphology of b-phase is strongly
dependent on the heat-treatment temperature. Aging
above eutectic temperature (575.7 °C) causes faster
growth of b-phase (in thickness) due to the faster
diffusion in liquid phase [20]; whereas below
575.7 °C, growth process is slow and fragmentation
across the length was observed.
(ii) Morphology of Si particles is also greatly dependent
on heat-treatment temperature. Aging below eutectic
temperature causes Si lamellae to become spher-
oidized, as shown in Fig. 4b. However, involvement
of liquid phase (eutectic) during heat-treatment would
give rise to zagged-blocky Si resembling to divorced
eutectic morphology.
(iii) Addition of Cu tends to destroy the Al–Si eutectic
structure rendering blocky shaped Si particles that
become spheroidized upon isothermal soaking.
Improved Recyclability of Cast Al-Alloys … 1143

Fig. 3 BSE images in as-cast

condition for a 6Si alloy and (a) (b)
b with 4 wt%Cu addition; note
the needle like white b-phase and
Al2Cu eutectic in (b). BSE
micrographs of c 6Si samples
held at 572 °C for 24 h reveals
remarkable refinement of b-phase
and fragmented yet aligned
b-phase particles (encircled).
d 6Si sample held at 580 °C for
2 h with coarse b-phase particles
and needle like Si (arrows) grown
within the liquid network

Si

Al2Cu

(c) (d)

Mechanism of Morphological Change
We see from Fig. 3a, b that the b-phase platelets are of high
aspect ratio; which is expected due to crystallographically
anisotropic growth while precipitating from the liquid phase
for faster accommodation of atoms across the liquid-beta
interface during solidification. As a result, the as-cast
microstructure is in morphologically metastable state due to
high surface area of the primary b-phase platelets as indicated
earlier. In order to minimize the surface energy two conditions
must be satisfied simultaneously; microscopically the lowest
energy crystallographic interface should prevail and macro-
scopically, surface area of b-phase platelet should be mini-
mized [21]. Thus, during aging a dynamic equilibrium can be
conceived, where atoms from b-phase diffused into matrix and
precipitates again on the existing b-phase platelets towards
satisfying these two conditions and thus minimizing the sur-
face energy as well as the aspect ratio. Naturally, minimization
of surface energy in this case would be a diffusion-controlled
phenomenon and aging at higher temperature or involvement
of a liquid phase would accelerate this process due to enhanced
diffusivity. On the other hand, aging in solid-state condition
1144
(a) (b)
Fig. 4 a BSE micrographs of 6Si samples held at 572 °C for 24 h with x-ray mapping using b Si–Ka and c Fe–Ka. Arrows in (c) indicate the
fragmented beta phase
would take longer time in order to achieve the low energy
morphology due to lower diffusivity.
We note that b-phase always inherits longitudinal and
transverse cracks as shown in Fig. 4a; which is studied in
details and reported in the literature [22]. Such cracks pro-
vide additional high-energy surface area through which
atomic diffusion could take place and eventually the platelets
would appear in fragmented-yet-aligned morphology in the
microstructure, as shown in Fig. 3c. In addition, the thick-
ness of the fragmented platelets should increase upon
isothermal treatment resulting in lower aspect ratio and
round-edged particle as evident from Fig. 3c, d. The phe-
nomenon of fragmentation and growth is depicted in Fig. 5
in a self-explained manner.
Tensile Properties
Based on the observations after aging, it was thought if a
combined heat-treatment involving aging at 580 °C for 2 h
followed by aging at 572 °C for 24 h would result in better
mechanical properties. Accordingly, this heat-treatment was
carried out for 6Si samples.
The tensile stress-strain curves of 6Si specimen with dif-
ferent heat-treated conditions are presented in Fig. 6a along-
side with that of the as-cast specimen. From the figure, it is
evident that the long-term soaking at 572 °C indeed causes
improvement in ductility with loss in strength and yield
strength. Tensile properties derived from the stress-strain
C.B. Basak and N. Hari Babu
(c)
Si-Kα Fe-Kα
Growth direction High
during energy
interface;
high index
Aging
Pre-
Growth direction
existing
Diffusion from Low energy interface during aging
high to low
Fig. 5 Schematic growth model of primary b-phase platelet during
solid-state aging. Shaded surface is the high-index crystallographic
plane (for accommodating higher growth speed during solidification)
representing high-energy interface and is perpendicular to the direction
of solidification. Eventually, the b-phase would appear as
fragmented-yet-aligned morphology with rounded edge and lower
aspect ratio than their as-cast morphology
curves are given in Table 2. This is also interesting to note the
serrated plastic flow (Fig. 6a) in the spheroidized sample due
to dynamic strain aging (DSA), which is also known as
Portevin-LeChatelier effect (PLC effect). PLC effect in alu-
minium alloy due to dynamic strain aging is a known
phenomenon and is reported in literature [23].
The correlations between the heat-treatment and corre-
sponding morphology of the phases as well as the tensile
properties appear to be straightforward. Improvement of the
tensile properties strongly depends on the elimination of stress
point rounded-off the existing eutectic Si phase and b-phase to
a lesser extent causing improvement concentrating features
(i.e. shape of existing b-phase or eutectic Si producing sharp
Improved Recyclability of Cast Al-Alloys … 1145

150
(a)
125

100

Stress, MPa
75

As-cast
50 o
24hrs. @ 572 C
o
2hrs. @ 580 C
25 o
2hrs. @ 580 C
o
+ 24hrs. @ 572 C
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Strain, %
250
(b) 0Cu
2Cu
200 4Cu
Stress, MPa

150

100

50

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Strain, %
250
(c) 0Cu
2Cu
200 4Cu
Stress, MPa

150

100

50

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Strain, %
Fig. 6 a Comparative stress-strain curves of 6Si alloys with different heat-treatments. b Stress-strain curve in as-cast condition with different Cu
level and c in solutionized condition for 24 h, at 572 °C for 0Cu and at 520 °C for 2Cu and 4Cu samples
1146 C.B. Basak and N. Hari Babu

Table 2 Typical tensile Sample, heat treatment ( ) Yield stress (0.2%) UTS Elongation
properties of 6Si alloy (with and (MPa) (MPa) (%)
without Cu addition) under
different heat-treatment 0Cu, as-cast 70 139.1 2.6
conditions 2Cu, as-cast 124.1 170.4 0.6
4Cu, as-cast 173.8 209.3 0.4
0Cu, 24 h @ 572 °C 59.8 130.4 3.9
2Cu, 24 h @ 520 °C 81.1 134.6 0.9
4Cu, 24 h @ 520 °C 107.8 188.8 1.1
0Cu, 2 h @ 580 °C 66.5 131.6 2.2
0Cu, 2 h @ 580 °C then 24 h @ 572 °C 61.8 143.6 3.8

corners) in high Fe bearing Al–Si alloy. Isothermal treatment
for prolonged time below eutectic in ductility in all alloys.
However, grain growth in base alloy causes reduction in 0.2%
offset yield strength and UTS. Addition of Cu was aimed to
improve the strength in as-cast condition and even after the
long-term isothermal spheroidizing treatment, as evident from
Fig. 6b, c. It is interesting to note that holding for a shorter
period slightly above eutectic temperature does not exhibit
better tensile properties than that of as-cast structure despite the
fact that b-phase grows with lowering in particle count (Ost-
wald ripening) and as a result many of the stress raisers (sharp
corners) are eliminated. This could be explained by consid-
ering the fact that upon solidification from 680 °C, the Si
morphology gives rise to zagged flaky shape with sharp cor-
ners (Fig. 3d) and at the same time, average grain size
increases, which reduces both ductility and strength. However,
the best result is obtained when the same sample is again
subjected to solid-state aging below eutectic temperature
causing rounding off the edges of eutectic Si along with the
rounded b-phase. Addition of Cu increases both YS and UTS,
albeit with a reduction in ductility. At this point the best
possible combination of tensile property could be achieved in
4 wt%Cu sample with isothermal treatment at 520 °C. We
emphasize that there is a large scope of optimization in terms
of alloy addition, spheroidizing temperature and soaking time
in order to obtain the best possible combination of the tensile
properties.
Conclusions
From the foregoing discussion the following concluding
points could be drawn:
(i) Morphological change of b-phase (via suitable
heat-treatment) in Al–6 wt%Si–2 wt%Fe alloy with
or without Cu addition was studied to counteract the
detrimental effect of Fe content.
(ii) Fragmentation theory has been proposed as the chief
mechanism for the refinement of the b-phase upon
solid-state spheroidizing treatment based on the
experimental evidences; this also improves tensile
properties.
(iii) Isothermal treatment above and below eutectic point
in 6Si alloy spheroidizes both b-phase and Si parti-
cles, causing further improvement in ductility and
ductility.
(iv) Addition of Cu increases the strength with a loss in
ductility, it also destroys the Al–Si eutectic structure
and Si appears as blocky particles.
Acknowledgements The authors acknowledge that the present work
has been carried out under the aegis of Marie Sklodowska Curie
Individual Fellowship (MSCA-IF-2014), European Commission (EU
project no. 656943).
References
1. J.A.S. Green (ed.), Aluminum recycling and processing for
energy conservation and sustainability (ASM International,
USA, 2007)
2. C. Schmitz (ed.), Handbook of aluminium recycling (Vulkan
Verlag, Germany, 2006)
3. G. Gaustad, E. Olivetti, R. Kirchain, Resour. Conserv. Recycl. 58,
79 (2012)
4. V.G. Rivlin, G.V. Raynor, Int. Met. Rev. 26, 133 (1981)
5. G. Ghosh, in Ternary Alloys, vol. 5, ed. by G. Petzow, G.
Effenberg (VCH Publishers, Germany, (1992)) p. 394
6. N. Krendelsberger, F. Weitzer, J.C. Schuster, Met. Mat. Trans.
A 38A, 1681 (2007)
7. M.C.J. Marker, B. Skolyszewska-Kühberger, H.S. Effenberger, C.
Schmetterer, K.W. Richter, Intermetallics 19, 1919 (2011)
8. A. Gorny, J. Manickaraj, Z. Cai, S. Shankar, J. Alloy Com. 577,
103 (2013)
9. C.B. Basak, N. Haribabu, Mat. Design 108, 277 (2016)
10. J.A. Taylor, Proc. Mat. Sci. 1, 19 (2012)
11. C.M. Dinnis, J.A. Taylor, A.K. Dahle, Scripta Mater. 53, 955
(2005)
12. S.G. Shabestari, Mat. Sci. Eng. A 383, 289 (2004)
13. E. Taghaddos, M.M. Hejazi, R. Taghiabadi, S.G. Shabestari,
J. Alloy. Comp. 468, 539 (2009)
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14. N.A. Belov, A.A. Aksenov, D.G. Eskin, Iron in aluminium alloys:
impurity and alloying element (Taylor & Francis Inc., New York,
2002)
15. H.L. de Moraes, J.R. de Oliveira, D.C.R. Espinosa, J.A.S. Tenorio,
Mater. Tran. 47(7), 1731 (2006)
16. S.L. Chen, F. Zhang, F.Y. Xie, S. Daniel, X.Y. Yan, Y.A. Chang,
R. Schmid-Fetzer, W.A. Oates, JOM 55(12), 48 (2003)
17. W.S. Rasband, in ImageJ, (U. S. National Institutes of Health,
Bethesda, Maryland, USA, 1997–2015), http://imagej.nih.gov/ij/
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18. ASTM B557-10 Standard Test Methods for Tension Testing
wrought and cast aluminium and magnesium alloy product (2015),
ASTM International, West Conshohocken, PA. www.astm.org
19. C.B. Basak, M. Krishnan, Phil. Mag. Lett. 95, 376 (2015)
20. J. Wang, P.D. Lee, R.W. Hamilton, M. Li, J. Allison, Scripta Mat.
60(7), 516 (2009)
21. C.B. Basak, J. Nucl. Mat. 416(3), 280 (2011)
22. X. Cao, J. Campbell, Mater. Tran. 47(5), 1303 (2006)
23. K. Peng, W. Chen, K. Qian, Mat. Sci. Eng. A 415(1–2), 53 (2006)
 Part XXVI
Electrode Technology: Electrodes:
Raw Materials and Anode Quality
 Influence of Calcination Temperature
and Sulfur Level on Coke Properties

Victor Buzunov, Victor Mann, Sergey Khramenko, and John Johnson

Abstract
The majority of RUSAL’s Russian smelters have to deal with challenges that are created by
blending and calcining green cokes with varying chemical and physical properties and,
especially, the problem is associated with high-sulfur cokes. It has been widely reported in
the literature that desulfurization, which occurs during petroleum coke calcination,
negatively affects coke quality. To assess the risks of desulfurization and its influence on
the coke physical structure, the RUSAL Krasnoyarsk Aluminum Smelter has run several
experimental trials regarding the calcining of petroleum coke in an industrial rotary kiln at
different temperatures. This paper discusses the physical changes in calcined coke with
different sulfur contents in an industrial rotary kiln where the real density and carboxy
reactivity of high-sulfur coke are shown to be extremely dependent on the temperature of
calcination and non-predictable from 1200 to 1350 °C.

Keywords
Petroleum coke Sulfur Calcination

Introduction In 2010–2011, the kilns were upgraded in order to

The Krasnoyarsk Aluminum Smelter remains one of the
largest in the world producing about one million tonnes of
aluminum per annum. Due to the capacity, it uses several
sources of green coke resulting in cokes with different
properties. The range includes all types of coke of different
sulfur content: low-sulfur—up to 1.5% of sulfur,
medium-sulfur—up to 3.0% and higher-sulfur more than
3.0%. All the cokes come from the C.I.S counties (Table 1).
Four hundred thousand tons of green coke is calcined at
the calcining facilities in the Krasnoyarsk Aluminum
Smelter per year using four kilns (Fig. 1). The main char-
acteristics of the four kilns are summarized in Table 2.
V. Buzunov (&)
S. Khramenko
J. Johnson
RUSAL ETC LLC, 37/1 Pogranichnikov Str, Krasnoyarsk,
660111, Russian Federation
e-mail: Victor.Buzunov@rusal.com
V. Mann
RUSAL Global Management B.V, 13/1 Nikoloyamskaya Str,
Moscow, 109240, Russian Federation
increase the throughput up to 12.5 tons/h by:
• Adding secondary air supply and control to the burning
zone,
• Installation of lifters in the volatile-producing area,
• A higher degree of kiln filling (a deeper coke bed).
The addition of the lifters reduced segregation, however
the problem of segregation within the coke bed inside the
kiln since during rotation, the coarse particles are concen-
trated in the outer upper layer, and fine particles go to the
center, where they get isolated from the radiant heat source
resulting in the finer fractions being under-calcined. In order
to increase the degree of calcination of fine factions, the
target temperature was increased by 40°—from 1240 to
1280 °C since the calcination temperature is very critical for
forming the desired structure and physical properties of
calcined petroleum coke.
The process of calcining petroleum coke with different
sulfur levels within the temperature range of 1200–1500 °C

© The Minerals, Metals & Materials Society 2017 1151

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_138
1152 V. Buzunov et al.

Table 1 Cokes properties Supplier %/year Volatile % S% Si % Fe % V% Na %

A 35.5 7.9 3.62 0.006 0.013 0.084 0.004
B 19 9.4 3.04 0.009 0.02 0.05 0.024
C 17 10.4 1.72 0.005 0.021 0.03 0.016
D 2.0 8.2 1.64 0.012 0.018 0.02 0.005
E 0.5 9.9 0.61 0.062 0.024 0.002 0.059
G 26 9.6 0.57 0.009 0.029 0.003 0.012

Fig. 1 Rotary Kiln

Table 2 Rotary kiln design Capacity, tonnes/h 10.0

characteristics
Kiln design
Diameter (mm) 3000
Length (mm) 45,000
Tilt angle (degrees) 3.5
Rotational revolutions/min 22
Power (kW) 75

has been studied in detail under laboratory conditions [1].
The results indicated that the properties of high-sulfur coke
at temperatures above 1300 °C are determined by the fol-
lowing two competing processes: graphitization and
desulfurization.
Moreover, the explosive-like release of sulfur during calci-
nation at temperatures above 1300 °C rearranges the crystal
structure of coke which negatively affects the coke structure in
ways that alter the reactivity and porosity of the resultant cal-
cined coke [2]. However, the literature does not provide enough
data on the process of calcining coke with different sulfur levels
under industrial conditions. Coupled with the experience at the
Krasnoyarsk Aluminum Smelter after modernization of the
kilns led to a large number of temperature excursions above
1300 °C (Fig. 2) the decision was made to study desulfuriza-
tion under industrial kiln operating conditions.
The rest of paper will discuss the results of calcining
high-sulfur coke in the rotary kiln under industrial conditions
to assess the risks of desulfurization. The RUSAL Krasno-
yarsk Aluminum Smelter ran several trials regarding cal-
cining petroleum coke in the rotary kiln at different
temperatures.
Influence of Calcination Temperature and Sulfur Level … 1153

1320
Coke A Coke B
1310
3,8
1300
1290
Temperature, oC

1280 3,6
1270
1260 3,4

Sulfer, %
1250
1240 3,2
1230
1220 3,0
0:00
3:00
6:00
9:00
12:00
15:00
18:00
21:00
0:00
3:00
6:00
10:00
13:00
16:00
19:00
22:00
1:00
4:00
Time, h 2,8

2,6
Fig. 2 Typical kiln daily temperature variations and a large number of 1150 1200 1250 1300 1350 1400
excursions above 1300 °C
Tempreture, C

Calcination Results
Fig. 3 Sulfur content in calcined coke at different temperatures

Two cokes, “Coke A” (S = 3.6%) and “Coke B” (S = 3.0%)

were calcined in the rotary kiln to assess the risk of desul-
furization within the temperature range of 1200–1350 °C. Coke A Coke B
The coke samples were subject to the following analysis:
2,07
sulfur content, real density, CO2 reactivity and attrition
2,06
strength. The coke properties before and after calcination are
given in Table 3. 2,05
Figures 3, 4, 5 and 6 show the coke properties as a
Density, g/ml

2,04
function of temperature.
2,03
Figure 3 shows that the desulfurization of Coke A and
Coke B begins at 1230 °C. The initial sulfur content in 2,02

Coke A reduced from 3.6% down to 3.0% at a temperature 2,01

of 1300 °C; Coke A lost 0.6% of sulfur. The initial sulfur 2
content in Coke B reduced from 3.0% down to 2.8% at a
1,99
temperature of 1300 °C; Coke B lost 0.2% of sulfur. This is 1150 1200 1250 1300 1350 1400
in accordance to the results obtained under laboratory con-
Temperature, C
ditions where the higher is the sulfur content, the greater is
the loss [2].
Figure 4 shows the real density of calcined coke as a Fig. 4 Real density of calcined coke at different temperatures
function of temperature. By comparing Fig. 2 with Fig. 3,
one can see that a monotonic decrease in the sulfur content is
not accompanied by a monotonic change in the real density: Moreover, it has been observed that CO2 reactivity and
both cokes show that the real density extremely depends on attrition strength are also extremely dependent on the cal-
the calcination temperature in the range of 1200–1350 °C. cination temperature (Figs. 5 and 6).

Table 3 Coke properties before Parameters Coke A Coke B

and after calcination
Calcination Calcination
Before After Before After
Moisture (%) 8.1 – 8.8 –
Volatiles (%) 7.8 – 10.1 –
Sulfur (%) 3.6 3.1 3.1 2.8
Real density max (g/cm ) 3
– 2.062 – 2.045
CO2 reactivity min (%) – 4.6 – 9.5
VBD max (g/cm3) – 0.84 – 0.82
Resistance to attrition (%) – 0.45 – 0.8
1154 V. Buzunov et al.

temperature. The previous studies [2] on high-sulfur coke

Coke A Coke B
calcination—carried out under laboratory conditions
14 show an increase in the pore volume in the size range of
12 0.014–0.1 lm.
In order to determine the characteristics of porous struc-
10
ture formation in high-sulphur coke, mercury porosimetry
Reactivity, %

8 was used to study the samples of cokes A and B taken from

6
an industrial kiln after calcined at 1300 °C, and the samples
of said cokes calcined at 1300 °C under laboratory
4
conditions.
2

0
1150 1200 1250 1300 1350 1400

Temperature, C Porous Structure Formation

Fig. 5 CO2 reactivity of calcined coke at different temperatures Lab calcination was carried out in a closed graphite crucible
under argon at a rate of 10 °C/min up to 1300 °C, with an
isothermal retention time of 1 h. The results of both lab and
Coke A Coke B industrial calcination are shown in Table 4 and in Figs. 7
3 and 8.
The results of mercury porosimetry were interpreted
2,5 within the framework of the “Dusty—Gas Model” [3].
Strength abrasion, %

According to this model, the total volume of pores was

2 divided in three structural zones, depending on the pore size.

1,5

1 Coke A Coke B
7,0

0,5 6,0

5,0
Pore Volume, mcL/g

0 4,0
1150 1200 1250 1300 1350 1400
Tempeture, C 3,0

2,0

1,0
Fig. 6 Attrition strength of calcined coke at different temperatures
0,0
100 10 1 0,1 0,01
The results show that a temperature of 1300 °C is the Pore Diameter, mkm
limit for high-sulfur coke. It can be assumed that
high-sulphur coke undergoes structural changes at this Fig. 7 Pore structure of coke A and coke B after kiln calcination

Table 4 Coke properties after Parameters Laboratory calcination Kiln calcination 1300 °C
laboratory and kiln calcination Coke A Coke B Coke A Coke B
Sulfur (%) 3.3 3.0 3.1 2.8
Real density (g/cm3) 2.072 2.056 2.062 2.045
CO2 reactivity (%) 4.0 6.6 4.6 9.5
VBD max (g/cm3) 0.88 0.85 0.84 0.82
Pore volume (mcL/g) – – – –
Total volume 84.5 85.9 110.5 136.4
Viscous zone 57.5 55.8 82.1 108.7
Diffusion flow 15.5 16.9 21.5 21.3
Knudsen flow 11.5 13.2 6.9 6.4
Influence of Calcination Temperature and Sulfur Level …
Coke A Coke B
7,0
6,0
5,0
Pore Volume, mcL/g
4,0
3,0
2,0
1,0
0,0
100 10 1 0,1
Pore Diametr, mkm
Fig. 8 Pore structure of coke A and coke B after laboratory calcination
Such zones differ from each other in terms of the nature of
gas flow through porous media:
– In the pores with a diameter of 0.012–0.1 lm, there is a
free molecular, or Knudsen, flow, in which the pore size
is less than the free-path length, and, in this particular
case, collisions between molecules can be neglected, as
opposed to the frequency of collisions with the surface of
the pores;
– In the pores with a diameter of 0.01–1.0 lm, there is
molecular diffusion through a continuous medium; it is
when the gases are moved under the influence of a
concentration gradient (normal diffusion). In this case,
intermolecular collisions occur more frequently than
collisions with the surface of the pores.
– Viscous flow; it is when the gas flows as a continuous
medium under a pressure gradient, and intermolecular
collisions dominate over collisions with the surface of the
pores. The pore diameter is 1.0–60 lm.
Table 4 shows the properties of cokes A and B calcined
both under lab conditions and in a rotary kiln, and the pore
volume distribution, by gas flow zone. The properties of the
cokes show an in real density and a reduction in CO2
reactivity under lab calcination. VBD (size 1.18–2.36 mm)
cokes increase calcination in the laboratory condition and
correlates to total pores volume.
Figure 7 shows the porous structure of cokes A and B
calcined in a rotary kiln. The pore size distribution shows
that coke B has a greater porosity than coke A under
industrial calcination. Coke B contains more volatiles
(Table 3), the release of which, under calcination, forms an
additional pore volume in the viscous flow zone, with a pore
diameter of more than 1.0 lm. The pore volume in the
diffusion zone and the Knudsen flow zone in the porous
structure of both cokes is the same.
1155
Figure 8 shows the structure of cokes A and B calcined
under lab conditions. Under lab calcination, there is a
decrease in the total pore volume, compared to industrial
calcination; the pore volume in all the zones for cokes A and
B is almost equal. Comparing the results of laboratory and
industrial calcination, one can see that porosity formation is
effected not so much by the content of volatiles as by the rate
of their release during calcination.
The comparison of porosity distribution under industrial
and laboratory conditions, as in the case of Coke B (Fig. 9),
shows that not only the total pore volume changes but also
0,01 the pore volume distribution between the three porosity
zones.
Figure 9 shows that, under industrial calcination, the
volume of pores in the viscous flow zone and in the molec-
ular diffusion zone is bigger, but the content of the Knudsen
pores (0.1–0.012 microns) is less than under laboratory
calcination. This suggests that the mechanism of
nanoporosity formation during rotary kiln calcination might
be different from what is described in [2].
It is likely that, under industrial calcination in a rotary
kiln, there is not only an explosive release of volatiles, the
result of which is an increase in the number of larger pores,
but also an explosive release of sulfur at 1300 °C, which is
accompanied by the formation of larger pores in the diffu-
sion zone.
We can also assume that such extreme dependence of the
properties of high-sulfur cokes calcined under industrial
conditions (for example, CO2 reactivity) can be explained by
the characteristics of the porous structure.
In general, CO2 reactivity is determined based on the
presence of catalytic impurities, the rate of mass transfer and
the reactive surface, the quantity of which is mainly deter-
mined by the amount of pores with a size of less than
0.01 lm.
Fig. 9 Porous structure coke B after industrial and laboratory
calcination
1156
However, the reactivity of industrially calcined cokes is
higher than those calcined in the laboratory (Table 4). This
is because the rate of reactions in porous media is deter-
mined mainly by the intensity of the mass transfer of the
reaction gas to the reaction zone, instead of the kinetic
characteristics of the reaction itself. And there is a larger
amount of big transport pores during industrial calcination.
Discussion
Sulfur compounds, which are present in coke, may be in the
form of sulfides, thioesters, mercaptans, as well as
heat-resistant thiophene rings [4]. The thermal stability of
sulfur compounds determines the sequence of thermal
transformations. First, in the course of desulfurization, the
link between RC and S is broken, and free radicals (RS–, –S)
are formed. Active –S may enter secondary reactions,
forming heat-resistant compounds, such as thiophene, or
transit into the vapor phase and escape [5]. The subsequent
high-temperature destruction of thiophene rings breaks the
crystal lattice and leads to the formation of pores of less than
0.1 µm.
The mercury porosimetry data show that the volume of
these pores under industrial calcination is less than under lab
calcination. Changes in the porous structure lead to an
increase in the reactivity of industrially calcined coke, due to
better conditions for the mass transfer of gas in larger pores.
It can be assumed that sulfur in coke is generally present
in the form of thermally stable thiophenic compounds, which
degrade at temperatures above 1300 °C. In the meantime, a
significant amount of sulfur in Coke A is present in the form
of acyclic compounds, which degrade at lower temperatures.
The results show that Coke A and Coke B, which have a
similar sulfur level, behave differently during calcination and
their characteristics may vary significantly.
Overall, the sulfur content continues to increase as new
sources of heaver crude oils are being processed in addition
to the lighter sources which results in higher sulfur content
in the petroleum cokes. Aluminium producers are forced to
blend coke of different sulfur content to meet the environ-
mental requirements. Increasing the calcination temperature
V. Buzunov et al.
improves the characteristics of coke, but there is a risk of
coke desulfurization.
Thus, high-sulfur coke calcination needs to be optimized,
since the natural desire to improve the performance prop-
erties of coke by increasing the calcination temperature may
lead to the opposite effect, i.e. desulfurization.
Conclusions
The character of changes in the properties high sulfur cokes
resulting by industrial calcination differs significantly from
the calcination in a laboratory. In the range of calcination
1200–1350 °C the real density, reactivity and abradability
have an extreme character at 1300 °C. Under industrial
calcination in a rotary kiln there is an explosive release of
sulfur at 1300 °C, which is accompanied by the formation of
larger pores in the diffusion zone. This increases the CO2
reactivity that determined mainly by the intensity of the mass
transfer of the reaction gas to the reaction zone.
To reduce the risk of desulfurization temperature 1300 °C
should be considered as limiting the calcination. To stabilize
the calcination temperature is necessary to improve the
existing system of controlling the operation of the furnace.
References
1. E.E. Hardin, C.L. Beilharz, L.L. Melvin, A comprehensive review
of the effect of coke structure and properties when calcined at
various temperatures. Light Metals (1993), p. 501
2. E.E. Hardin, C.L. Beilharz, P.J. Ellis, L. McCoy, A comprehensive
review of the effect of coke structure and properties when calcined
at various temperatures. Part II: Light Metals (1994), p. 73
3. E.A. Mason, A.P. Malinauskas, Gas Transport in Porous Media:
The Dusty—Gas Model (Elsevier, Amsterdam; Oxford, New York,
1983), p. 202
4. M.M. Akhmetov, Production of low-sulfur coke from sulphurous
oils. Acad. SUE INKhP RB. UFA in 2010, p. 180
5. B.S. Dyskin, Y.V. Kolupaeva, A.S. Korolev, in Analysis of the
Desulfurization of Petroleum Coke. Science SUSU: Proceedings of
the 66th Scientific Conference. Section of Natural Sciences (2011),
pp. 357–362
 Pilot Anode Properties of Binder Pitches
Softening Between 110 and 150 °C

Winfried Boenigk, Christopher Kuhnt,

Jens Stiegert, Joris Claes, and Les Edwards

Abstract
Today there is a growing trend towards the use of higher melting binder pitches in the
manufacture of prebaked anodes. Although 110–115 °C softening point Mettler
(SPM) pitches are still the dominant quality for prebaked anodes, the use of 120 M
pitches is growing and some anode producers are even using 130 M pitches on a routine
basis. Due to their increased coking value, higher softening point pitches provide several
property benefits over standard binders and total PAH levels are lower. Binders up to
150 M can be still produced with conventional distillation technology and processing as
well as storage of these binders should be achievable in modern paste plants with relatively
minor upgrades. Today’s generation of paste mixers are already capable of processing
carbon paste up to 250 °C. The paper gives an overview of binder properties in the range of
112–150 M and presents the results of pilot anode testing with these binders.

Keywords
Pilot anode testing Anode binder High softening point

Introduction
The Hall-Héroult process for the production of aluminium
uses prebaked carbon anodes manufactured from calcined
petroleum coke (CPC) and coal tar pitch (CTP). CTP can
still be considered as an indispensible binder for carbon
anodes despite the environmental and occupational chal-
lenges due to its content of polycyclic aromatic hydrocar-
bons (PAHs).
Today’s standard pitch quality for anode manufacturing is
a 110–120 °C softening point Mettler (SPM) pitch but there
is a growing trend towards higher softening point pitches
W. Boenigk
C. Kuhnt (&)
J. Stiegert
RÜTGERS Germany GmbH, Kekuléstr. 30, 44579
Castrop-Rauxel, Germany
e-mail: christopher.kuhnt@raincarbon.com
J. Claes
RÜTGERS Belgium NV, Vredekaai 18, 9060 Zelzate, Belgium
L. Edwards
RAIN CII Carbon LLC, 1330 Greengate Drive, Suite 300,
Covington, LA 70433, USA
(SPM > 120 °C). These pitches are considered as an evo-
lutionary alternative to the standard quality due to their
performance benefits driven by an increased carbon yield
and decreased PAH levels.
In two previous papers [1, 2], bench scale and pilot anode
results with HMR 180 M were given to illustrate the
potential of a further softening point increase. HMR 180 M
is a very high softening point binder (SPM 180 M) produced
via a different distillation process. RÜTGERS produces a
range of these pitches with softening points up to 250 °C
which are used in a variety of specialty applications such as
carbon bonded refractory bricks.
Although the pilot anode properties achieved with the
HRM 180 M binder were very promising including a
reduced PAH content, the technology has to overcome two
challenges on the smelter side. First, it is not possible to ship
binders with a SPM of 180 °C in liquid form given that
shipping temperatures need to be *100 °C above the soft-
ening point. Almost all smelters receive pitch in liquid form
today and it is not realistic to move back to deliveries in
solid form. The second problem is that the mixing

© The Minerals, Metals & Materials Society 2017 1157

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_139
1158 W. Boenigk et al.

temperatures of at least 230–240 °C are needed to com-
pensate for the higher softening point to allow for adequate
processing.
A short or mid-range compromise is the use of higher
softening point pitches in the range of 120–150 M. These
pitches are produced with conventional distillation technol-
ogy and can be shipped in liquid form (e.g. riverbarge
shipping up to 250 °C). The elevated mixing temperature
needed for these materials should be achievable in modern
paste plants with relatively minor upgrades. Some anode
producers already use 130 M pitch on a routine basis. These
pitches are produced with conventional distillation technol-
ogy which enables an incremental approach to increasing
softening points and anode properties.
The study reported in this paper was undertaken to
determine the benefits of using higher softening point
pitches and provides results for pilot anodes prepared with
these binders.
Materials and Methods
Binder
Four straight-run vacuum distilled pitches in the softening
point range of 112–150 M were sampled from industrial
batches. The properties of the binders are shown in Table 1.
The coking value of the binder increases with increasing
softening point, in good agreement with the literature [5].
The very distinct difference in BaP content of the 112 M
quality relative to the 125 M is partly related to the relatively
small increase in SPM but also due to a different tar quality.

Table 1 Properties of binders used for pilot anode production and CANTOX-calculations according to [3, 4]
CTP 112 M CTP 125 M CTP 130 M CTP 150 M
Softening point DIN (°C) 112 123.6 128.7 149.6
Mettler 51920
Coking value (Alcan) DIN (%) 57.6 59.1 62.9 68.3
51905
Toluene insoluble DIN (%) 25.7 28 28 34.5
51906
Quinoline insoluble DIN (%) 5.1 4.8 5.2 8.3
51921
Ash (800 °C) DIN (%) 0.17 0.08 0.11 0.14
51922
Density DIN (%) 1.316 1.309 1.311 1.327
51907
XRF-analysis DIN
51418
S (%) 0.59 0.49 0.47
Na (ppm) 80 129 135
Si (ppm) 153 123 164
Ca (ppm) 36 7
Fe (ppm) 142 90 153
Zn (ppm) 284 138
Pb (ppm) 222 66 96
Distillate 020–230 °C GC (%) 0.03
Distillate 230–270 °C GC (%) 0.01
Distillate 270–360 °C GC (%) 0.84 0.78 0.57 0.15
Distillate 360–440 °C GC (%) 5.18 4.38 3.44 1.45
Distillate 440–500 °C GC (%) 15.60 13.29 10.05 9.38
Distillate >500 °C GC (%) 13.70 9.34 12.03 11.60
Sum of distillates GC (%) 35.36 27.78 26.09 22.57
(continued)
Pilot Anode Properties of Binder Pitches … 1159

Table 1 (continued)
CTP 112 M CTP 125 M CTP 130 M CTP 150 M
GC-analysis RPF PAH BaP-equiv PAH BaP-equiv PAH BaP-equiv PAH BaP-equiv
(cantox) (ppm) (ppm) (ppm) (ppm)
Naphthalene 0.000 28 0 0 0 0
Acenaphthylene 0.000 0 0 0 0 0
Acenaphthene 0.000 714 0 277 0 186 0 118 0
Fluorene 0.000 195 0 219 0 135 0 50 0
Phenanthrene 0.000 2377 0 2476 0 1501 0 605 0
Anthracene 0.000 544 0 498 0 349 0 137 0
Fluoranthene 0.034 9639 328 6562 223 4348 148 1879 64
Pyrene 0.000 8269 0 5853 0 3911 0 1759 0
Benzo[a] anthracene 0.033 9123 301 5343 176 4472 148 2378 78
Chrysene 0.260 9201 2392 5645 1468 4500 1170 2483 646
Benzo[e]pyrene 0.050 10173 509 4461 223 4340 217 3001 150
Benzo[b] fluoranthene 0.100 10994 1099 6861 686 6644 664 4761 476
Benzo[k] fluoranthene 0.010 5224 52 3587 36 3203 32 2353 24
Benzo[a]pyrene 1.000 12176 12176 7139 7139 6880 6880 5231 5231
Dibenzo[a,h] 1.400 1907 2670 1249 1749 1175 1645 1137 1592
anthracene
Benzo[ghi]perylene 1.000 9150 9150 6233 6233 5857 5857 6139 6139
Indeno[12,3-cd]pyrene 0.100 8354 835 5302 530 5973 597 5606 561
Total 98068 29513 61705 18463 53474 17358 37637 14960
Average toxicity index 1.07 0.67 0.63 0.54

Notwithstanding this, the PAH content decreases with

increasing SPM as clearly seen when comparing the 125,
130 and 150 M qualities.
Micro-TGA (thermogravimetric analysis) results illustrate
the shift in volatile release to higher temperatures for increased
softening point binders due to the improved removal of lighter
boiling components during distillation (Fig. 1).

Calcined Petroleum Coke and Butts

The CPC properties are summarized in Table 2. This CPC is

a typical rotary kiln coke blend and is used as a reference for
RAIN Carbon Inc. pilot anode testing. The butts material is
baked anode scrap from an anode plant which was selected
specifically for its low sodium level. Fig. 1 TGA of 20 mg binder samples

Dry Recipe
The dry aggregate recipe is shown in Fig. 2. The dry recipe
follows an industrial recipe but the top particle size was
limited to 8 mm to minimize crushing in the Eirich mixer.
To ensure tight control on particle size variations, the recipe
consists of 6 fractions and 2 different size butts fractions in
the range of 1.7–8 mm. The CPC material prepared for each
fraction was homogenized using a rotary splitter to ensure a
consistent granulometry throughout the trials.
1160 W. Boenigk et al.

Table 2 Properties of CPC and Coke A Butts

butts material
Physical analysis
Real density (g/cm3) 2.052 2.070
CO2 reactivity (%) 9.5 23.6
Ash (%) 0.17 0.66
Lc (Å) 25.2 30.7
VBD ASTM D4292 28  48 3
(g/cm ) 0.893 0.935
Chemical analysis
S (%) 2.94 2.13
V (ppm) 320 241
Ni (ppm) 189 144
Fe (ppm) 174 784
Ca (ppm) 87 211
Si (ppm) 70 272
Na (ppm) 87 115

The green anode is removed, cooled to ambient temper-

100 ature and the green apparent density calculated. Anode
batches are baked to an equivalent temperature of 1250 °E
80
using a heating rate of 20 °C/h due to the relatively small
60 scale compared to industrial anodes. The equivalent tem-
sum [%]

perature method (TEq), taking into account temperature as

40
well as time is described more in detail in [6]. After baking,
20 the anode weight and physical dimensions are measured to
calculate the shrinkage and baking loss. Three 50 mm Ø
0
cores are drilled per anode. The cores are analyzed according
0.1 1 10
sieve width [mm]
to the R&D Carbon standard procedure [7]. Baked apparent
density, specific electrical resistivity, flexural strength,
Fig. 2 Particle size distribution of aggregate recipe
compressive strength, elasticity modulus, air permeability
and CO2 reactivity of the resulting core samples are deter-
mined. Additional measurements are performed as required.
The CPC fines are milled to 45% below 32 µm with A more detailed overview of the equipment used for pilot
control via laser particle size analysis. The Blaine Index of anode preparation can be found in [2].
the ball mill fines used for the pilot anodes produced for the
study was *4500.

Pilot Anode Study

Pilot Anode Production Procedure
5.5 kg of the dry aggregate is preheated to the mixing
temperature, transferred to a preheated 10 L Eirich mixer
(RV02/E) and homogenized for one minute. The liquid
binder is preheated to a temperature 100 °C above the SPM
and added after the 1 min dry mix. The anode paste is mixed
for 10 min at 68 °C above the SPM of the binder. After
mixing, the paste is cooled to 20 °C above the SPM,
transferred into a preheated pilot anode press and subse-
quently pressed at 42 MPa for one minute. Typical green
anode sizes are: diameter 146 mm; height 190–200 mm;
weight 5.2–5.5 kg.
The following section presents the pilot anode results using
the previously described binder pitches.
The green apparent densities (GAD) are shown in Fig. 3
with binder levels in the range of 13–15%. GAD results for
all four binders are in the same ballpark. The reason for this,
is that the density increase of the binder itself is only minor
when increasing the SPM. When higher mixing temperatures
are used to compensate for the increase in binder viscosity,
the net effect is that the GAD stays within the same range.
The significant advantage of the elevated softening point
binders becomes obvious when looking at the baked
apparent density (BAD) results in Fig. 4. BADs compared to
Pilot Anode Properties of Binder Pitches … 1161

the standard 112 M binder increase by 0.011 g/cc for the

Air Permeability
130 M binder and by 0.021 g/cc for the CTP 150 M. This CTP112 CTP 125
can be attributed to the lower baking loss as shown in Fig. 5. CTP130 CTP150
This highlights the higher carbon yield of the binder with 0.6

Air Permeability [NPm]

increased SPM. Higher BADs are also reflected in a lower 0.5
0.4
air permeability (Fig. 6). Optimum pitch levels are at 14%
0.3
except for the CTP125 M where it was found at about 0.2
14.5%. 0.1
Specific electrical resistivity (SER) and flexural strength 0
12 13 14 15 16
(FS) data are shown in Figs. 7 and 8 respectively. It can be Binder Level [%]

Fig. 6 Air permeability versus pitch level

Green Apparent Density

Green Apparent Density [kg/dm³]

CTP112 CTP 125

CTP130 CTP150
Specific Electrical Resistance
1.68 CTP112 CTP 125

Specific Electrical Resistance [μΩm]

1.67 CTP130 CTP150

1.66 70
1.65 65
1.64
60
1.63
12 13 14 15 16 55
Binder Level [%]
50
12 13 14 15 16
Fig. 3 Green apparent density versus pitch level Binder Level [%]

Fig. 7 Electrical Resistivity versus pitch level

Baked Apparent Density

CTP112 CTP 125
Baked Apparent Density [kg/dm³]

CTP130 CTP150 Flexural Strength

CTP112 CTP 125
1.64
CTP130 CTP150
1.63
14
Flexural Strength [MPa]

1.62
12
1.61
10
1.6
8
12 13 14 15 16
Binder Level [%] 6
12 13 14 15 16
Binder Level [%]
Fig. 4 Baked apparent density versus pitch level

Fig. 8 Flexural strength versus pitch level

Baking Loss seen that these values also improve with increased softening
CTP112 CTP 125
CTP130 CTP150
point. The SER for example, decreases from 55.3 µΩm for
5.5
CTP 112 M to 53.7 µΩm for CTP 150 M. The same trend is
even more pronounced for the 180 M pitch investigated
Baking Loss [%]

5
4.5 previously [2].
4 Binders with increased SPM have a positive impact on
3.5 the overall structural integrity of the anode carbon. This is
3 most likely due to the reduced porosity associated with the
12 13 14 15 16 lower volatile emission.
Binder Level [%]
The compressive strength also increases, especially for
Fig. 5 Baking loss versus pitch level the lower pitch levels for the CTP 130 M and the CTP
1162 W. Boenigk et al.

Vapor Phase During Mixing

Compressive Strength
CTP112 CTP 125
CTP130 CTP150 As previously discussed, the PAH content decreases with
Compressive Strength [MPa]
60 increasing binder softening point. This lower PAH level of
55
the binder causes less PAH exposure when handling green
anode scrap. An investigation was started to better under-
50
stand the vapor level and composition when mixing pitch
45
and CPC. To achieve adequate CPC wetting and a low
40 enough viscosity for mixing, higher SP pitches require a
12 13 14 15 16
Binder Level [%] higher mixing temperature. This could influence the PAHs in
the vapor phase during mixing.
Fig. 9 Compressive strength versus pitch level Vapor phase sampling was tested in an effort to correlate
PAHs in the pitch and vapor phase. Volatiles from trials with
different binders (e.g. CTP 112 M, CTP 140 M and HMR
180 M) were extracted from the mixer bowl using a gas
Elasticity Modulus Static collector and further adsorbed on an XAD2 resin tube and
CTP112 CTP 125
CTP130 CTP150
evaluated using GC analysis (Fig. 12). The experimental
6
setup is not trivial. Directly connected and indirectly con-
Elasticity Modulus Static [GPa]

5.5 nected collection systems were tried. The indirect system

5 using a funnel assures that no vacuum is applied to the mixer.
4.5
Results of one of the trials using a direct measurement
4
3.5
can be seen in Fig. 13. The following binders with
3 increasing SPM and decreasing total PAH content were used
12 13 14 15 16 for the trials:
Binder Level [%]

Fig. 10 Elasticity modulus static versus pitch level • CTP 112 M: 98068 mg/kg total PAHs
• CTP 140 M: 44444 mg/kg total PAHs
• HMR 180 M: 19532 mg/kg total PAHs
150 M, Fig. 9. The static elasticity modulus is not affected
over the softening point range of these binders, Fig. 10. The sum of PAHs per m3 of collected vapor varies over a
Figure 11 summarizes the BADs from this study in wide range for all the binders and the testing has not proven
addition to some HMR data from [2]. This clearly shows to be repeatable enough to draw definitive conclusions. More
the good correlation between the Alcan coking value of realistic results are likely to be generated in a paste plant
the binder and BAD of the anode for vacuum distilled under actual production conditions with whatever fume
binders. collection systems are in place.

1.655
1.65 y = 0.002x + 1.4992
BAD of pilot anode [g/cc]

R² = 0.9988
1.645
HMR 180M
1.64
1.635
1.63
1.625
1.62
1.615
1.61
55 60 65 70 75 80
Coking Value (Alcan) of binder [%]

Fig. 11 Correlation of the coking value of the different binders used in

this study and the BAD of the pilot anodes, together with HMR 180 M
from [2] Fig. 12 Setup for vapor phase sampling
Pilot Anode Properties of Binder Pitches …
CTP 112M CTP 140M HMR 180
2000
1800
1600
Sum PAH [mg/m3]
1400
1200
1000
800
600
400
200
0 balanced with increased anode quality. It is also easier in
Trials
Fig. 13 Sum of PAH measured during trials with different binders
Discussion and Conclusions
The pilot anode results highlight the potential benefit of
these binders for prebaked anodes on an industrial scale. One
important point to make is the strong correlation between
SPM, coking yield and BAD. GADs on the other hand, are
more or less unaffected by the binder softening point as long
as the mixing temperature is increased accordingly. This
shows why it can be misleading to compare GADs between
anode plants.
The higher carbon yield of the binder offers a density
benefit that could be of interest for smelters evaluating
opportunities to improve anode density. This may be nec-
essary with an amperage increase if there are constraints on
increasing anode size.
A binder SPM increase can also help to mitigate to some
extent, the negative effect of lower CPC vibrated bulk den-
sities (VBDs).
Other properties like specific electrical resistivity and
mechanical properties are improved as well, providing a
good overall improvement in anode production with the use
of higher SPM binders. This is consistent with feedback
from smelters that have already converted to using a 130 M
pitch for routine anode production.
1163
Other potential benefits include, for example, faster baking
cycles. Due to the decreased pitch volatiles, a faster heat-up
rate may also be possible. One potential difference however,
is the change in energy balance of the baking furnace.
The energy delivered by the combustion of the pitch
volatiles will decrease with increased softening point and
this has to be compensated for by increased natural gas or
heavy fuel oil addition. The lower baking loss of the higher
SPM binders can give an indication of the deficit here. In
most cases, especially today, natural gas or heavy fuel oil are
cheaper fuels than pitch volatile matter and this has to be
principal, to control the bake furnace operation with an
external fuel versus extracting and combusting volatiles.
Higher softening point binders up to 150 M are available
on an industrial scale and can be accessed using a stepwise
approach. The business case for the use of binders softening
>120 °C depends on the individual situation of the particular
smelter.
References
1. W. Boenigk, C. Boltersdorf, F. Lindner, J. Stiegert, Property profile
of lab-scale anodes produced with 180 °C Mettler coal tar pitch.
Light Metals, 889–893 (2011)
2. W. Boenigk, C. Boltersdorf, C. Kuhnt, J. Stiegert, L. Edwards,
M. Lubin, Pilot anode testing of alternative binder and CPC raw
materials. Light Metals, 889–893 (2011)
3. A. Mirtchi, L. Noel, Polycyclic aromatic hydrocarbons (PAHs) in
pitches used in the aluminium industry. Proc. Carbon, 794 (1994)
4. R.F. Willes, S. Friar, J. Orr, B. Lynch, in Application of Risk
Assessment to Point Sources of Polycyclic Aromatic Hydrocarbons
(PAHs). Proceedings 5th Conference on Toxic Substances, Mon-
treal (1992), pp. 75–100
5. W. Boenigk, A. Niehoff, R. Wildförster, A high-melting coal-tar
pitch as binder for anode production? A bench scale approach. Light
Metals, 581 (1992)
6. ISO 17499 (2006) Carbonacious Materials Used in the Production
of Aluminium—Determination of Baking Level Expressed by
Equivalent Temperature
7. U. Bühler, R. Perruchoud, Dynamic Process Optimization (Anodes
for the Aluminium Industry, R&D Carbon Ltd. Publication, 1995),
pp. 227–240
 Uniform Bulk Density for Calcined
Petroleum Coke

Ravindra Narayan Narvekar, Gajanan Bandodkar,

and Jagmohan Chhabra

Abstract
Aluminium smelters are tightening bulk density specifications for Calcined Petroleum Coke
while refiners are sacrificing green coke densities at the cost of outputs. Previously,
Apparent Density using mercury was popular for defining CPC density. But after AD
testing was discontinued owing to environmental issues arising out of mercury usage, each
smelter has come out with its own Bulk Density measurement method and specs. The
industry specifies Vibrated Bulk Density, Tapped Bulk Density and that too, on a different
size fraction viz. (1–2) mm, (−8 + 14) mesh, (−20 + 35) mesh, crushed and uncrushed
particles etc. The calciners are confused and GOA CARBON LTD. has made an attempt to
analyze various Bulk Densities on different size fractions using crushed/uncrushed basis, to
explore, if there exists, a co-relation internally, among all the densities and in particular
with mercury AD.

Keywords
Bulk density Calcined petroleum coke Aluminium smelters

Introduction (CPCs), manufactured using different blends of Green Cokes

The mercury Apparent Density used to be a critical param-
eter for defining quality of anode grade CPC until a few
years ago. Then for environmental reasons, mercury AD was
discontinued and various forms of Bulk Density viz VBD,
TBD on different size fractions like (1–2) mm, (−8 + 14)
mesh, (−20 + 35) mesh were introduced by Aluminium
smelters as per their convenience. Some used uncrushed
particles by sieving while others crushed bigger particles and
then sieved desired fractions.
The calciners find it difficult to meet all these BD specs
and look for some uniform BD measurement acceptable to
all the smelters.
GCL has tried to address this issue by exploring if mer-
cury AD can be correlated to some sort of density. For this
GCL selected seven types of Calcined Petroleum Cokes
R.N. Narvekar (&)
G. Bandodkar
J. Chhabra
Goa Plant, Goa Carbon Ltd., Goa, India
e-mail: ravindran.narvekar@gmail.com
(GPCs). Samples from these CPCs were analysed for dif-
ferent types of densities specified by smelters.
Experiments
Seven CPC samples manufactured with different blends of
green cokes in Rotary Kiln at Goa, were selected for this
study.
Each sample was analysed for following parameters
(i) Mercury Apparent Density, AD, g/cc as per Alcan
Pechiney method no. MSALAB.S.641.01.12.033
[2].
(ii) Real Density, RD, g/cc, measured on a sample
ground to −200 mesh and the density is measured
using water as the displacement media [1].
(iii) Bulk Density, BD, g/cc on (−8 + 14) mesh as per
ASTM D4292. Analysis done using uncrushed par-
ticles sieved out from parent sample for uncrushed

© The Minerals, Metals & Materials Society 2017 1165

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_140
1166 R.N. Narvekar et al.

basis and particles sieved out after grinding parent
sample for crushed basis [4].
(iv) Bulk Density, BD, g/cc on (1–2) mm as per ISO
10236 using both crushed and uncrushed samples [4].
(v) Bulk Density, BD, g/cc on (−20 + 35) mesh as per
Alcan method 883-88.
(vi) Bulk Density, BD, g/cc on (−12 + 20) mesh as per
GCL developed method, based on ASTM D 4292,
but modified to have particles size used for mercury
AD.
(vii) Hard Grove Index, HGI, as per ASTM D409 [3].
(viii) Weight in kg/m3 was calculated mathematically after
determining the weight of one cubic foot of material
as per Kaiser method.
In the first set of experiments, we tried to check the effect
on density for sample generated by crushing the oversized
particles vis a vis just sieved out particles from parent
sample.
When we use a plain sieved out sample, only a few
particles represent the CPC while when we crush oversize,
there is wider representation of all the particles in the testing.
In the second set of experiments, we assumed AD as the
basic parameter and compared all the BDs with the AD for
the particular sample.
Results
Table 1 gives the results of AD, RD, (−8 + 14) mesh, BD
on crushed and uncrushed particles, (1–2) mm BD on cru-
shed and uncrushed particles, (−20 + 35) mesh BD on
crushed and uncrushed particles, (−12 + 20) mesh BD on
crushed particles, HGI and Cubic metre weights of all 7
samples. The samples were numbered from 1 to 7 with
ascending order for AD with lowest AD sample as sample
no. 1 and highest AD sample as sample no. 7.
The BDs using crushed samples are marginally higher
than BDs using uncrushed samples.
As AD increases, RD does not increase correspondingly.
All BDs show increasing pattern with increase in AD but
the increase necessarily not in same proportion as AD.
HGI increase or decrease did not find any correlation with
AD pattern.
The weight in kg/m3 which is also a sort of BD, is
increasing as AD increases.
We also tried to analyse the data statistically. Statistical
coefficient R2 was determined for all the densities wrt AD.
As R2 approaches a value of unity, the co-relation is sup-
posed to be very good.
Discussion
1. Comparison between Crushed and Uncrushed samples:
Looking at first 3 graphs—K (Fig. 1), L (Fig. 2) and M
(Fig. 3), we observe that crushed BD is significantly higher
than uncrushed one for the same sample.
Moreover, crushed sample is more representative of the
given lot while uncrushed contains only a small fraction of
the particles.
2. Density Co-relation graphs:
We have taken AD as the basic parameter and checked if
any other BD finds strong co-relation with AD.

Table 1 Listing of AD, RD, Parameter↓ Sample 1 2 3 4 5 6 7

BDs, HGI and Cubic Metre No.→
weights for seven samples
AD, gm/cc 1.634 1.68 1.697 1.702 1.734 1.749 1.75
RD, gm/cc 2.012 2.006 2.05 2.036 2.047 2.045 2.014
(−8 + 14) mesh BD Crushed 0.676 0.73 0.73 0.709 0.763 0.87 0.847
(gm/cc) Uncrushed 0.641 0.709 0.719 0.694 0.73 0.943 0.909
(1–2) mm BD (gm/cc) Crushed 0.68 0.769 0.735 0.763 0.758 0.87 0.862
Uncrushed 0.68 0.735 0.725 0.73 0.735 0.943 0.909
(−20 + 35) mesh BD Crushed 0.74 0.759 0.789 0.789 0.789 0.952 0.896
(gm/cc) Uncrushed 0.769 0.779 0.769 0.8 0.759 0.896 0.896
(−12 + 20) mesh BD Crushed 0.709 0.746 0.752 0.763 0.787 0.893 0.885
(gm/cc)
HGI 42.17 43.05 48.3 42.12 47.25 38.95 38.41
kg/m3 726.12 739.18 787.54 772.01 836.61 988.75 977.1
Uniform Bulk Density for Calcined Petroleum Coke 1167

Fig. 1 (−8 + 14) mesh crushed 1 2 3 4 5 6 7

Graph – K: sample no→
and uncrushed BD, g/cc (Y-axis)
wrt sample nos (X-axis) (-8+14) mesh crushed BD,g/cc 0.676 0.730 0.730 0.709 0.763 0.870 0.847
(-8+14 )mesh uncrushed BD,g/cc 0.641 0.709 0.719 0.694 0.730 0.943 0.909

Fig. 2 (1–2) mm crushed and

uncrushed BD, g/cc (Y-axis) wrt Graph – L : sample no → 1 2 3 4 5 6 7
sample nos (X-axis) (1-2) mm crushed BD,g/cc 0.680 0.769 0.735 0.763 0.758 0.870 0.862
( 1-2 ) mm uncrushed BD,g/cc 0.680 0.735 0.725 0.730 0.735 0.943 0.909

Fig. 3 (−20 + 35) mesh crushed

and uncrushed BD, g/cc (Y-axis)
Graph – M : sample no → 1 2 3 4 5 6 7
wrt sample nos (X-axis) ( -20 + 35 ) mesh crushed BD,g/cc 0.740 0.759 0.789 0.789 0.789 0.952 0.896
( -20 + 35 )mesh uncrushed BD,g/cc 0.769 0.779 0.769 0.800 0.759 0.896 0.896

2:1 Graph—A (Fig. 4): Real Density R.D. could not be
co-related with A.D. for different samples. The
co-relation coefficient R2 is very low at 0.205
2:2 Graph—B (Fig. 5): (−8 + 14) mesh crushed BD seen
in good agreement with AD with co-relation coeffi-
cient R2 = 0.775
2:3 Graph—C (Fig. 6): (−8 + 14) mesh uncrushed BD
not in agreement with AD as good as crushed coun-
terpart of the same sample with co-relation coefficient
R2 = 0.695
2:4 Graph—D (Fig. 7): (1–2) mm crushed BD in fair
agreement with AD with R2 = 0.755
2:5 Graph—E (Fig. 8): (1–2) mm uncrushed BD not in
agreement with AD as good as crushed counterpart of
the same sample with R2 = 0.635
2:6 Graph—F (Fig. 9): (−20 + 35) mesh crushed BD
could not find co relation with AD with R2 = 0.666
2:7 Graph—G (Fig. 10): (−20 + 35) mesh uncrushed BD
couldnt find co-relation with AD with R2 as low as
0.455
2:8 Graph—H (Fig. 11): (−12 + 20) mesh crushed BD in
very good agreement with AD with R2 = 0.797. In
fact AD is determined on this particular size fraction
2:9 Graph—I (Fig. 12): Cubic metre weight is Bulk
density for overall material as all particles participate.
The co-relation with AD was fairly good with
R2 = 0.765
2:10 Graph—J (Fig. 13): HGI which is also an indication
of density, had poor co-relation with AD with
R2 = 0.065.
1168 R.N. Narvekar et al.

Fig. 4 RD, g/cc (Y-axis) wrt

AD, g/cc (X-axis)
DENSITY CO-RELATION GRAPHS (A & B)
Graph A: s.no→ 1 2 3 4 5 6 7
A.D. g/cc 1.634 1.680 1.697 1.702 1.734 1.749 1.75
R.D. g/cc 2.012 2.006 2.05 2.036 2.047 2.045 2.014

Fig. 5 (−8 + 14) mesh BD, g/cc Graph B: sample no → 1 2 3 4 5 6 7

using crushed sample (Y-axis)
wrt AD, g/cc (X-axis) A.D. g/cc 1.634 1.68 1.697 1.702 1.734 1.749 1.75
(-8+14) mesh crushed BD,g/cc 0.676 0.73 0.73 0.709 0.763 0.87 0.847

Fig. 6 (−8 + 14) mesh

uncrushed BD, g/cc (Y-axis) wrt
DENSITY CO-RELATION GRAPHS (C & D)
AD, g/cc (X-axis) Graph - C: sample no → 1 2 3 4 5 6 7
A.D. g/cc 1.634 1.68 1.697 1.702 1.734 1.749 1.75
(-8+14) m uncrushed BD,g/cc 0.641 0.709 0.719 0.694 0.73 0.943 0.909
Uniform Bulk Density for Calcined Petroleum Coke 1169

Fig. 7 (1–2) mm crushed BD,

Graph - D : sample no → 1 2 3 4 5 6 7
g/cc (Y-axis) wrt AD, g/cc
(X-axis) A.D. g/cc 1.634 1.68 1.697 1.702 1.734 1.749 1.75
( 1 -2 ) mm Crushed BD, g/cc 0.68 0.769 0.735 0.763 0.758 0.87 0.862

Fig. 8 (1–2) mm uncrushed BD,

g/cc (Y-axis) wrt AD, g/cc
DENSITY CO-RELATION GRAPHS (E & F)
(X-axis) Graph – E : sample no → 1 2 3 4 5 6 7
A.D. g/cc 1.634 1.68 1.697 1.702 1.734 1.749 1.750
( 1-2 ) mm uncrushed BD,g/cc 0.680 0.735 0.725 0.730 0.735 0.943 0.909

Fig. 9 (−20 + 35) mesh crushed

Graph – F : sample no → 1 2 3 4 5 6 7
BD, g/cc (Y-axis) wrt AD, g/cc
(X-axis) A.D. g/cc 1.634 1.68 1.697 1.702 1.734 1.749 1.75
(-20 + 35 )m crushed BD,g/cc 0.74 0.759 0.789 0.789 0.789 0.952 0.896
1170 R.N. Narvekar et al.

Fig. 10 (−20 + 35) mesh

uncrushed BD, g/cc (Y-axis) wrt
DENSITY CO-RELATION GRAPHS (G & H)
AD, g/cc (X-axis) Graph – G : sample no → 1 2 3 4 5 6 7
A.D. g/cc 1.634 1.68 1.697 1.702 1.734 1.749 1.75
(-20 + 35 ) m uncrushed BD,g/cc 0.769 0.779 0.769 0.8 0.759 0.896 0.896

Fig. 11 (−12 + 20) mesh

crushed BD, g/cc (Y-axis) wrt Graph – H : sample no → 1 2 3 4 5 6 7
AD, g/cc (X-axis) A.D. g/cc 1.634 1.68 1.697 1.702 1.734 1.749 1.75
(-12 + 20 ) m crushed BD, g/cc 0.709 0.746 0.752 0.763 0.787 0.893 0.885

Fig. 12 kg/m3/1000, g/cc

(Y-axis) wrt AD, g/cc (X-axis)
DENSITY CO-RELATION GRAPHS (I & J)
Graph – I : sample no → 1 2 3 4 5 6 7
A.D. g/cc 1.634 1.68 1.697 1.702 1.734 1.749 1.75
Kg/ m3 /1000, g/cc 0.726 0.739 0.787 0.772 0.836 0.988 0.977
Uniform Bulk Density for Calcined Petroleum Coke 1171

Fig. 13 HGI/50 index (Y-axis)

Graph – J : sample no → 1 2 3 4 5 6 7
wrt AD, g/cc (X-axis)
A.D. g/cc 1.634 1.68 1.697 1.702 1.734 1.749 1.75
HGI / 50 0.8434 0.861 0.966 0.8424 0.945 0.779 0.7682

Summary 2. (−12 + 20) mesh sample prepared for AD could be used

1. Particular size BD using crushed sample shows signifi-
cantly higher value as compared to BD using uncrushed
sample for the same blend.
2. Co-relation coefficient R2 is much higher for all BDs
when analysed using crushed samples as compared to the
uncrushed samples.
3. BD using crushed samples for particles sizes (−12 + 20)
mesh are seen to be in good agreement with corre-
sponding AD.
4. Cubic Metre Weights are seen to be in good agreement
with corresponding AD.
Conclusion
1. Sample preparation for B.D. measurement is very criti-
cal. It is most desirable to have the upper size particles
crushed and accounted for in analysis, rather than origi-
nal particles isolated by sieving alone.
for determining BD and will hold good co-relation with
AD. This test can be used as a substitute for AD.
3. Cubic Metre Weight can be used to determine the overall
density of the material and finds good correlation with
AD. This test is simple as does not involve sieving and
sample preparation.
References
1. M. Lubin, L.P. Lossius, L. Edwards, Calcined coke round robin 19
and the precision of bulk density tests, in Light Metals (2013)
2. R. Barral, Coke apparent density by mercury pycnometery,
Aluminium Pechiney Standard Procedure, A.07.11.V06 (1999)
3. K. Van Saun, Everything you always wanted to know about
Petroleum Coke
4. Anodes for the Aluminium Industry, R&D Carbon Ltd
 Use of Thermally Desulfurized Shaft CPC
for Anode Production

Les Edwards, Kevin Harp, and Christopher Kuhnt

Abstract
Thermal desulfurization (TDS) of petroleum coke during calcination is a well-known
phenomenon which results in a significant decrease in bulk density. In 2011, Rain Carbon
began experimenting with TDS in a shaft calciner and some results were unexpected,
particularly an increase in real density. This paper reports on the results of extensive work
to explore the fundamental differences between TDS in shaft calciners and rotary kilns.
Pilot anode studies have been completed to explore the potential of using TDS coke from
shaft calciners in anode production. The attraction is both commercial and environmental.
High sulfur (S) cokes are readily available and cheaper than low S cokes and removing SO2
during calcination is more efficient than removing SO2 from potroom flue-gas streams to
meet emission limits.

Keywords
Petroleum coke Anodes Shaft calcining Sulfur Desulfurization

Introduction important conclusion is that these functional groups exist

Thermal desulfurization (TDS) of petroleum coke is a
well-studied phenomenon and two papers from 2007 and
2008 [1, 2] provide a detailed review including problems
TDS creates during calcining and anode baking. A recent
paper by Xiao et al. [3], provides an excellent overview of
the structural changes occurring during TDS. The paper uses
molecular modelling to show changes occurring for sulfur
(S), nitrogen and oxygen containing molecules. An
L. Edwards (&)
RAIN CII Carbon LLC, 1330 Greengate Drive, Suite 300,
Covington, LA 70433, USA
e-mail: les.edwards@raincarbon.com
K. Harp
RAIN CII Carbon, Lake Charles Calcining Plant,
1920 Pak Tank Rd, Sulphur, LA 70665, USA
e-mail: kevin.harp@raincarbon.com
C. Kuhnt
RÜTGERS Basic Aromatics GmbH, Kekuléstr. 30,
44579 Castrop-Rauxel, Germany
e-mail: christopher.kuhnt@raincarbon.com
along the periphery of the coke structure making their
removal easy during calcination.
Table 1 shows the results of a TDS trial in a rotary kiln
with green petroleum coke (GPC) containing 4.6% S. The S
loss under normal calcining conditions is 9–14% and it is
important to note that this is not caused by TDS [1]. At
higher calcining temperatures, the S loss increases to 30 and
47% due to TDS. This is accompanied by a drop in vibrated
bulk density (VBD), real density (RD) and particle strength
(shown as crush strength). Lc results are included to show
the relative level of calcination (higher Lc = higher
temperature).
The decrease in VBD (ASTM D4292, 30  50 mesh)
and RD of calcined petroleum coke (CPC) resulting from
TDS has previously been attributed to an increase in
micro-porosity [4]. The best analytical method to charac-
terize this is high pressure mercury (Hg) intrusion
porosimetry. The pore size distribution curves of TDS coke
show the appearance of a peak in the 0.01–0.10 µm pore
size range that increases significantly as the level of TDS

© The Minerals, Metals & Materials Society 2017 1173

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_141
1174 L. Edwards et al.

increases. An example is included later in the paper to show
this.
Attempts to use TDS CPC from a rotary kiln to produce
anodes have been unsuccessful. In a recent publication [5], a
coke heated to 1500 °C with TDS was added to the ball mill
fines (BMF) fraction of an anode recipe. The study con-
cluded that it was not viable due to the significant drop in
baked anode density (*0.04 g/cc) and deterioration of other
anode properties.
The interest in TDS of coke is both an economic and
environmental one. High S cokes are well known to sell at a
significant discount to low S cokes due to their more plentiful
supply [6]. Their use increases SO2 emissions however, which
must be reduced via scrubbing to meet permitted emission
limits. In principal, it is more efficient/economic to remove
SO2 during coke calcining than aluminum production. SO2
concentrations are much higher and flue gas volumes much
lower compared to the high volume flows and low SO2 con-
centrations from smelter (potline) exhaust gas streams.
In 2011, Rain Carbon began experimenting with TDS in a
shaft calciner to investigate any potential benefits. Some
unexpectedly high RD results led to extensive work over the
2011–2016 period. In August 2015, a shaft calcining com-
pany in China reported that it was constructing a high
temperature shaft calciner specifically for TDS of coke.
The objective of this paper is to review the fundamental
differences between TDS in a rotary kiln and shaft calciner
and to report on the results of pilot anode testing. The paper
will discuss the potential of using TDS to reduce smelting
raw material costs and to deal with future SO2 emissions
issues.
2011 Shaft Calciner TDS Trial
The differences between rotary kiln and shaft calciners have
been described previously [7]. Rain Carbon operated a small
20 kt/yr shaft calciner in China from 2009–2015. In 2011, a
trial was carried out with two high volatile matter (VM), fine
particle size GPC’s. One was a very low S coke (0.4%)
with *13% VM and the other was a very high S coke
(*6%) with 12.5% VM.
During the four-day trial, the low and high S cokes were
fed to a separate group of four shafts each and a 50/50 blend
was fed to another set of four shafts. The trials were run
without recycle coke and in combination with the relatively
high VM content, the operating temperatures were 30–50 °C
higher than normal. Some key results are shown in Table 2.
The S level of the high S GPC decreased from 6 to 3% in
the CPC indicating significant TDS (50% S loss). The S
level of the low S coke appeared to increase slightly but this
was likely due to contamination from the higher S blend
used prior to the trial. The most significant finding was the
high RD of the sample with extensive TDS. The VBD
results were also of interest. When these high VM cokes are
calcined in a rotary kiln, the VBD’s are significantly lower
(*0.83–0.86 g/cc) and the trial confirmed the VBD benefits
of using a shaft calciner.
The VBD’s for the high S sample and the blend were a
little lower than the low S coke by itself but still very good
relative to the rotary kiln TDS results in Table 1. When a Hg
apparent density (AD) test was run however, the results were
dramatically different. The Hg AD result was substantially
lower for the high S coke and the blend. Very few labs have
the capability to run the Hg AD test due to its hazardous
nature but it can still provide useful information. Values
below 1.70 g/cc are considered undesirable for anode
applications.
Figure 1 shows Hg porosimetry results (up to 380 MPa)
for the three cokes. The pore size distribution plots show the
characteristic TDS peak at 0.01–0.10 µm for the high S coke
and the 50/50 blend.
Relative to the rotary kiln results in Table 1, the shaft
CPC with a TDS level of 50% has a much higher RD. This is
despite a similar level of micro-porosity as measured by Hg
porosimetry. This means that the decrease in RD from TDS
in a rotary kiln cannot be due to the increase in
micro-porosity.

Table 1 Results from rotary kiln Sample S (%) S loss (%) VBD (g/cc) RD (g/cc) Crush St. (kg) Lc (A)
TDS trial
Normal 4.0 13 0.862 2.078 3.4 29.5
Moderate TDS 3.2 30 0.775 2.029 3.3 39.3
Aggressive TDS 2.4 47 0.733 2.041 1.1 42.1

Table 2 2011 shaft calciner trial Sample GPC S (%) CPC S (%) VBD (g/cc) RD (g/cc) Hg AD (g/cc) Lc (A)
results
Low S 0.5 0.7 0.917 2.114 1.79 34.5
High S 6.0 3.0 0.885 2.110 1.67 36.9
Blend 3.2 2.1 0.881 2.112 1.72 35.3
Use of Thermally Desulfurized Shaft CPC for Anode Production 1175

The thermal expansion profile for the high S coke heated

Fig. 1 Mercury porosimetry graphs
Thermal Dilatometry Testing
A key set of experiments to understand the above was
thermal dilatometry testing. Large, single pieces (*50 mm)
of a low and high S GPC (0.5 and 5.5% S) were calcined in a
lab furnace to 1100 °C to remove the VM. The pieces were
cut with a thin-bladed diamond saw to produce rectangular
samples 20  10  10 mm. The work was difficult due to
the brittle nature of the CPC and it took multiple attempts to
get two samples of each coke for testing.
A dilatometer measures the thermal expansion of samples
and an instrument capable of operation at 1500 °C with an
inert atmosphere and variable heating rates was used. The
coke samples were heated at fast (50 °C/min) and slow
(1 °C/min) heating rates to simulate the difference between a
rotary kiln and shaft calciner. The results (Fig. 2), showed a
fundamental difference between TDS in a shaft calciner and
rotary kiln.
2.E-02
High S, Fast Rate
2.E-02 Low S, Fast Rate
dL/Lo
at a fast rate is very different from the three other results.
A large, irreversible expansion starts at around 1400 °C and
continues until the measurement is stopped at 1500 °C. No
such expansion occurs for the high S coke sample heated at
the slow rate or for either of the low S coke samples. The
large expansion is caused by the sudden loss of S from the
coke. This phenomenon is well-known to graphite electrode
producers and is referred to as “puffing”. Numerous papers
have been published on the subject [8] and puffing inhibitors
like iron oxide are often added to reduce the disruptive and
damaging effect of puffing during graphitization.
The above results show clearly that TDS of high S GPC
in a rotary kiln results in puffing which contributes to a
reduction in both RD and VBD. Puffing only occurs at high
heating rates whereas TDS occurs at all heating rates and is
independent of the calcining technology. The lack of puffing
in a shaft calciner explains why the VBD drop is lower. TDS
still occurs however, and has a damaging impact on the final
coke structure.
SEM and 3D X-Ray Nano-Tomography
Three samples of a high S (5.1%) GPC were calcined to
different temperatures at the same fast heating rate of a rotary
kiln. The S level of the CPC samples was 4.5, 2.5 and
0.85%. The 0.85% S level was achieved by increasing the
soak time from 15 min to 1 h. Table 3 shows selected
properties to highlight the VBD decrease, the initial RD
decrease and the BET surface area increase. The surface
areas were measured with nitrogen adsorption on samples
milled to a Dv 50 particle size of *25 µm.
The three samples were analyzed first by high resolution
scanning electron microscopy (SEM) and significant differ-
ences were observed. The non-TDS sample calcined at
1250 °C with 4.5% S was largely featureless at high reso-
lution except inside pores and cracks. Both samples with
TDS showed a very different structure with clear evidence of

High S, Slow Rate

1.E-02
Low S, slow rate
layering and ordering. Figure 3 shows high resolution SEM
images of the 4.5 and 0.85% coke samples. The 0.85% S
5.E-03 sample shows a high level of porosity between domains of a
well-formed plate-like and ordered carbon microstructure.
0.E+00
0 200 400 600 800 1000 1200 1400 1600 The samples with 4.5 and 0.85% S were then examined
Temperature°(C) using a nanoscale, 3D X-Ray microscope (ZEISS Xradia
Fig. 2 Thermal expansion of high and low S coke samples 810 Ultra). Details of the system theory and use can be

Table 3 Results of TDS trial Sample S (%) VBD (g/cc) RD (g/cc) Lc (A) BET SA (m2/g)
with high S CPC
1250 °C 4.49 0.943 2.077 29.5 5.5
1500 °C (15 min) 2.45 0.800 2.040 41.3 9.0
1500 °C (1 h) 0.85 0.769 2.100 44.5 13.3
1176
Fig. 3 High res. SEM images of 4.5 and 0.85% S sample
found elsewhere [9]. The microscope captures images of the
sample at high magnification while rotating in an X-Ray
beam. Specimens were prepared by selecting a single coke
particle (*50 µm size) and attaching to the tip of a pin with
epoxy. Scan times ranged from 16–34 h depending on the
x-ray transmission and imaging mode.
The 3D images generated by the imaging software are
best viewed via video simulation but Fig. 4 shows some
representative 2D images. A low resolution image is inclu-
ded for the *50 µm, 4.5% S particle (Fig. 4a) and low and
high resolution images (Fig. 4b, c) are included for
the *60 µm, 0.85% S particle.
The difference between the two samples is dramatic. The
0.85% S coke shows a very layered structure and a high
level of porosity. Whilst the level of TDS in the 0.85% S
sample is very high, the images give a good indication of
what happens to the coke structure when S is lost and why
the particle strength decreases and the surface area increases
significantly.
The increase in RD at 1500 °C with the one-hour soak
time is likely due to the rupture of closed porosity and pore
coalescence which makes the porosity accessible during the
helium pycnometry RD test. This gives a good indication of
what is likely happening at the much slower heating rates in
a shaft calciner and why the RD shows no decrease with
TDS. The S has more time to outgas and generates porosity
which is connected to the outer surface of particles ground
to <75 µm for the RD test. At faster heating rates, closed
4a 4b 4c
Fig. 4 a–c X-ray 3D nano-tomography images
L. Edwards et al.
pores are created which contribute to puffing of the coke
structure. These closed pores result in a lower RD.
The increase in Lc of the 1500 °C samples supports the
transition to a more ordered structure. The S is likely to be
playing a significant role via the mechanism of
sulfur-enhanced graphitization described previously [10].
All of this shows that the coke microstructure is significantly
changed through TDS and it cannot be considered as
something which just increases porosity and decreases VBD.
Pilot Anode Studies
Numerous pilot anode studies have been completed since
2011 on coke which has been TDS in a shaft calciner and
rotary kiln. A brief overview of some key results is presented
in the following section.
Example 1
In this first example, a regular blend of high and low S cokes
was TDS in a rotary kiln with the results shown in Table 4.
Only the high S cokes in the blend (65% of total) underwent
TDS and that is why the RD does not appear to decrease too
much. The first sample is labelled “Normal” and the samples
with 26 and 46% sulfur loss are labelled as TDS 1 and TDS
2.
Pilot anodes (150 mm Ø and 200 mm high) were pro-
duced in Rain Carbon’s pilot anode facility [11] using a coke
blend containing 30% of the TDS 1 and TDS 2 cokes. The
balance of the blend was a regular rotary kiln coke labeled
BL = “Baseline” coke. To simplify the testing, none of the
TDS coke was added to the BMF fraction. Baked anode
scrap was added at a level of 20% to all anodes to simulate
the butts addition in an anode plant. Results for selected pilot
anode properties are shown in Table 5.
The results highlight the significant negative impact of
adding TDS coke from a rotary kiln to an anode. Despite a
modest addition of only 30% of this coke to a regular CPC
blend, a significant reduction in anode density, strength,
elasticity and an increase in the specific electrical resistivity
were measured.
Example 2
In this next example, the high S shaft CPC with 50% TDS in
Table 2 was blended at a ratio of 50/50 with a regular rotary
kiln, low S coke. The sample is labelled 50TDS/50LS.
Another sample was generated with a blend containing 50%
of the same low S coke and 50% of a regular rotary kiln,
high sulfur (HS) coke with no TDS (labelled 50HS/50LS).
Use of Thermally Desulfurized Shaft CPC for Anode Production 1177

Table 4 CPC results for normal CPC sulfur (%) Sulfur loss (%) VBD (g/cc) RD (g/cc)
and TDS CPC
Normal calc. 3.53 13.0 0.886 2.064
TDS 1 2.95 20.7 0.862 2.052
TDS 2 2.19 45.9 0.806 2.055

Table 5 Pilot anode properties Anode properties BL BL + TDS1 BL + TDS2

for rotary kiln blends
Baked apparent density (g/cc) 1.61 1.58 1.55
Spec. elect. resist. (lXm) 55 64.1 73.9
Compressive strength (MPa) 54 41 33
Elasticity modulus (GPa) 4.2 2.9 2
Air permeability (nPm) 0.39 0.39 0.61

Bench scale anodes were prepared at an external lab to
determine the optimum pitch level and pilot anodes were
produced at the optimum pitch level for property measure-
ment. No butts fraction or baked scrap was added to the
anodes and selected results are shown in Table 6.
Both sets of anode densities were very low and air per-
meabilities were high due to a paste mixing problem at the
lab. On a relative basis however, the deterioration in anode
properties with the addition of TDS shaft CPC was not as
dramatic as in a rotary kiln. This highlights the advantage of
using a shaft calciner to TDS coke versus a rotary kiln due to
the absence of puffing.
Looking at the other results in Table 6, the negative
impact on anode strength and elasticity modulus when TDS
coke is used is clear. The CO2 reactivity residue and dust
levels were also adversely impacted but this is partly
explained by the higher calcium level (the S levels were
similar at *2.7%). The silicon (Si) level is also much higher
and this will be discussed later under the refractory wear
section.
The above work was repeated later at Rain Carbon’s pilot
anode lab but the coke with 50% TDS was added at a rate of
35% in a blend with BL rotary kiln coke. The TDS coke was
added to the blend in three different ways:
1. Split uniformly across all aggregate fractions
2. Added to the BMF fraction and coke fines fraction only
3. Added only to the coarser coke fractions
20% baked anode scrap was added to all recipes. The
baked anode densities were much better in this study ranging
from 1.58 to 1.60 g/cc versus 1.61 g/cc for the 100% BL
coke anodes. Adding the TDS coke to the BMF fraction had
a very negative effect on electrical resistivity and mechanical
properties like flexural strength however and increased the
optimum pitch level by *2%. When the TDS coke was
added to the coarse fractions only, the mechanical properties
and electrical resistivity were quite similar to the BL anodes
and the only negative result was a lower baked anode density
of 1.59 g/cc at an optimum pitch level 0.5% higher.
Example 3
In this next more comprehensive study, pilot anodes were
produced at Rain Carbon’s lab with coke TDS to a level
of *40% (40% S loss). For comparative purposes, the study
includes reference anodes made with 100%, normal shaft
CPC (no TDS) and anodes made with 100% normal rotary
kiln CPC. All anodes were made with the addition of 20%
baked anode scrap. The following labels are used in the
graphs to identify the coke blends:
• BL Rotary: Baseline, 100% rotary kiln calcined coke.
• BL Shaft: Baseline, 100% shaft calcined coke.
• TDS Shaft/NCS Fines: TDS shaft coke used in all the
coarse fractions and Normal Calcined Shaft coke (base-
line shaft) used in the BMF fraction.
• TDS Shaft: TDS shaft in all fractions including BMF.
Selected results are presented in Fig. 5. The pilot anodes
were produced at different pitch levels to determine the
optimum.
The first point to make is that the baked anode densities
for anodes made with 100% rotary kiln CPC (BL Rotary) are
within the normal industry range. At the optimum pitch level
of 14%, the baked density is 1.617 g/cc. The low air per-
meabilities for all the anodes in this study (<1 nPm) gives
confidence that the anode paste was well mixed and well
formed. As expected, the anodes made with 100% shaft CPC
(BL Shaft) showed a higher baked anode density
(1.647 g/cc) and a lower optimum pitch level (13% vs. 14%)
relative to the BL rotary blend.
Anodes made with TDS shaft coke in all parts of the
aggregate recipe (except baked scrap) showed significantly
inferior results to the other anodes. The only property that
1178 L. Edwards et al.

looks reasonable is the baked anode density where the
results were similar to the BL rotary kiln coke. The com-
pressive strength, flexural strength and elasticity modulus are
poor and the slope of the specific electrical resistivity curve
is very steep and increases rapidly at lower pitch levels.
It is clear from this study that it would not be possible to
make anodes with 100% of a coke that has undergone a
moderate level of TDS (40% S loss) in a shaft calciner.
The most interesting results from the study were those
generated using TDS shaft coke only in the coarser part of

Table 6 Pilot anode properties Property 50TDS/50LS 50HS/50LS

for TDS and non-TDS blend
Pitch level (%) 17.5 16.5
Baked anode density (g/cc) 1.447 1.464
Air permeability (nPm) 4.3 3.7
Spec. elect. resist. (lXm) 63.5 63.0
Compressive strength (Mpa) 32 39
Elasticity modulus (GPa) 3.5 4.3
CO2 reactivity residue (%) 88.7 95.2
CO2 reactivity dust (%) 3.5 0.2
Calcium (ppm) 274 101
Silicon (ppm) 437 171

Baked Apparent Density Specific Electrical Resistance

BL Rotary 0 0 0 0 BL Shaft BL Rotary 0 0 0 0 BL Shaft

TDS Shaft/NCS Fines TDS Shaft TDS Shaft/NCS Fines TDS Shaft
110
Spec. Elec. Resist. µΩ m

1.66
Baked Density g/cc

1.64 100
1.62 90
1.60 80
1.58 70
1.56 60
1.54 50
10 12 14 16 10 12 14 16
Pitch Level [%] Pitch Level [%]

Compressive Strength Elasticity Modulus Static

BL Rotary 0 0 0 0 BL Shaft BL Rotary 0 0 0 0 BL Shaft

TDS Shaft/NCS Fines TDS Shaft TDS Shaft/NCS Fines TDS Shaft
60 4500
Elast. Mod. Static MPa
Comp. Strength MPa

55 4000
50
3500
45
40 3000
35 2500
30 2000
25 1500
10 12 14 16 10 12 14 16
Pitch Level [%] Pitch Level [%]

Flexural Strength Air Permeability

BL Rotary 0 0 0 0 BL Shaft
BL Shaft BL Rotary 0 0 0 0
TDS Shaft/NCS Fines TDS Shaft
TDS Shaft/NCS Fines TDS Shaft
14
Flexural Strength [MPa]

1.5
12
Air Perm. nPm

10 1.3
8 1.0
6 0.8
4 0.5
2 0.3
0 0.0
10 12 14 16 10 12 14 16
Pitch Level [%] Pitch Level [%]
Fig. 5 Pilot anode properties at different pitch levels
Use of Thermally Desulfurized Shaft CPC for Anode Production 1179

the aggregate recipe. With a ball mill fines content of 26%, Jet Milling Trials
that means the anodes contained 54% of the TDS shaft coke.
These anodes still showed better baked anode densities than It has been suggested that grinding CPC to a fine enough
the anodes made with 100% rotary kiln coke and the opti- particle size will eliminate the TDS micro-porosity problem.
mum pitch level of 14% was similar. The anode mechanical Work was done in this area using a jet mill to grind coke that
properties were also similar to the BL rotary and shaft had been TDS to a level of 50%. The CPC was ground to a
anodes with the exception of the compressive strength which size of 90% <22 µm. This ultrafine coke was then added to
was a little lower. the BMF fraction of a regular anode recipe and a modified
recipe which used roughly half the amount of fines to
compensate for the much higher surface area.
Example 4 For brevity, the results will not be included in this paper
but they were poor. In fact, Rain Carbon recorded its
In this last example, a very high S coke (8.5%) was calcined highest ever electrical resistivity with one of the anode
in a lab furnace at the same heating rate as a shaft calciner. batches made using the TDS ultrafine coke (135 µXm).
The aim was to see if a low cost, high S coke could be Anodes made with jet milled fines from non-TDS coke
aggressively TDS and still used as a minor blend compo- showed very comparable results to BL anodes. This work
nent. The S was driven down to a level of 3.4% representing showed clearly that there is no way to grind-out the
a S loss of *60%. Three sets of anodes were prepared as micro-porosity because it is too fine to be penetrated by the
shown below and key results are shown in Fig. 6. CTP binder.

• BL = baseline anodes with 100% normal, rotary kiln

CPC Refractory Wear Problem
• BL + TDS Fines = Baseline CPC with TDS coke milled
and added to fines fraction (26% of the recipe) One problem with TDS in a shaft calciner is accelerated
• BL + TDS Coarse = Baseline CPC + 26% TDS CPC refractory wear. The inner shaft walls are built with high
added to coarse fractions of aggregate. silica (*95% SiO2) bricks. These bricks are cost effective
and readily available in China. At temperatures between
The above results are very poor in terms of anode quality. 1200 and 1300 °C however, the partial pressure of SiO (a
Adding only 26% of this aggressively TDS CPC to either the product of C reacting with SiO2) increases and causes
BMF fraction or the coarser part of the aggregate recipe has refractory wear. In the presence of sulfur bearing gases like
a very negative effect on anode properties. Adding the TDS H2S and S8, SiO2 reacts to form SiS. The equilibrium partial
coke to the coarse fractions is marginally better, especially pressure of SiS is an order of magnitude higher than SiO
for specific electrical resistivity. In combination with the which creates a second, more significant refractory wear
results from Examples 1–4, these results suggest that the mechanism.
amount of TDS that can be tolerated from a shaft calciner From 1200–1300 °C, the activity of SiO increases by a
decreases rapidly at levels above *40% sulfur loss. factor of five and the partial pressure of SiS increases about
Baked Apparent Density Specific Electrical Resistance
threefold. This will cause a rapid deterioration of the
BL BL+TDS F
BL+TDS C
BL
Bl+TDS C
BL+TDS F
refractory lining and most shaft calciner operators are aware
Spec. E;lec. Resis.µΩ m
Baked App. Dens. g/cc

1.63 100
90
of this problem. It can reduce the refractory life from an
1.61
1.59
80 average of 8–10 years to <2 years. This problem also causes
70
1.57
60
Si contamination of the CPC product. This is why the Si
1.55
12 13 14 15 16
50
12 13 14 15 16
level is so high in Table 6 for the TDS anode blend. The
Binder Level [%] Binder Level [%] projected Si level was 160 ppm versus an actual level
Elasticity Modulus Static of >400 ppm.
Flexural Strength BL BL+TDS F
BL BL+TDS+F Bl+TDS C The above will significantly limit the ability of shaft
Elast. Mod. Static [GPa]

5.5
Flexural Strength [MPa]

Bl+TDF C
12 4.5
calciners to TDS coke. The solution is to change the type of
10
8
3.5 refractory brick but this will increase the cost. At least one
6 2.5
shaft calciner is testing this idea based on a patent [12]
4 1.5
2 12 13 14 15 16 which discloses the use of refractory materials like ZrO2,
12 13 14 15 16 Binder Level [%]
Binder Level [%] magnesite etc. The patent claims stable operation at 1350–
1500 °C and targets a sulfur reduction level of 42–72%. The
Fig. 6 Pilot anode results for shaft CPC with 60% S loss challenge will be production of a usable product for the
1180
reasons outlined in this paper and the high RD of the product
(>2.10 g/cc) which is undesirable for anode production.
H2S Generation
One final potential problem with aggressive TDS is gener-
ation of H2S gas. Rain Carbon experienced a problem with
H2S emissions at one point when running high S cokes. The
problem was evident when draft levels were low during
discharge of the CPC. In the reducing atmosphere inside the
coke bed, H2S generated from TDS should travel up through
the coke bed and into the flue walls where it will mix with
oxygen and combust to form SO2. Under low draft condi-
tions, some of the H2S stays with the product and is very
noticeable by its odor during product discharge.
At one stage, the above problem was compounded by
water leaks from the cooling water jackets. Water which
leaks into the coke bed will generate steam and then
hydrogen gas via the reaction:
H2 O þ C ! CO þ H2
The hydrogen gas can potentially accelerate the TDS of
coke which will exacerbate the H2S emission problem by
reacting with elemental S gaseous species to the point where
it can be both a significant operator safety risk as well as a
community odor problem. A patent was filed in 2009 [13]
claiming the use of a shaft calciner in this way but the patent
was never examined.
Although the presence of hydrogen gas has the potential
to lower the TDS temperature [14], detailed studies funded
by Rain Carbon at an external research lab (Kingston Pro-
cess Metallurgy Inc.) were not successful in demonstrating
any meaningful benefits [15].
Discussion and Conclusions
The results from this study highlight a fundamental differ-
ence between TDS in a shaft calciner and rotary kiln. In a
rotary kiln, the high heating rates and rapid S loss lead to an
irreversible volume expansion and “puffing” of the coke
structure which causes a significant reduction in bulk den-
sity. The creation of micro-porosity in coke during TDS
cannot be avoided in a shaft calciner or rotary kiln and
permanently damages the CPC. As the S loss increases, the
damage increases to the point where it negatively effects the
strength, porosity and microstructure of the CPC.
It is difficult to say exactly what level of TDS can be
tolerated when making an anode but pilot anode testing
suggests the S loss needs to be <40% and a lower level will
always be better. The study also shows that it is not possible
L. Edwards et al.
to make an anode with 100% of a coke that has been TDS to
a level of 40% or more. It can only be used as a blend
component at levels of 50% or lower. It is also better to keep
TDS coke out of the BMF fraction.
Although the above may sound like a major constraint,
this study has shown that it should be possible for the
industry to use coke that has undergone moderate TDS (15–
35%) in a shaft calciner if it is blended with other normally
calcined cokes. In a world where GPC S levels are expected
to continue increasing on average, this approach can bring
value for the industry. CPC and GPC may appear to be
readily available in 2016 but this situation could change very
quickly once global aluminum production resumes its
inevitable expansion to meet growing product demand.
Many smelters have learned to deal with higher trace
metal impurities in CPC like vanadium and nickel and the
tolerance depends to a large extent on the metal product mix
of the smelter. S represents a more challenging problem
because the global pressure to reduce SO2 emissions is
increasing. From this perspective, it is more economic to
remove S from coke and scrub SO2 at the calciner than it is
to scrub SO2 from the low concentration, high flue gas
volumes found in a smelter.
TDS in a shaft calciner is not without its problems
however, and most shaft calciners will not pursue this given
the significant negative impact on refractory life. It would
never be economic to rebuild a shaft calciner every 2 years
and most calciners are looking for ways to increase refrac-
tory life. Rebuilding a shaft calciner with different refractory
bricks to mitigate this problem is an option but it will
increase the capital cost significantly.
The other practical limitation of TDS in a shaft calciner is
the H2S emissions problem. This would not be a problem in
a new shaft calciner with good draft levels but it can become
more problematic as the furnace ages (and lining cracks
develop) and/or when flue walls become partially blocked
with unburned VM and draft levels drop. H2S is a very toxic
gas and care needs to be taken if detected.
The H2S problem may also not be confined to the cal-
ciner. Rain Carbon’s lab has reported an H2S odor when
opening sample buckets containing TDS CPC. Crushing and
milling of the samples has also led to the detection of H2S.
The human nose can detect very low concentrations with its
characteristic rotten egg gas smell. It is not clear what creates
this additional H2S problem other than entrapment of minute
levels of H2S inside pores in the CPC. This could be become
an issue for a carbon plant but larger scale trials are needed
to make this determination.
One final point to make with TDS is that traditional bulk
density test methods do a poor job of detecting its presence.
A coke which has undergone TDS may appear to look okay
on the basis of ASTM 30  50 or 20  35 VBD tests but a
Hg AD test can show quite a different result. One definitive
Use of Thermally Desulfurized Shaft CPC for Anode Production
way to check for evidence of TDS is to run a Hg porosimetry
test. A peak in the 0.01–0.10 µm pore size range as shown in
Fig. 1 acts as a fingerprint for TDS and can be used to
determine whether a coke has undergone TDS.
Acknowledgements The authors would like to thank Zeiss for con-
ducting the 3D-Xray nano-tomography work and to Dr Malisja deVries
at CSIRO Manufacturing for the SEM work and help in setting up the
collaboration with Zeiss. Thanks also to Kingston Process Metallurgy
Inc. for TDS experiments with hydrogen and other gases.
References
1. L. Edwards, K. Neyrey, L.P Lossius, A review of coke and anode
desulfurization, in Light Metals (2007), pp. 895–900
2. L.P Lossius, K. Neyrey, L. Edwards, Coke and anode desulfur-
ization studies, in Light Metals (2008), pp. 881–886
3. J. Xiao et al., Modelling the change of green coke to calcined coke
using qingdao high sulfur petroleum coke. Energy Fuels 29, 3345–
3352 (2015)
4. R.E. Gehlbach et al., Effect of calcination temperature on real
density of high sulfur cokes, in Light Metals (1977)
1181
5. A. Gagnon et al., Impurity removal from petroleum coke, in Light
Metals (2013), pp. 1057–1062
6. L. Edwards, The history and future challenges of calcined
petroleum coke production and use in aluminum smelting. JOM
67(2), 308–321 (2015)
7. L. Edwards, Quality and process performance of rotary kilns and
shaft calciners, in Light Metals (2011), pp. 895–900
8. M. Whittaker, L. Grindstaff, The irreversible expansion of carbon
bodies during graphitization, in Carbon, vol. 7 (1969), pp. 615–
621
9. A.P. Merkle, J. Gelb, The ascent of 3D x-ray microscopy in the
laboratory, in Microscopy Today (2013), pp. 18–23
10. S. Brandtzæg, H. Oye, Structural changes of petroleum coke
during sulphur evolution, in Light Metals (1986), pp. 593–604
11. W. Boenigk et al., Pilot anode testing of alternative binder and
CPC raw materials, in Light Metals (2015), pp. 1033–1038
12. Chinese Patent, CN104555982, Inventors—王征宇, 赵满生, Pri-
ority date Dec 23, 2014
13. Dr. S. Wilkening, DE102009 015 027A1, Process and apparatus
for the desulfurization of green petroleum coke during its
calcination in vertical shaft furnaces (2009)
14. C.P. Goforth, J.A. Hamshar, US Patent 4,289,388, Desulfurization
of petroleum coke, 22 Feb 1982
15. S. Bell, Desulfurization of coke, Report Prepared by Kingston
Process Metallurgy Inc for Rain Carbon, July 2014
 Anode Carbon Aggregate Packing Description
Compared to Relevant Industrial
and Engineering Practises

Bjarte Øye and Lorentz Petter Lossius

Abstract
The primary aluminium metal production carbon anode is a high volume product even on
the global scale, which can benefit from optimising the aggregate packing. The general
impression from literature is that the industry employs relatively simple methods for
particle sizing, modified and enhanced by specific knowledge about the materials in
question. The study lists examples of current and possible methods for measurement and
control. A common approach is techniques based on sieving, like the Fuller curves:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Cumulative % finer than ¼ ðparticle diameter=maximum particle diameterÞ  100%

The packing of a given particle size distribution is substantially affected by surface

roughness and particle shape, factors that normally is addressed only empirically if at all.
The focus is on carbon anode production for aluminium metal reduction, but a comparison
is made with other industries.

 
Keywords
Aluminium Anode Aggregate

Introduction in common that they are relatively simple, robust and easy to
apply.
Proper aggregate grading is important for good and consis-
tent anode quality. Correct sizing of particles serves both the
purpose of obtaining good packing density (low amount of Particle Packing
binder) and maintaining a good workability of the paste.
These factors are closely related in packing of particle beds; Generally, the particle packing density a in a volume is
as optimal particle-size distribution and low binder volume defined as the ratio of the, solid volume of the particles Vp to
generally results in favourable rheology of the mix. the bulk volume Vb , Eq 1, where qbulk is the bulk density,
The civil engineering and concrete industry have long and the qp is the particle density:
experience with grading of particles of similar size as the
carbon anode aggregate. A variety of methods has been Vp qbulk
a¼ ¼ ð1Þ
developed in the course of time; the most widely used have Vb qp

The content of voids e is the volume not occupied by

B. Øye (&) particles, Vb  Vp , divided by the bulk volume Vb :
SINTEF Materials and Chemistry, 7465 Trondheim, Norway
e-mail: bjarte.oye@sintef.no V b  Vp
e¼ ¼1a ð2Þ
L.P. Lossius Vb
Hydro Aluminium, 6882 Øvre Årdal, Norway

© The Minerals, Metals & Materials Society 2017 1183

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_142
1184 B. Øye and L.P. Lossius

Fig. 1 Relative size and relative amount of particles influence packing density. Maximum packing density (left) is achieved when smaller
particles fit exactly into the voids created by larger ones

The achievable packing density depends on the particle

sizes and shape. Figure 1 illustrates in 2D the interactions
between large and smaller particles, indicating how maxi-
mum packing density is achieved when smaller particles fit
exactly into the voids created by larger ones.

Packing Models

Traditionally, models describing particle packing can be

divided into two types:
Discrete models: Use idealised sets of specifically sized
particles in creating packing models. Example: Furnas
model, which uses a bimodal approach.
Continuous models: Use continuous gradations of parti-
cle sizes (multimodal). Examples are Fuller Thompson,
Andreasen, and Rosin-Rammler.
Fuller curves: Fuller and Thompson [1] described in 1907
a grading curve with a minimum of voids determined by
experimental work, made by the formula in Eq. 3. The
equation would provide a well-graded mixture with maxi-
mum density for spherical particles:
 0:5
d
CPFT ¼  100% ð3Þ
Dmax
where
CPFT Cumulative percent finer than,
d particle size and
Dmax the maximum particle size.
The equation is of type “cumulative percentage finer
than”, in that they yield the percentage of the total mass
being finer than the given particle diameter. The CPFT value
calculated for a series of particle diameters can be plotted in
a Fuller curve (or Fuller Thompson curve), shown in Fig. 2.
By passing an aggregate through an array of sieves the CPFT
can easily be determined, plotted, and compared to the Fuller
curve.
Fig. 2 Example of Fuller curve, Dmax = 16 mm
Furnas Theory
In 1928, Furnas [2, 3] derived a theory for the maximum
packing density of bimodal mixtures, i.e. a bed containing
two non-interacting particles of two discrete particle diam-
eters. Assuming that the fractional void volumes, m, of the
individual monomodal beds are identical and that the ratio of
the two particle diameters is large, the composition of
maximum density is obtained if the small particles fill the
interstices of the large particles, shown in the left example of
Fig. 1, such that the total bed volume does not increase. In a
unit cell, the absolute volume of large particles is ml = 1 − m.
Filling the void volume m with small particles, the absolute
volume of small particles is ms = m (1 − m). The volume ratio
of large particles to small particles is 1/m and the void vol-
ume of the mixed bed is m2.
Fennis [4] sums up the simple cases of the Furnas model
like this: By definition the volume of each monosized par-
ticle class can be expressed in its partial volume ui , which is
the volume occupied by size class i in a unit volume. Fur-
thermore, the relative volume of each size class can be
expressed as its volume fraction ri :
Anode Carbon Aggregate Packing Description Compared … 1185

Xn  n 
ri ¼ ui = ui ð4Þ Di  Dns
i¼1 
CPFTi ¼ n   100% ð8Þ
Dl  Dns
X
n
ri ¼ 1 ð5Þ where
i¼1
CPFT Cumulative Percent Finer Than (volume)
With only one size class, ri ¼ 1, the partial volume of this Ds Smallest particle size
size class ðui Þ is equal to the total occupied volume or total Di Particle size
packing density at . When there are two size classes present, Dl Maximum particle size
the following two cases can be distinguished: n ln r/ln q
where
• The volume fraction r of the large particles is much
larger than the volume fraction of the small particles q is the diameter ratio of successive size frac-
ðr1  r2 Þ. tions. Furnas theory is derived from geometri-
Small particles (diameter d2) can be added to a container cal series of discrete particle sizes
filled with large particles (diameter d1). By adding the r is the volume ratio of the successive size
small particles into the voids between the large particles, fractions. Furnas approximated this ratio to be
the voids are filled and thus the total occupied volume constant, assuming that the theorem also holds
and the packing density increase. The total volume for any q, however small, with the provision
occupied by particles in a container is expressed by: that the volume ratio of consecutive size
fractions is no longer the same as for the
a1 a1
at ¼ u 1 þ u 2 ¼ a1 þ u 2 ! at ¼ ¼ ð6Þ optimum mixture at large values of q.
1  r2 r1

In this case, the total packing density equals the volume
of the large particles (which is restricted by the maximum
packing density of the large particles) plus the volume of
the small particles, in a unit volume.
• The volume fraction of the small particles is much larger
than the volume fraction of the large particles ðr2  r1 Þ.
Large particles can be added t no a container filled with a
matrix of small particles. By adding some large particles
into a matrix of small particles, the large particles fill up
the volume they occupy by 100%. Their contribution to
the packing density is therefore equal to their partial
volume u1 . The small particles can fill up the rest of the
unit volume ð1  u1 Þ with their maximum packing
density:
1 D
at ¼ u1 þ u2 ¼ u1 þ a2 ð1  u1 Þ ! at ¼
r1 þ ðr2 =a2 Þ
Andreasen Models
Simultaneously to Furnas, Andreasen arrived at a similar,
semi-empirical model for ceramic materials [8]. The Andreasen
model can be regarded as a development of the Fuller curve, and
is more practical to apply than the Furnas model.
The Fuller curve (Eq. 3), did not provide satisfactory
results with real crushed rock, which deviated from spherical
form. Andreasen found that better results were obtained
when the exponent (q) was lowered from 0.5 towards 0.4.
The theoretical approach of the model is to start with small
particles, adding coarser and coarser particles, leading to the
general equation:
 q
d
CPFT ¼ 100% ð9Þ
ð7Þ
where

In this case the total packing density equals the volume
of the large particles plus the remaining volume filled
with the maximum amount of small particles (which is
restricted by the maximum packing density of the small
particles), in a unit volume.
These relationships has been utilised in many industries
for discrete particle mixtures. Andreasen and Andersen in
1930 [5] and Furnas in 1931 [6] extended the theory to
continuous variable particle diameters.
The extended Furnas model [7]:
CPFT Cumulative Percent Finer Than (volume)
d Particle size
D Maximum particle size
q Distribution coefficient (q-value). The Fuller curve
is the case where q = 0.5, and will give the straight
line in the log-lin diagram.
A limitation of the Andreasen model is that the distri-
bution implies an infinite distribution with no defined min-
imum particle size. To deal with this issue Andreasen
developed a modified version of the model, where minimum
particle size is introduced:
1186 B. Øye and L.P. Lossius

 
dq  dmq where
CPFT ¼ q  100% ð10Þ
ðD  dmq Þ A area projection
P perimeter projection.
where
In the same way, the circularity of the projection can be
CPFT Cumulative Percent Finer Than (volume)
defined as
d Particle size
dm Minimum particle size of the distribution P
D Maximum particle size Circularity ¼ pffiffiffiffiffiffiffiffiffiffi ð12Þ
2 pA
q Distribution coefficient (q-value).
The relationship between sphericity and circularity is
SPHT = 1/Circ2.
Adapting the sphericity definition on Fuller curves of
Particle Shape and Sizing crushed sands of different sphericity, Osthreeren found that
the optimal Fuller exponent was equal for all sphericity,
Particle Shape although the calculated packing densities varied [11].

The measurement of non-spherical particles depend on the

measuring method, and the measured size of a particle is
linked to its shape and deviation from sphericity. Hence,
caution should be exerted when comparing particle size
distribution obtained by different methods. Table 1 sums up
commonly used particle size analysis equipment, and how
they assess equivalent particle spherical diameters, and this
is also illustrated in Fig. 3.
Definitions of particle shapes are described in ISO 9276-6
(2008): Descriptive and quantitative representation of parti-
cle shape and morphology. The standard operates with dif-
ferent levels of shape; there might be a 2013 version as the
ISO review cycle is 5 years
Sieving
The practice of sieving is very old; however, it is only the
last century that focus has shifted from craft experience to
approaches that are more theoretical. Today sieving is per-
haps still the most common technique of particle sizing in
the civil engineering section, mainly because the method is
fast and simple. A sieve analysis can be performed on any
type of non-organic or organic granular materials including
sands, crushed rock, clays, granite, feldspars, coal and soil, a
wide range of manufactured powders, grain and seeds, down

– First level being overall form (elongation, sphericity).

– Second level being roundness (radius of the curvature at
the particle—e.g. the sharp edges of crushed rock vs the
more rounded edges on gravel).
– Third level being surface texture and roughness.

According to ISO 9276-6.2008(E), the sphericity of a

particle is the ratio of measured circumference of particle
projection and the circumference of a circle of the same area:

4pA
SPHT ¼ ð11Þ Fig. 3 Illustration of the concept of equivalent spheres [10]
P2

Table 1 Commonly used Name Equivalent spherical diameter

particle size analysis equipment
[9] Microscope Projected area
Sieve Mesh size
LasentecTM (particle chord length) Length
MalvernTM (Fraunhofer diffraction) Area; light scattering properties
TM
Coulter counter (electric zone sensing) Volume
SedigraphTM and Andreasen pipette Sedimentation
Anode Carbon Aggregate Packing Description Compared …
to a minimum size depending on the exact method. Standard
sieve analysis is probably the fastest and most widely used
quality control procedure in any powder process control
industry. Whether hand or machine sieving, wet or dry
preparations, analysis or production work, testing sieves
have found a niche in the quality control laboratory [12].
Standard methods for sieve analysis are described in
standards, for example in
– ISO* 6274:1982 Concrete—Sieve analysis of aggregates
– ASTM** C136–06 Standard Test Method for Sieve
Analysis of Fine and Coarse Aggregates
– ASTM C33/C33M—11a Standard Specification for
Concrete Aggregates
*International Organization for Standardization
**The American Society for Testing and Materials.
Practical Effects
Dealing with particles with strong deviation from sphericity
is mostly a question of experience and material knowledge.
Figure 4 shows two sets of aggregate of about the same
shape and size, smooth fluvial gravel (left) and crushed rock
of high surface roughness (right), and the various shape
parameters for the two types are shown in Table 2. It is
difficult to distinguish the two series directly from the shape
parameters, and yet they will behave very differently in a
concrete mix. The reason for this is that the workability of a
concrete is strongly dependent of the surface roughness and
inherent friction differences between different materials and
these parameters are not found in a typical shape parameter
Fig. 4 Representative particles from fluvial gravel (left) and from crushed rock (right)
1187
analysis. The overall picture is very complicated, and
experience with the type of aggregate in question will be
important in the overall assessment. When knowing what
type of aggregate being used, and having experience with
them, the shape parameter analysis can be a useful tool in the
hands of an experienced concrete designer, making it pos-
sible to predict the effect of the deviation on the overall
concrete workability.
Industrial Practice and Applicable to Anode
Carbon
The industry frequently uses particle-sizing methods adapted
to their specific activity. Such tailoring allows for simplified
methods without losing accuracy. Here, the Fineness module
and the Particle Matrix model will be dealt with in brief.
Ceramic industry, as a rule, is typically handling smaller
particle sizes than the concrete industry or in an anode plant.
In most ceramic forming techniques, particle surface
properties/effects are prominent, both because of the smaller
particle size range, and due to the polar nature of most
ceramics making surface effects more prominent. A consid-
erable part of refractories consists of clay, like chamotte,
kaoline and montmorillonite [13], normally coming as small,
flaky particles with equivalent diameter *2 µm, leading to
low degree of packing. This is counteracted by adding larger
particles of burned and crushed clay, grog, which broadens
the particle size distribution [14]. 4 mm is considered to be a
common maximum particle size for refractories.
The refractory particle distribution (red large circles) is
compared to anode carbon and the Fuller/Andreasen curves
in Fig. 5. The porcelain industry only use fines, the practical
1188 B. Øye and L.P. Lossius

Table 2 Particle shape parameters obtained by quantitative analysis of 100

projection image

Aggregate, per cent larger than

Shape parameter Fluvial Crushed
gravel rock 80
2
Area (cm ) 2.427 2.823
Perimeter (cm) 6.120 6.914 60
Max axis length (cm) 2.067 2.293
Breadth (cm) 1.563 1.812 40
Arithmetic mean of elongation ratio 1.330 1.281 Carbon, FM = 9.1
(length/breadth) 20 Fuller (q=0.5), FM = 12.1
Weighted mean of elongation ratio 1.315 1.276 Andreasen q = 0.37, FM = 10.6
Aspect ratio (Fmax/Fmin) 1.367 1.355 Modified Andreasen q = 037, FM = 10.9
0
Circularity [perimeter /(4p  area)] 2
1.257 1.359 0.05 0.5 5
Rectangularity (area/area of bounding 0.730 0.682 Particle size (mm)
rectangle)
Fullness [area/(Fmin  Fmax)] 0.733 0.712 Fig. 6 The fineness module calculated for the particle distributions
Flakiness ratio k (thickness/breadth) 0.393 0.325 shown in Fig. 5

Sphericity ratio 0.607 0.591

Shape factor 0.342 0.290 Fineness Module
Mean volume per particle V 1.590 1.673
The Fineness Module, FM, is an empirical method wide-
Area of projection profile A 2.427 2.823
spread in the concrete industry, summing up the particle
Perimeter of the projection profile Lp 6.120 6.914 sizing curves in one figure. The method is directly derived
Specific surface S=V 3.211 3.118 from sieving, hence its frequent use.
Mean surface per particle S 5.105 5.216 It is defined as the figure obtained by adding the total
percentage of the sample of an aggregate retained on each of
a specified series of sieves and dividing the sum by 100:
X
100 FM ¼ Cumulative percent aggregate retained=100
Aggregate, per cent larger than

ð13Þ
80
Figure 6 shows the FM calculated for a series of particle
distributions included a typical anode carbon aggregate
60 grading curve. The FM figures are derived from the sieve
stack in question, and are only comparable when the same
40 Carbon
stack of sieves is used. Generally, coarser material returns a
Fuller (q=0.5)
higher FM figure.
20 Andreasen q = 0.37
Modified Andreasen q = 0.37
Refractory ramming/pressing mix Particle Matrix Model
0
0.05 0.5 5 Also widely used in concrete proportioning, this is an effi-
Particle size (mm) cient way of simplifying a concrete recipe normally con-
sisting of 7–8 materials. The Particle Matrix model divides
Fig. 5 Typical refractory ramming or pressing mix grain distribution
compared to anode carbon and Fuller/Andreasen distribution curves the mix into only two phases, matrix and particles [15]:

• Matrix phase: The “fluid” phase, counting in the liquids

upper limit of particle size is considered about 0.2 µm. An and the high surface area particles <125 µm. The matrix
exception is larger and more massive porcelains structures, phase is regarded a viscous fluid, with the particles acting
like high-voltage insulators, which involves larger particles as viscosity modifiers. Increased content of particles
<0.5 mm. results in increased viscosity.
Anode Carbon Aggregate Packing Description Compared … 1189

A typical way of characterising the matrix is by emptying 100

a filled cylinder through a nozzle, measuring the flow

Aggregate, per cent larger

(m3/s) versus the liquid column height (m). The particles 80
present in the matrix cause a reduction in the flow, ter-
med flow loss. The average ratio between the flow loss 60

than
and the flow of the idealized fluid without particles, is
called the flow resistance, kQ, which is a dimensionless 40 Carbon
figure between 0 and 1. For an ideal fluid kQ = 0, for Andreasen q = 0,23
water kQ = 0.1, the matrix in high strength concrete has a 20 Andreasen q = 0,30
kQ of about 0.5–0.6, and in self-compacting concrete Andreasen q = 0,37
0
kQ = 0.55–0.70.
0.05 0.5 5
Used in anode carbon proportioning, the matrix phase
Particle size (mm)
will consist of pitch and carbon fines, and important
100
factors will be pitch type, amount of fines, and

Aggregate, per cent larger than

temperature.
80
• Particle phase: Consisting of particles >125 µm. This is
regarded as the friction phase. “Moving” the fine parti-
60
cles into the matrix phase significantly reduces the par-
ticle. The remaining particles are characterized by the 40
size distribution and the grain shape. A common method Carbon
of characterizing the particle phase is to determine the 20 Fuller (q=0,5)
void (p) which the matrix has to fill: p ¼ 1qq  ð100%Þ,
b Andreasen q = 0,37
p
Modified Andreasen q = 0,37
where qb is the bulk density and qp is the particle density. 0
Ordinary concrete mixtures have a p of 25%. 0.05 0.5 5
Particle size (mm)
Figure 7 shows the Particle Matrix mods at a glance. The
Fig. 8 Example of an anode carbon sieving curve (red) together with
model approach can also be feasible for anode carbon Fuller and Andreasen distribution. The carbon curve is richer in fines
grading, provided it can be shown that the pitch matrix compared to the others (Color figure online)
behaves in a similar way as the water phase of which the
model originally was developed. The temperature of the
pitch is s an additional parameter for which has to be Applicability on Sizing of Anode Carbon
incorporated in the model.
The carbon qualities used in the manufacturing of anodes are
from delayed coke. Two qualities are used in the manufac-
turing of anodes:

• Sponge: Irregular grains with porous microstructure with

walls that are generally anisotropic and with pores and
walls that vary in size. Typical particle size <14 mm.
Volume • Shot: Higher degree of sphericity than sponge. Ribbon and
raƟo bet- lenticular anisotropic domains arranged in concentric pat-
ween matrix terns to form shot-like coke. Typical particle size <2 mm.
and parƟcle phase
Green anodes typically contain about 15% pitch and 85%
coke, of which is 25% recycled anode. The pitch is reduced
to 5% after baking. Density green anode: 1.60–1.65 g/cm3.
Baked 0.03–0.04 g/cm3 lower. Mass loss during baking is
Castability
about 4–5 wt%.
An example of a carbon grading curve1 is shown in
Matrix ParƟcle Fig. 8, where carbon aggregate sieving curves are compared
properƟes properƟes
1
Fig. 7 The particle matrix model Provided by [16].
1190 B. Øye and L.P. Lossius

Fig. 9 Examples of green anode carbon recipes calculated by combining the particle matrix model and the modified Andreasen distribution
(Color figure online)
Anode Carbon Aggregate Packing Description Compared …
to the most common particle distribution models, the Fuller
curve and the Andreasen distributions. The anode coke is
significantly richer in fines than the Fuller and Andreasen
curves with distribution coefficient q = 0.37, which is a
typical value for dense packing of aggregate.
The relative high fraction of fines makes these materials
suitable for employing the Particle Matrix model, thus
defining the fines as part of the matrix together with the
pitch. This approach also act to simplify the particle sizing
by narrow down the particle size spectrum. Figure 9 shows
two examples of applying this approach, recipe #33 and #35
represented by white lines. In both recipes fines smaller than
0.125 mm diameter are regarded part of the Matrix phase,
while larger grains are treated as part of the particle phase
and sized by applying the Modified Andreasen distribution
(MA). The MA has a set point for minimum particle size,
which makes the model suitable for use together with the
Particle Matrix model.
Examining the graphs in Fig. 9: Both recipes includes
24% matrix phase, the particle (aggregate) phase making up
the balance of 76%. The red dotted curve shows the Modi-
fied Andreasen model with distribution coefficient (q-value)
of 0.26 for #33 (top) and 0.52 for #35 (bottom). Not that
higher particle distribution results in recipes higher in large
particles. The blue line represent the reference recipe. The
multiple coke fractions making up the recipe are shown as
the thin lines in the lower part of the graph.
An advantage with this procedure is that it provides an
instant overview at a glance, of a rather complex mixing
situation, and tweaking of the recipes are swift and simple.
Conclusions
The paper describes and compares various particle-packing
models, and briefly discuss suitable models for the deter-
mination of anode mixes. In general, the Andreasen model
seems to offer a good balance between relatively simple and
swift sizing of the particles, and sufficient control over the
particle packing. Attention must be given to the optimization
of the distribution coefficient q. In addition, the balance
between flow and particle packing has to be optimized.
Generally, increased amounts of fines (lower values of
q) provide a better flow, however the particle packing suffers
slightly with subsequent higher amount of pitch.
Optimal particle packing (higher values of q) ensures a
lowest possible pitch fraction, however the flow might suffer
slightly.
Another simplifying approach for sizing of aggregate is
the Fineness Module, FM, where a grading curve is
reduced to one figure by summing the percentage retained
1191
for each sieve fraction. When operating within a
specific set of materials and sieves this can be a quick and
reliable way to check upon the particle grading, albeit with
very little detail control of the actual grain size
distribution.
The Particle Matrix model is another method of concrete
proportioning, where the liquid phase (matrix) and the par-
ticle phase are treated separately. This model treats all par-
ticles of diameter <125 µm as a liquid, the particles regarded
as viscosity modifiers. Mixing the remaining particles cre-
ates a void p the Matrix has to fill. The Matrix Particle
Model is designed for water as the prime liquid; if it can be
adapted to the far more viscous pitch in the anode mix
remains to be clarified.
An example is given of two green anode aggregate/pitch
recipes prepared by combining the Particle Matrix model
and the Modified Andreasen distribution model.
Acknowledgements The work was carried out in the research pro-
grams HAL UP and SHIFT, led by Nancy J. Holt of Hydro Aluminium.
The programs were funded by Hydro Aluminium and the Research
Council of Norway. Permission to publish the method and results is
gratefully acknowledged.
References
1. W. Fuller, S.E. Thompson, The laws of proportioning concrete.
Trans. Am. Soc. Civil Eng., 67–143 (1907). Paper no. 1053
2. C.C. Furnas, Bureau of Mines, Report of Investigation Serial
No. 2894, vol. 7 (1928)
3. C.C. Furnas, Bur. Mines. Bull. 307, 74–83 (1929)
4. S.A.A.M. Fennis, Design of Ecological Concrete by Particle
Packing Optimization. PhD dissertation, Technische Universiteit
Delft, 2011. Gildeprint, the Netherlands, ISBN 978-94-6108-
109-4, p. 49
5. A.H.M. Andreasen, J. Andersen, Kolloid-Z 50, 217–228 (1930)
6. C.C. Furnas, Ind. Eng. Chem. 23(7), 1052–1058 (1931)
7. C.B. Henderson, R.S. Scheffee, The optimum particle-size distri-
bution of coal for coal-water slurries. Symposium on coal to liquid
products, general papers, Seattle, 1983
8. Aa. Hundere, B. Myhre, B. Sandberg, Free flowing castables—a
prerequisite for wet-gunning og refractory castables, in VII
International Metallurgical Conference, Ustron, Poland, May,
1997
9. Loughborough University Department of Chemical Engineering,
Educational Resources for Particle Technology, online book,
Chap. 2, http://www.particles.org.uk/particle_technology_book/
index.htm
10. Malvern, A Basic Guide to Particle Characterisation, http://www.
atascientific.com.au/publications/wp-content/uploads/2012/07/
MRK1806-01-basic-guide-to-particle-characterisation.pdf
11. K. Osthreeren, The Future of Crushed Sands? AT Mineral
Processing, 01-02-2011, http://www.at-online.info/download/
215793/Research_Development.pdf
12. Test Sieving: Principles and procedures (Advantech Manufactur-
ing, Inc., 2450 S Commerce Drive, New Berlin, Wisconsin, USA),
1192
http://www.advantechmfg.com/pdf/principles_procedures_manual_
with_tables-2.pdf
13. A. Seltveit, Ildfaste materialer (Tapir Forlag, 1992), pp. 234–245
14. O.J. Siljan, “Ildfaste materialer for aluminiumindustrien og annen
prosessindustri” Ildfaste materialer i aluminiumindustrien (Qual-
ity Kristiansand Hotel, Kristiansand, 1997)
B. Øye and L.P. Lossius
15. NTNU Course: TKT4215 Betongteknologi 1, UM4 Betonpro-
porsjonering, Sverre Smeplass, Skanska Norge AS, 17. Aug 2004,
pp. 3–8
16. L.P. Lossius, Hydro Aluminum, Årdal, Norway
 CPC Testing and Relationship Between Coke
and Anode Physical Properties

Marvin L. Lubin, Les Edwards, Kevin Harp, and Christopher Kuhnt

Abstract
Rain Carbon completed its 20th global CPC round robin (RR) in 2016 with five CPC
samples covering a wide range of chemical and physical properties as well as both rotary
kiln and shaft calcining technologies. Twenty-three labs participated in the RR and the
paper summarizes repeatability and reproducibility data for the different test methods.
Particular emphasis was given to bulk density testing. Pilot anodes were prepared with each
coke to examine the relationship between coke bulk density, anode density and other anode
physical properties. The study generated some interesting findings with respect to bulk
densities measured on naturally occurring coke particles. As coke particle size increases,
particle shape has a greater influence on the bulk density result. An alternative envelope
density test gives a more reliable indicator of anode density. The paper also provides an
update on a new ASTM bulk density test being developed.

Keywords
Pilot anode testing Coke bulk density Round robin

Introduction will give updated repeatability and reproducibility (r&R)

Round Robin 20 (RR20), like most other RR studies was
intended to be an inter-laboratory study to evaluate industry
standard procedures and precision levels. Rain Carbon’s
previously published RR19 study [1], highlights the large
amount of work needed to complete a study like this. RR20
was the 20th RR undertaken by Rain Carbon and included
twenty-three, well-established calcined petroleum coke
(CPC) testing laboratories from 12 countries. Five different
CPC samples were evaluated as part of the RR. This paper
M.L. Lubin (&)
L. Edwards
Rain CII Carbon, 1330 Greengate Drive, Suite 300,
Covington, LA 70433, USA
e-mail: mlubin@raincii.com
K. Harp
Rain CII Carbon, 1920 Pak Tank Rd, Sulphur,
LA 70665, USA
C. Kuhnt
RÜTGERS Germany GmbH, Kekuléstr. 30, 44579
Castrop-Rauxel, Germany
precision statements for the common industry analytical
methods.
Three recent papers [1–3] have focused on improving the
overall precision of the different CPC test methods. With the
CPC quality changes that have occurred over the last
10 years [4, 5], the industry continues to struggle with
adopting a universally accepted coke bulk density test with
good precision that correlates well to anode density and
pitch demand. Many of the methods have relatively poor
repeatability and reproducibility. This paper will illustrate
which methods are capable of giving improved precision to
enhance the comparability of results between different labs.
In previous studies [1, 2] the Geopyc1360 pycnometer
used in Trans Axial Pressure Mode (TAP) has proven to be a
measuring device suitable for use with a range of coke bulk
density methods and/or coke particle sizes. Rain Carbon has
also continued to evaluate the Envelope Density (ED) test
that can be run on the GeoPyc. This test uses a DryFlo media
(100–150 µm) to surround or “envelope” each coke particle.
This gives an average particle bulk density which is

© The Minerals, Metals & Materials Society 2017 1193

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_143
1194 M.L. Lubin et al.

independent of particle shape and packing differences. None
of the other current bulk density methods offer this capability.
In a major extension of the RR20 work, aggregate frac-
tions were prepared for the five cokes and used to produce
and test pilot anodes at Rain Carbon’s facility in Germany.
The paper will examine the relationship between coke bulk
density, anode density and other anode physical properties.
A key objective of this RR was to examine the relationship
between CPC bulk density, baked anode density and opti-
mum pitch levels.
Overview of Round Robin 20 and CPC Quality
instructions to prepare and analyze the samples in duplicate
according to each lab’s capability. A summary of key RR20
average results are shown below in Table 1.
RR20 was separated into two phases; Phase I was a tra-
ditional RR where each lab received samples of the five
“unprepared” CPC’s. The labs were asked to split the coke
samples and perform preparation and analysis for each split
in duplicate on different days. Phase II used a different
approach and focused only on coke bulk density testing.
Each lab was sent “pre-prepared” portions of samples for
bulk density testing. The goal here was to quantify the
variation introduced by the different bulk density measuring
devices by removing sample preparation biases.

The five CPC’s cover a wide range of qualities and include a

shaft CPC. Each coke originated from a 300 kg batch and all
were produced at Rain Carbon calciners. A summary of the
five cokes is given below.
• Coke A—100% straight run, low sulfur, rotary calcined
• Coke B—Blended mid-sulfur, rotary calcined
• Coke C—Blended high-sulfur, shaft calcined
• Coke D—Blended low sulfur, rotary calcined
• Coke E—100% straight run, mid-sulfur, rotary calcined.
Cokes C and D were blended as green cokes prior to
calcination and coke B was blended post-calcination in the
lab. The coke samples were split into two 150 kg lots; one
was homogenized and split into 3.5 kg sublots and shipped
to each lab. The second 150 kg lot was used to prepare pilot
anode fractions. Each participating lab was provided with
Analytical Methods and Results
All results from participating labs were compiled and ana-
lyzed using the ASTM organization’s standard statistical
methods and a common set of tools were used to identify
outliers. The outliers were removed from lab averages and
standard deviations to make them more representative of
normal analysis levels and ranges. Comprehensive reports
for the Phase I and Phase II study were prepared and dis-
tributed to all participants [6, 7]. Each lab was assigned a
randomly generated code and these codes were used
throughout the final report. Copies of the final reports are
available on request from the authors.
The most commonly performed tests in RR20 were sulfur
and trace metals and real density with 21 labs returning
results. The next most reported result was crystallite size or

Table 1 RR20 CPC average results for cokes A–E

Property A B C D E
Sulfur (%) 1.88 3.31 4.43 1.15 3.41
Nickel (ppm) 171 209 194 273 198
Sodium (ppm) 40 84 23 69 117
Silicon (ppm) 98 264 146 211 124
Calcium (ppm) 95 145 72 199 219
Phosphorous (ppm) 27 17 6 10 9
Vanadium (ppm) 186 423 403 104 498
Iron (ppm) 233 282 133 241 145
D4292 VBD (30  50) (g/cc) 0.863 0.842 0.954 0.892 0.829
D7454 VBD (20  40) (g/cc) 0.800 0.805 0.900 0.847 0.773
TBD (1–2 mm) (g/cc) 0.755 0.725 0.854 0.854 0.734
Real density (g/cc) 2.046 2.063 2.079 2.057 2.040
Crystallite size, Lc (Å) 24.9 31.2 30.0 26.8 27.0
CPC Testing and Relationship Between Coke and Anode …
Lc with 17 labs. The least performed tests were D7454 VBD
(5) and TBD 10236 (2).
Sulfur and Trace Metal Impurities
Sulfur and trace metals including sodium, silicon, calcium,
vanadium, nickel, iron, titanium, manganese, and aluminum
were analyzed by multiple methods including XRF, AA,
ICP, and high temperature combustion (for sulfur).
An example of one of the graphs from the RR20 report
[6] for nickel is shown in Fig. 1. It shows how each lab
performed on an average basis for all five cokes. The con-
sistency of the results is highlighted with only one lab
clearly outside the two standard deviation outlier limit.
Real Density
Real density (RD) is used as an indirect measure of calci-
nation level. Samples are ground to −200 mesh (75 lm) and
the average particle density is measured by displacement
using helium (He) or xylene in a pycnometer. Two labs
calculated the RD by an Lc-RD algorithm developed using
He and xylene, and calculated by Lc. Results are included in
Table 1.
Lc, Crystallite Size
The Lc method measures the average crystallite size and is
an alternative and very reliable method for determining the
calcination level.
It uses as an X-ray diffraction method as described in
ASTM 5187.
Fig. 1 RR nickel averages (ppm) by lab
1195
Bulk Density—Vibrated Bulk Density and Tapped
Bulk Density
The traditional vibrated bulk density (VBD) methods require
the use of both a vibrating feeder and table. They measure a
specific size fraction in a graduated cylinder. The size frac-
tion typically requires a standard crushing and screening
sequence covering the following coke fractions:
• ASTM D4292—30  50 US mesh (0.3–0.6 mm)
• ASTM D7454—20  40 US mesh (0.42–0.83 mm)
The tapped bulk density (TBD) is similar to the VBD test
but uses a tapping table instead of a vibrating table. This
method has a very simple preparation step which requires
only separating the coke into natural occurring fractions
(NOF’s) by screening with no crushing involved. The most
commonly used fraction for CPC specifications is the
1–2 mm coke fraction as reported in Table 1.
• ISO 10236—0.25–0.5 mm, 0.5–1 mm, 1–2 mm, 2–4 mm,
and 4–8 mm
Bulk Density—GeoPyc
The GeoPyc method uses a fully automated instrument for
measuring bulk density. A well-controlled force is applied to
a coke sample with a piston inside a horizontal glass
cylinder. The piston compresses the coke bed and measures
the displacement to accurately calculate the bulk density.
The method has been described extensively [2] and has
shown improved precision in both RR19 and RR20. A new
ASTM method based on the equipment is being evaluated
by the ASTM D02 Sub-committee. The precision data
generated in this study has been accepted for use by ASTM
using the same NOF’s as the ISO 10236 procedure.
CPC Bulk Density Comparison
The versatility of the GeoPyc equipment gives the instru-
ment the ability to measure VBD’s and TBD’s using frac-
tions prepared by any of the standard industry methods
mentioned above. Table 2 shows a detailed comparison
between traditional bulk density methods and the GeoPyc
results for each RR coke.
1196 M.L. Lubin et al.

Table 2 RR20 VBD/TBD versus GeoPyc comparison

Property A B C D E Average
D4292_VBD(30  50) 0.863 0.842 0.954 0.892 0.829 0.876
GeoPyc (30  50) 0.863 0.852 0.944 0.891 0.834 0.877
D7454_VBD(20  40) 0.800 0.805 0.900 0.847 0.773 0.825
GeoPyc (20  40) 0.815 0.800 0.918 0.867 0.784 0.837
TBD (8  4 mm) 0.658 0.701 0.728 0.726 0.650 0.693
GeoPyc (8  4 mm) 0.656 0.693 0.714 0.720 0.651 0.687
TBD (4  2 mm) 0.692 0.712 0.780 0.792 0.668 0.729
GeoPyc (4  2 mm) 0.686 0.710 0.763 0.782 0.669 0.722
TBD (2  1 mm) 0.755 0.725 0.854 0.854 0.734 0.784
GeoPyc (2  1 mm) 0.755 0.721 0.845 0.845 0.729 0.779
TBD (1  0.5 mm) 0.814 0.754 0.910 0.860 0.776 0.823
GeoPyc (1  0.5 mm) 0.824 0.763 0.920 0.880 0.776 0.833
TBD (0.5  0.25 mm) 0.871 0.807 0.971 0.885 0.833 0.873
GeoPyc (0.5  0.25 mm) 0.885 0.818 0.977 0.901 0.836 0.883

density cokes, Coke C and D, showed conflicting results

Fig. 2 Bulk density by particle size
Particle Size/Shape Impact on Bulk Density
RR20 generated some interesting findings with respect to
bulk densities measured on NOF’s. The two highest bulk
between VBD’s measured on prepared fractions vs NOF’s.
Coke C (shaft CPC) shows a substantially higher VBD than
Coke D and all other CPC’s. which is consistent with the
well-known VBD benefit of a shaft calciner [8]. Coke D
however, gave the same and/or higher bulk density on
NOF’s >1 mm. This is highlighted in Fig. 2 and the results
were similar using both the GeoPyc and the industry stan-
dard ISO TBD test.
The root cause is believed to be due to particle shape
differences between the larger coke particles. The two cokes
were sent to Fluid Imaging Technologies, Inc. which has
developed an instrument called a FlowCAM® which
performs fluid particle analysis [9], to investigate the particle
shape of both cokes. Results of these measurements can be
seen in Table 3.
The NOF of the rotary calcined Coke D has a five times
higher elongation factor than Coke C for particles >1 mm in

Table 3 RR20 coke C and D image analysis summary

Particle Size 250–500 lm 500–1000 lm 1000–2000 lm
Sample Coke C Coke D Coke C Coke D Coke C Coke D
Aspect ratio 0.69 0.74 0.66 0.70 0.65 0.68
Circularity (Hu) 0.89 0.90 0.85 0.87 0.85 0.83
Diameter (ESD) 500 465 780 818 1737 1998
Elongation 1.6 1.9 2.2 2.5 2.5 12.0
Geodesic aspect ratio 0.77 0.70 0.66 0.70 0.65 0.68
Length 556 547 931 964 2072 2429
Geodesic length 546 521 949 1023 2232 3530
Geodesic thickness 355 319 461 469 906 699
Width 365 370 591 642 1317 1558
CPC Testing and Relationship Between Coke and Anode …
Fig. 3 Coke C—1 mm image analysis
Fig. 4 Coke D—1 mm image analysis
size. Figures 3 and 4 show the 1 mm particle shape differ-
ence of coke C and D.
The above data shows that care must be taken when using
1–2, 2–4 or 4–8 mm NOF’s to compare bulk densities
between different CPC’s using either the GeoPyc or ISO
01236 method. The pilot anode densities shown later in this
paper show very clearly that Coke C has a higher bulk density
and produces significantly higher baked anode densities.
Precision Statistics for Analytical Methods
The RR20 report [6] provides precision statistics for all the
methods analyzed and Table 4 summarizes “within lab”
repeatability (r) and “between lab” reproducibility (R) for
some selected test methods. It also compares each test to the
precision stated in the ASTM/ISO test methods. All r&R
precision calculations are done according to ASTM E691.
The chemical properties in RR20 showed good overall
precision especially sulfur and vanadium. This is important
given that these elements are a main focus of customer
specifications for CPC quality. The lower atomic weight
trace element impurities (sodium, silicon, calcium, and alu-
minum) showed better precision on the single source cokes
than the blended cokes, where there was some elevated
variation. Both manganese and titanium concentrations were
Table 4 RR20 precision statements for coke chemical properties
r Sulfur (%) Nickel (ppm) Sodium (ppm)
RR20 0.11 14 12
Stated 0.12 10 26
R Sulfur (%) Nickel (ppm) Sodium (ppm)
RR20 0.24 38 39
Stated 0.24 14 36
1197
very low in the cokes in this RR, so insufficient precision
data was obtained.
Coke B showed higher variability than the other cokes in
the RR. This is believed to be due to the manual,
post-calcination blending of two different CPC’s at the Rain
Carbon Lake Charles lab. One was a low-sulfur, high RD
coke and the other was a high-sulfur, low RD coke.
The RR20 labs performed well on measuring the calcination
level using RD. The RD r&R values are remarkable given that
three different methods were used. The combined r&R results
yielded 0.006 and 0.023 g/cc respectively which is within the
ASTM D2638 standard’s r&R limits of 0.006 and 0.025 g/cc.
Precision Statistics for Coke Bulk Density
Methods
The five cokes represent a wide range of bulk densities and
the precision of these methods is important in monitoring
CPC quality. The traditional VBD methods, D4292 and
D7454, continue to show poor precision with reproducibil-
ity’s of 0.052 and 0.038 g/cc respectively. All results are
shown in Tables 5 and 6. This means there is still significant
uncertainly when comparing results from one lab to another.
The results of this study support the results of previous
studies [2, 3] where the GeoPyc equipment shows signifi-
cantly better between-lab precision than the standard VBD
equipment. The reproducibility of the D4292 procedure
decreases from 0.052 to 0.029 g/cc when the GeoPyc
instrument is used for the final measurement instead of the
traditional vibrating table.
The ASTM D7454 VBD method, which uses
semi-automated vibration equipment, is used by a relatively
small number of labs in the world. The reproducibility was
higher than the published R value. The within-lab precision
was however, acceptable.
The study was unable to determine r&R values for the
ISO 10236 TBD because only two labs provided results. On
the other hand, seven labs provided results with the GeoPyc
equipment using NOF’s which yielded a precision of
r = 0.016 and R = 0.031 g/cc. These data have been
Silicon(ppm) Calcium (ppm) Vanadium (ppm) Iron (ppm)
60 21 15 27
45 9 24 19
Silicon (ppm) Calcium (ppm) Vanadium (ppm) Iron (ppm)
83 42 37 82
66 11 32 28
1198 M.L. Lubin et al.

Table 5 Bulk density repeatability (r) statistics for each coke

Repeatability D4292 VBD D4292 GeoPyc D7454 VBD 4 mm  2 mm 2 mm  1 mm 1 mm  0.5 mm
(g/cc) (g/cc) (g/cc) GeoPyc (g/cc) GeoPyc (g/cc) GeoPyc (g/cc)
Coke A 0.021 0.007 0.02 0.027 0.005 0.015
Coke B 0.027 0.031 0.01 0.030 0.038 0.005
Coke C 0.016 0.007 0.02 0.005 0.016 0.019
Coke D 0.012 0.013 0.01 0.024 0.019 0.025
Coke E 0.017 0.012 0.01 0.028 0.008 0.007
RR20 avg. [r] 0.018 0.014 0.015 0.023 0.017 0.014
Stated ASTM [r] 0.014 0.02 0.016 0.016 0.016

Table 6 Bulk density reproducibility (R) statistics for each coke

Reproducibility D4292 VBD D4292 GeoPyc D7454 VBD 4 mm  2 mm 2 mm  1 mm 1 mm  0.5 mm
(g/cc) (g/cc) (g/cc) GeoPyc (g/cc) GeoPyc (g/cc) GeoPyc (g/cc)
Coke A 0.027 0.018 0.04 0.028 0.020 0.024
Coke B 0.079 0.033 0.03 0.034 0.048 0.026
Coke C 0.050 0.036 0.05 0.032 0.040 0.031
Coke D 0.049 0.045 0.04 0.022 0.024 0.019
Coke E 0.052 0.012 0.03 0.038 0.026 0.024
RR20 avg. [R] 0.052 0.029 0.038 0.031 0.032 0.025
Stated ASTM [R] 0.046 0.02 0.031 0.031 0.031

submitted to the ASTM inter-laboratory study program and Repeatability (R)

an official ASTM research report will be produced for future
reference by the committee.
Sources of CPC VBD Precision Problems
The RR20 Phase II report [7] focused on the variation
introduced by different bulk density measuring devices by
removing sample preparation biases. This was accomplished
by having one lab (Rain Carbon Lake Charles) prepare coke
fractions for all the different bulk density tests. Two prepared
samples were supplied to each lab according to their mea-
surement capability. The labs then split each sample in two
and measured/reported bulk density results on a total of four
samples. The aim was to run the samples in duplicate on
separate days by different lab personnel. The data from
Phase II provided a second set of r&R values for direct
comparison to the Phase I precision values.
The Phase II report compares the “within lab” repeata-
bility (r) and “between lab” reproducibility (R) for each
specific test method and compares Phase I (as-received)
versus Phase II (prepared) precision.
Table 7 compares the repeatability results between the
Phase I and Phase II studies. The 30  50 D4292 VBD
method showed a 50% reduction in r when the labs analyzed
the “prepared” fractions versus each lab preparing the test
fractions independently. The 30  50 D4292 GeoPyc
method also showed improved r values but not to the same
extent as the D4292 VBD method. The measurement of
naturally occurring fractions via the GeoPyc showed a slight
overall improvement in the r values.
Reproducibility
Table 8 compares reproducibility (R) results between the
Phase I and Phase II studies. It was anticipated that there
would be a significant improvement in R for the
30  50 D4292 VBD method with the prepared VBD
samples but this was not the case. The naturally occur-
ring fractions via GeoPyc showed a slight improvement
in R with the Phase II study without the sample
preparation variability.
CPC Testing and Relationship Between Coke and Anode … 1199

Table 7 Repeatability values for RR20 studies

Methods Phase I Phase II
30  50 D4292 VBD (g/cc) 0.018 0.009
30  50 GeoPyc (g/cc) 0.014 0.009
20  40 D7454 VBD (g/cc) 0.015 0.010
8 mm  4 mm GeoPyc (g/cc) 0.016 0.015
4 mm  2 mm GeoPyc (g/cc) 0.023 0.014
2 mm  1 mm GeoPyc (g/cc) 0.017 0.013
1 mm  0.5 mm GeoPyc (g/cc) 0.014 0.014
0.50 mm  0.25 mm GeoPyc (g/cc) 0.009 0.005

Table 8 Reproducibility values for both RR20 phases

Methods Phase I Phase II
30  50 D4292 VBD (g/cc) 0.052 0.050
30  50 GeoPyc (g/cc) 0.029 0.028
20  40 D7454 VBD (g/cc) 0.038 0.034
8 mm  4 mm GeoPyc (g/cc) 0.030 0.018
4 mm  2 mm GeoPyc (g/cc) 0.031 0.034
2 mm  1 mm GeoPyc (g/cc) 0.032 0.027
1 mm  0.5 mm GeoPyc (g/cc) 0.025 0.019
0.50 mm  0.25 mm GeoPyc (g/cc) 0.025 0.022

Fig. 5 Baked apparent density versus pitch level Fig. 6 Specific electrical resistivity versus pitch level

Pilot Anode Production and Results Pilot Anode Results

Although requiring a lot of additional work, the production
of pilot anodes provided a good opportunity to correlate
CPC properties with anode properties. A decision was made
to exclude butts/baked anode scrap from this study to better
measure the differences between the five cokes. The pilot
anodes were prepared and tested using the same aggregate
recipe and production conditions as described in an earlier
paper [8]. A standard 112 °C Mettler softening point pitch
with a QI level of *5% was used as the binder for all
anodes.
For all the RR20 cokes, 4–6 anodes with different pitch
levels were produced. Figure 5 shows the baked apparent
density (BAD) results for the five cokes.
Coke C has the highest BAD and the optimum pitch level
of *13% is lower than the other cokes. This was expected
given that it was a shaft CPC. Coke D also shows a good
BAD, especially considering the absence of any butts
material. The coke shows a flat response to changes in pitch
level however which is very unusual. Based on the specific
electrical resistivity (SER) results, Fig. 6, the optimum pitch
1200 M.L. Lubin et al.

level for Coke D is likely to be *14%. Coke E had the Table 10 R2 values for coke bulk density and anode density at
lowest BAD in this study which is consistent with the D4292 optimum pitch levels
and D7454 VBDs. The optimum pitch level is also high at Test R2, BAD R2, OPL
15%. D4292 VBD 0.96 0.97
The SER decreases with pitch level for all the cokes used. D4292 GeoPyc 0.97 0.99
The SER of coke C achieved a minimum of only *60 µXm D7454 VBD 0.93 0.99
whereas all the other cokes had their minimums closer to
8  4 mm GeoPyc 0.88 0.96
55 µXm. This could be related to the lower optimum binder
4  2 mm GeoPyc 0.59 0.64
level but this trend has been noted in several other pilot
anode studies with shaft CPC. The root cause is not known 2  1 mm GeoPyc 0.74 0.71
but SER’s are often slightly higher with shaft CPC blends at 1  0.5 mm GeoPyc 0.88 0.81
optimum pitch levels. Coke D shows the lowest resistivity’s 0.5  0.25 mm GeoPyc 0.91 0.83
in this study which highlights the favorable properties of the 8  4 mm ED 0.89 0.93
coke. The other cokes show similar behavior with SER’s 4  2 mm ED 0.86 0.87
ranging around 55–60 µXm at optimum pitch level. 2  1 mm ED 0.93 0.86
The CO2 reactivity residues of the anodes, Fig. 7, follows
expectations based on their sulfur and trace element levels.
Sodium and calcium have a negative catalytic effect on CPC and Anode Density Correlations
carboxy reactivity, whereas sulfur has a positive, passivating
effect. Coke D has the lowest CO2 reactivity residue con- CPC bulk density and porosity has a major impact on carbon
sistent with its low sulfur content. The CO2 reactivity residue anode physical properties as this study shows. Despite
of coke C on the other hand, is excellent due to its high numerous publications, the industry remains divided on
sulfur content and relatively low Na and Ca levels Table 9. which bulk density test correlates best with baked anode
density (BAD) and optimum pitch level (OPL). To examine
the correlations in this study, Table 10 shows the R2, or
Coefficient of Determination values for the different bulk
density tests and BAD’s and OPL’s.
The data show that most of the traditional VBD tests have
strong correlations to BAD and OPL. In general, however,
tests that involve crushing and screening to generate a
specific size fraction for testing have stronger correlations
than tests with NOF’s. The ASTM D4292 method in par-
ticular, showed excellent correlations in this study.
In Fig. 8, the 2  1 NOF’s for each coke were analyzed
Fig. 7 CO2 reactivity residue versus pitch level by the Envelope Density method and compared to the

Table 9 RR20 Anode results at Optimum Pitch Levels %

Property A B C D E
Optimum pitch level (%) 14.5 14.5 13.0 14 15
Green app. dens. (g/cc) 1.62 1.61 1.68 1.64 1.57
Baking loss (%) 4.9 4.8 4.5 5 5
Baking shrinkage (%) 2.8 2.3 1.6 2.2 3.2
Baked app. dens. (g/cc) 1.59 1.57 1.63 1.59 1.55
Spec. elec. resistance (µXm) 61.5 60.3 61.9 55.5 57.6
Flexural strength (MPa) 8.8 8.5 9.3 8.2 10.6
Compressive strength (MPa) 43.8 – 43.0 44.5 45.9
Elasticity mod. static (GPa) 4.2 – 3.4 4.1 4.1
Air permeability (nPm) 0.48 0.41 0.48 0.59 0.44
Coef. therm. expan. (10−6/K) 4.0 4.4 4.1 4.0 4.2
CO2−reactivity residue (%) 93.7 95.6 97.2 90.7 96.4
CO2−reactivity dust (%) 0.6 0.2 0.0 2.1 0.2
CPC Testing and Relationship Between Coke and Anode … 1201

GeoPyc as well as a vibrating table. Both these procedures

are expected to go to ballot in late 2016.
As coke particle size increases, particle shape has a
greater influence on the bulk density result. In this study,
NOF’s larger than 1 mm from a rotary kiln showed higher
elongation which resulted in a higher VBD result. The coke
particles pack more efficiently with less inter-particle void
space relative to shaft CPC with a lower level of elongation.
The traditional VBD methods are not influenced as much by
particle shape because they are crushed and the particles
become more uniform in size which negates the effect of
Fig. 8 Scatterplot of BAD versus ED (2  1 mm) particle shape.
The RR20 study showed that the correlation between
coke bulk density and BAD and OPL is very high with some
Table 11 Coke ED in descending order w/BAD of the traditional CPC bulk density methods. The study has
BAD 8  4 ED 4  2 ED 2  1 ED not settled the question of which method is the best and as
Coke C 1.63 1.43 1.45 1.38 long as labs perform the tests with good consistency, they
Coke D 1.59 1.37 1.40 1.29 should see reasonable correlations to BAD’s and OPL. What
Coke A 1.58 1.26 1.24 1.18 the study does show however, is that the traditional D4292
method using a GeoPyc for the final measurement gives the
Coke B 1.56 1.27 1.22 1.07
best overall combination of good anode correlations and
Coke E 1.54 1.22 1.17 1.06
good repeatability and reproducibility.
The BAD’s and pitch demand of the pilot anodes showed a
large spread over the five cokes as a result of the deliberately
BAD’s. The ED results in Table 11 graded the cokes in the
wide spread in coke quality, particularly the bulk densities.
same order as the D4292 VBD. This reinforces the impact of
The spread in coke VBD’s was higher in this study than what a
particle shape and packing density differences highlighted in
typical smelter might see but not dramatically so given that
Table 3. The ED test eliminates particle shape interferences
many smelters are now using a combination of rotary and
seen on NOF’s with the GeoPyc bulk density and ISO 10236
shaft CPC. The ability to correlate CPC properties to anode
TBD that indicated Coke D (rotary) > Coke C (shaft). From
properties remains an important goal and this study shows it is
this perspective, the ED test remains a promising alternative
possible to achieve this with coke bulk density testing.
to traditional BD tests.
All the anodes for this study were produced without butts
to help build better relationships between CPC properties
and anode properties. Due to space constraints, only selected
Discussion and Conclusions
anode properties were reported in the paper but most prop-
erties fell in line with expectations. The anode CO2 reac-
The RR20 Phase I and II studies showed that the
tivity’s for example, correlated well with impurities like
between-lab variation in bulk density tests remains high even
sulfur, vanadium, and sodium. The one anode property that
with the removal of sample preparation differences when
was more difficult to correlate with CPC properties was
using vibrating table measuring devices as required in the
specific electrical resistivity. Coke C showed a higher SER
ASTM D4292 method.
and a similar observation has been made with other Rain
The D4292 “30  50” GeoPyc method showed a sub-
Carbon studies with shaft CPC. Additional work is planned
stantial improvement in overall reproducibility compared to
in this area to try and better understand the cause of this
the standard D4292 VBD measurement equipment. This
behavior.
paper shows that the final measuring techniques are the
primary cause of variability in the bulk density test methods
rather than sample preparation. This finding was unexpected.
The NOF’s measured using the GeoPyc showed the
References
lowest between-lab variation of all the bulk density methods.
As a result, the ASTM committee is considering a new bulk 1. M. Lubin, L. Edwards, L.P. Lossius, Calcined coke round robin 19
and the precision of bulk density tests. Light Met. 1063–1068
density method based on the use of this equipment and (2013)
NOF’s. The committee is also considering a modification of 2. M. Lubin, L. Edwards, J. Marino, Improving the repeatability of
the existing D4292 to allow final measurement by the coke bulk density testing. Light Met. 947–952 (2011)
1202
3. M. Lubin, L. Edwards, L.P. Lossius, Relationship between coke
properties and anode properties—RR19. Light Met. 1183–1188
(2013)
4. L. Edwards, The history and future challenges of calcined petroleum
coke production and use in aluminum smelting. JOM 67(2), 308–
321 (2014)
5. L. Edwards, N. Baghouse, H. Darmstadt, M. Dion, evolution of
anode grade coke quality. Light Met. 1207–1212 (2012)
6. M. Lubin, Round Robin 20 Phase I Report, Report distributed to
RR20 participants on 15th Apr 2016
M.L. Lubin et al.
7. M. Lubin, Round Robin 20 Phase II Report, Report distributed to
RR20 participants on 26th Aug 2016
8. W. Boenigk, C. Boltersdorf, C. Kuhnt, J. Stiegert, L. Edwards, M.
Lubin, pilot anode testing of alternative binder and CPC raw
materials. Light Met. 1033–1037 (2015)
9. R. Bowers, S. Ningileri, D.C. Palmlund, B. Vitchus, F. Cannova,
New analytical methods to determine calcined coke porosity, shape,
and size. Light Met. 875–880 (2008)
 Effect of Coke Properties on the Bubble
Formation at the Anodes During Aluminium
Electrolysis in Laboratory Scale

Wojciech Gebarowski, Arne Petter Ratvik, Stein Rørvik,

Lorentz Petter Lossius, Hogne Linga, and Ann Mari Svensson

Abstract
The anodic reaction of aluminium electrolysis cells leads to the formation of CO2 bubbles,
which partly screen the anode surface and leads to an increase in the cell voltage. An
advantage of these bubbles is that the formation and release contribute to the stirring of the
electrolyte, however, the screening of the surface increases the irreversible energy losses.
The voltage and current oscillation due to the bubble evolution during electrolysis for
different anode materials have been determined in a laboratory cell. The effect of coke
sulphur content and grain sizes were investigated. Anodes with finer coke fraction showed
lower oscillations than coarser fraction equivalents. Additionally, the influence of current
density on the amplitude of the anode potentials was measured. A 64% increase of current
density caused an increase of anode potential oscillations from 79 to 170%.

Keywords
Carbon anodes Aluminium electrolysis Gas bubbles

Introduction conversion to, mainly, CO2. Assuming a current density

0.8 A cm−2, 0.02 M of CO2 per 1 m2 of anode every second
The majority of primary aluminium production is based on is produced, which at 960 °C corresponds to a volume of
electrochemical reduction of alumina using prebaked carbon about 2.13 dm3. Due to the horizontal placement of anodes
anodes. During electrolysis, carbon anodes are consumed by in the cells, with the active part of the electrode facing
downwards, such large amount of gas produced on the
W. Gebarowski (&)
A.M. Svensson surface has a significant impact on the process. According to
Department of Materials Science and Engineering, Norwegian Haupin and Kvande [1], the presence of gas bubbles in an
University of Science and Technology, 7491 Trondheim, Norway industrial cell increases the cell voltage by 0.25 V which is
e-mail: wojciech.gebarowski@ntnu.no
about 6% contribution to the total cell voltage. In the liter-
A.M. Svensson ature it is very common to denote this component of the cell
e-mail: annmari.svensson@ntnu.no
voltage as bubbles overpotential, which is slightly confus-
A.P. Ratvik
S. Rørvik ing, because, in fact, bubbles increase cell voltage by two
SINTEF Materials and Chemistry, 7465 Trondheim, Norway
main mechanisms: increase of ohmic resistance of the
e-mail: arne.p.ratvik@sintef.no
electrolyte and increase of activation polarization [2]. An
S. Rørvik
increase of ohmic resistance of electrolyte may be described
e-mail: stein.rorvik@sintef.no
by Bruggemann’s equation for dispersed bubble phase
L.P. Lossius
H. Linga
fraction in an electrolyte [3, 4]. The presence of bubbles on
Primary Metal Technology (PMT), Hydro Aluminium AS,
P.O. Box 303NO-6882 Øvre Årdal, Norway an anode effectively decreases active surface area, which in
e-mail: Lorentz.Petter.Lossius@hydro.com turn increases real current density and causes an increase of
H. Linga the activation polarization. Bubbles also have a beneficial
e-mail: Hogne.Linga@hydro.com

© The Minerals, Metals & Materials Society 2017 1203

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_144
1204 W. Gebarowski et al.

influence on electrolysis, providing agitation of an elec-

trolyte which reduces the concentration polarization.
Considering the high electrical current in an industrial
cell, the presence of bubbles contributes to significant losses
of energy which is the reason for the considerable interest in
bubble behaviour in reduction cells. The biggest step in this
matter was the introduction of slots in anodes in 1998, which
substantially reduced voltage drop and voltage/current
oscillations by changing the bubbles flow pattern [5].
However, still more profound understanding of bubbles
formation and release mechanisms in order to make further
improvements of process efficiency is needed.
The bubbles lifetime can be divided into two stages:
nucleation and transport. Nucleation takes place on active
sites which are defects and pores on the anode surface [6, 7].
Therefore, the quantity of nucleation sites depends on the
anode structure. Subsequently, when the bubble reaches a
certain size, buoyancy forces detach bubble from the active
site and the travel towards the edge of electrode commences.
The size of bubble when detaching occurs is influenced by the
wetting angle between the electrolyte and the anode. Better
wetting between anode and electrolyte promotes detachment
of smaller bubbles [8, 9]. The transport stage is controlled by
Fig. 1 Experimental setup of the electrochemical cell with electrical
anode shape, inclination, surface roughness, electrolyte flow connections. V1—cell voltage; V2—working electrode (sensing point)
and wetting properties. An additional phenomenon that versus counter electrode (crucible); V3—working electrode (sense
occurs in both stages is the coalescence of bubbles. Bubbles point) versus reference electrode (thermocouple and auxiliary electrode
are not shown for clarity of drawing)
may also coalesce at nucleation sites when two adjacent
bubbles overlap during growth. Coalescence can also happen
during bubbles movement when two bubbles collide. Materials and Methods
Previous studies of bubbles in aluminium electrolysis
process can be separated into three groups: (i) measurements The experiments were conducted in a cell as depicted in
in industrial environment (ii) measurements in lab scale and Fig. 1. The cell was made of a graphite crucible (G330,
(iii) theoretical physical models. The first group has provided Tokai Carbon) and placed in a closed cylindrical metal
very direct and practical results, but has some limitation in reactor, which in turn was placed in a resistance heated
the control of parameters in the complex processes taking furnace with controlled temperature. During experiments, an
place, which is more convenient in the case of laboratory inert atmosphere inside reactor was maintained by passing
experiments. In most of the laboratory studies, graphite is argon at flow of 200 ml min−1.
used as an anode material in the investigations and only a few An alumina saturated cryolite based electrolyte was used
papers focus on the influence of carbon materials on bubbles with following composition: 76.15 wt% of Na3AlF6
evolution during electrolysis. A significant discrepancy in (  97%, Sigma-Aldrich), 11 wt% of AlF3 (in-house sub-
bubbles behaviour between graphite and carbon anodes has limed from industrial grade), 4.5 wt% of CaF2 (  99.8%,
been found in a study using various anodes of different, Merck), 8.35 wt% of Al2O3 (  99.5%, Merck) with bath
single source cokes [10]. The study was, however, limited to molar ratio acidity, MR = 2.2. During the experiment, the
coke material of with small particle fractions, 0–2 mm, which alumina parts in the melt dissolve and prevent depletion
is significantly lower than industrial practice. from the saturated state. The temperature of electrolyte was
The aim of this work is to investigate the correlation maintained at 960 °C providing a superheat of about 26 °C.
between carbon anodes properties and the formation of The cylindrical crucible acted as a cathode with sidewall
bubbles in a laboratory cell, including the development of shielded by a sintered alumina tube, leaving only the bottom
bubble oscillation patterns over time, and at various oper- as working part. Cylindrical anodes were made according to
ating current densities. Sample anode materials were differ- Fig. 2. Electrodes were shielded by sintered alumina to
ent in terms of impurities level, mainly sulphur, as well as ensure that the exposed surface area of the electrode was
size of coke grains used, 0–2 and 0–6 mm. dominantly horizontal. A stainless steel tube connected to
Effect of Coke Properties on the Bubble Formation …
Fig. 2 Electrode assembly used for bubbles oscillations measurements
the carbon anode by a threaded end was used as current lead.
A sensing wire was placed inside the current lead, insulated
from the main lead by an alumina tube. The sensing wire
was connected close to the working electrode to avoid sig-
nificant voltage drop across the current lead.
The anodes were made of three different single source
calcined petroleum cokes which varied in impurity content
and isotropy. Each coke was used to manufacture two anode
materials with coke grains fractions up to 2 and 6 mm,
respectively. A pitch level optimization pre-study was run
for each coke. This was done to ensure the test anodes had
comparable pitch level adjusted to the coke porosity and
Table 1 Properties of cokes and Coke 1
anodes used for measurements
Impurities
S (wt%) 1.42
V (ppm) 116
Ni (ppm) 192
Fe (ppm) 178
Anode properties
Coke fraction <2 mm
Density (g cm−2) 1.56
Permeability (nPm) 3.53
1205
bulk density. The properties of cokes and prepared anodes
are summarized in Table 1.
Working electrode potentials were measured against an
aluminium reference electrode made by placing pure alu-
minium in a sintered alumina tube with a small hole to
provide ionic contact to the electrolyte. A tungsten wire was
used as electrical contact to the aluminium pool.
A laboratory power supply (Agilent 6032 A) controlled
by LabVIEW software was used as power source. Sense
inputs of the power supply were connected to the same
points as V1 (see Fig. 1). Three voltages and current (using a
50 mX shunt resistor) were logged simultaneously using an
ADC module (National Instruments, NI 9225) with speed
100 Sa/s. Input impedance of the module is high enough to
avoid load to the reference electrode.
Results and Discussion
The procedure for each anode sample consisted of electrol-
ysis at constant current (CC) density 1 A cm−2 as well as at
constant voltage (CV) by maintaining an average current
density of 1 A cm−2. This allowed observing potential and
current oscillations due to bubbles release during the CC and
CV period, respectively. Voltage in the CV mode was
determined based on the average value of the last 15 s of
voltage oscillations from the preceding CC mode. Figure 3
shows voltages recorded at three different points corre-
sponding to V1, V2 and V3 in Fig. 1 during CV mode.
Discrepancies in regulation of different points are clearly
visible.
Considering the relatively high currents and rapid chan-
ges of load due to bubbles oscillations, even moderately low
inductances of anode and cathode leads caused voltage
oscillations—the greater the further from the sense points of
the power supply (sense inputs of the power supply were
connected across the cell voltage—V1—therefore this volt-
age is the best regulated in CV mode).
Coke 2 Coke 3
5.54 3.56
432 402
192 210
316 264
<6 mm <2 mm <6 mm <2 mm <6 mm
1.65 1.63 1.62 1.64 1.63
0.44 0.57 1.39 0.30 0.44
1206 W. Gebarowski et al.

Figure 4 shows cell voltage oscillations in the CC mode

3.9
Cell Voltage Sense w.r.t. CE Sense w.r.t. Al with switching to the CV mode, where, in contrast, oscil-
3.8 lations of current are visible. The shapes of voltage and
3.7 current oscillations are qualitatively similar, except for the
fact that they are inverted with respect to each other. The
Voltage / V

3.3 oscillations obviously reflect changes in active surface area

3.2 of the anode due to growth of gas bubbles and their release
after reaching a certain bubble size. The growth of bubbles
3.1
decreases the active surface area causing an increase of real
current density in the CC mode, which causes an increase of
2.6
the anode potential until a bubble is released, when a rapid
2.5 drop of voltage is observed.
2.4
Correspondingly, in CV mode, a decrease of active sur-
face area causes a decline of current because the voltage is
105 110
fixed, and the release of bubbles produce a rapid increase of
Time / s
current. The two graphs in Fig. 4 represent early and late
Fig. 3 Voltage measured at different points during constant voltage stage of electrolysis. During the early stage (first minutes),
electrolysis the oscillations are very regular with saw tooth shaped

Fig. 4 Switch from oscillations 4.50 1.5

of cell voltage at constant current coke-2 >6mm early
(CC) mode to oscillations of 4.25 1.4
current at constant voltage
(CV) mode electrolysis. The top

Current density / A·cm-2

graph is recorded between 60 and 4.00 1.3
Cell Voltage / V

100 s, and the bottom graph

between 960 and 1000 s 3.75 1.2

3.50 1.1

3.25 1.0

3.00 0.9

2.75 0.8
70 80 90

4.50 1.5
late
4.25 1.4
Current density / A·cm-2
4.00 1.3
Cell Voltage / V

3.75 1.2

3.50 1.1

3.25 1.0

3.00 0.9

2.75 0.8
970 980 990
Time / s
Effect of Coke Properties on the Bubble Formation …
waveform. The amplitudes are *0.75 V and *0.3 A cm−2
in CC and CV mode respectively. In the later stage of
electrolysis, the oscillations are much less regular and have
smaller amplitudes—*0.5 V and *0.2 A cm−2, respec-
tively. The changes in the oscillations illustrate the change of
the bubbles release pattern with time. At the beginning, a
machined anode has smooth surface and a sharp edge.
Smooth surface facilitates the growth of larger bubbles.
Additionally, a sharp edge is a barrier which prevents bub-
bles escape from the horizontal part of the anode. Therefore,
bubbles can grow larger and cause more screening of the
anode surface before they are released. Flow patterns seem
to be well ordered.
With electrolysis time, the surface of an anode becomes
rougher due to preferential oxidation of the binder phase in
the carbon matrix. What is more, because of higher local
current density on the edges of the anode, the consumption
in this area is higher, causing rounding of the electrode
edges. These two effects are depicted in Fig. 5 where the
surface of an anode after experiment is shown. Therefore, a
rougher surface enables more paths for bubbles movements
Fig. 5 Computed tomography of a carbon sample after experiment.
a whole electrode; b zoomed edge. Dotted line presents the outline of
the electrode before polarization
1207
across the anode surface and rounded edges improve the
ease of releasing smaller bubbles. Hence, the flow pattern is
more random which is clearly visible in the shape of the
oscillations.
Figure 6 shows the oscillations of cell voltage and current
density during an early period of electrolysis for the same
anode material, but different coke fractions. In the case of
<2 mm coke fraction, smaller amplitude of voltage and
current oscillations in respect to <6 mm fraction is observed.
It means that in the latter case, bigger bubbles are released.
Smaller bubbles in the case of smaller coke fraction result
from the presence of a larger number of active sites where
bubbles can nucleate.
The graph in Fig. 7 contains a comparison of anode
potential oscillations in CC mode for all three materials, each
in two variations of the coke grain sizes. Instead of the
amplitude of oscillation, a standard deviation of mean value
of the potential is shown. This provides a more representa-
tive statistical description of the oscillations, avoiding effects
of single events (single big spikes). For all samples, a
decrease of oscillations with time was observed during
electrolysis, which may be attributed to changes of electrode
shape and roughness. The highest oscillations for <2 mm
fraction was measured for coke 1 in both the early and late
stages of electrolysis. Coke 1 has the lowest content of
sulphur. In case of the <6 mm fraction, coke 2 shows the
highest oscillation amplitudes in the early and late stages.
Coke 2 has the highest content of sulphur. This extreme
divergence can be explained when looking at permeability
values for the anodes—both materials (coke 1 < 2 mm and
coke 2 < 6 mm) have the highest permeability. By com-
paring only anodes with low permeability (coke 1, <6 mm,
coke 2, <2 mm and coke 3, both fractions), we observe that
the voltage oscillations are quite similar, and the lowest for
coke 2, with the highest sulphur content. This is in line with
previous results, where the most impure cokes showed the
lowest voltage oscillations for anodes of <2 mm fraction
[10]. Also in this work, there were challenges with differ-
ences in permeability. Based on the results, it is reasonable
to assume that permeability affects the bubble overvoltage
by the presence of surface pores, in which CO2 bubbles are
known to reside and possibly escape.
Oscillations of current recorded in CV mode allowed
direct calculation of a maximum fraction of an anode surface
blocked by bubbles using the following formula:
jmin
bubbles coverage ¼ 1 
jmax
Results presented in Fig. 8 are similar to the results in
Fig. 7, (except for the highly permeable anodes), for which
there is correlation between potential and current
oscillations.
1208 W. Gebarowski et al.

Fig. 6 Comparison of voltage 4.50 1.5

and current oscillations in early coke-1, early stage < 2 mm
period for coke 1 with fraction 4.25 1.4
<2 mm (top figure) <6 mm
(bottom figure)

Current density / A·cm-2

4.00 1.3

Cell Voltage / V
3.75 1.2

3.50 1.1

3.25 1.0

3.00 0.9

2.75 0.8
65 70 75 80 85 90 95

4.50 1.5
< 6 mm
4.25 1.4

Current density / A·cm-2

4.00 1.3
Cell Voltage / V

3.75 1.2

3.50 1.1

3.25 1.0

3.00 0.9

2.75 0.8
65 70 75 80 85 90 95
Time / s

early stage 0.30 early stage

0.20
late stage late stage
<2mm <2mm
0.25
<6mm <6mm
Surface coverage

0.15
0.20
σ/V

0.10 0.15

0.10
0.05
0.05

0.00 0.00
COKE-1 COKE-2 COKE-3 COKE-1 COKE-2 COKE-3

Fig. 7 Standard deviation of potentials during oscillations in CC mode Fig. 8 Bubbles coverage of surface in CV mode at javerage = 1 A cm−2
at j = 1 A cm−2 for different cokes in saturated electrolyte, fractions for different cokes in saturated electrolyte, fractions and stage of
and stage of electrolysis calculated from 1 min periods in 2–3rd and electrolysis calculated from 1 min periods in 2–3rd and 15–16th min of
15–16th min of electrolysis for early and late stage, respectively electrolysis for early and late stage, respectively

In Fig. 9, anode potential oscillations for increasing cur- density, the average anode potential increases as well as the
rent densities are presented. The potentials were measured in oscillation frequency and amplitudes. Assuming a linear
the late stage of electrolysis. With the increase of current relation between current density and potential of an anode
Effect of Coke Properties on the Bubble Formation … 1209

3.2 2.5

Anode potential
3.0 Current density
2.0

Current density / A·cm-2

2.8
Sense w.r.t. Al / V

2.6
1.5

2.4 1.15 A·cm-2

-2
1 A·cm
1.0
2.2 0.85 A·cm-2
0.7 A·cm-2
2.0
1050 1100 1150 1200 1250
Time / s

Fig. 9 Anode potential oscillations at different current densities in late period of electrolysis

(activation overpotential) in the range of 0.7  1.15 A cm−2, for the coke 2 < 6 mm—the highest content of sulphur.
which is a reasonably assumption [11], a linear increase of Interestingly, this sample shows the highest amplitude of all
the average value of the potential, as well as the amplitude of samples for all current densities. However, as suggested
the oscillations with increasing current density, is expected. above, it may be related to the high permeability of this
Figure 10 shows the amplitudes of anode potential oscilla- material.
tions against current density for all anode materials. In all Figures 11 and 12 show FFT (Fast Fourier Transform)
cases, an increase in potential oscillation with increased analysis of potential oscillations during period between 8th
current density is observed. The trend of these relations is and 16th min of electrolysis for <2 and <6 mm samples,
relatively linear. Anodes with fraction <6 mm have higher respectively. The oscillations consist of components from a
oscillation amplitudes with respect to the <2 mm equivalents. quite wide range of frequencies with a predomination of
The increase of potential oscillation amplitude between cur- lower frequencies. The maximums on the spectra are around
rent density 0.7 and 1.15 A cm−2 is in the range 79–170% 0.3–0.6 Hz which corresponds to the main frequency of the
which is a significant value considering the increase in cur- oscillations. Lower frequencies are attributed to bigger
rent of 64%. bubbles releasing, whereas higher frequencies are produced
The highest increase is observed for coke 1 < 6 mm—the by bubbles coalescences on the electrode surface as well as
lowest content of sulphur. The lowest increase is observed the escaping of smaller bubbles from the electrode surface.
There are slight differences in FFT spectra. Comparing
<2 mm fraction samples, for coke 3 main frequencies are
Coke-1 <2mm
shifted towards higher frequencies. Both coke 1 and coke 3
Coke-2 <2mm show distinguishable peaks whereas coke 2 has more even
0.8 Coke-3 <2mm distribution of frequencies. In case of <6 mm fractions, coke
Potential oscillations amplitude / V

Coke-1 <6mm
Coke-2 <6mm 3 shows the sharpest peak for the main frequency, while
Coke-3 <6mm coke 1 and coke 2 have more low frequency components.
0.6
Thus, the <6 mm fraction tend to produce larger bubbles.

Conclusions
0.4
In this work voltage and current oscillations caused by
bubbles during electrolysis of different coke materials were
studied.
0.2 Voltage and current oscillations due to bubbles showed
0.7 0.85 1 1.15
regular saw tooth waveform at the beginning of electrolysis
Current density / A·cm-2
Fig. 10 Potential oscillations amplitude at different current densities
and became less regular and with lower amplitude with
for different samples
1210 W. Gebarowski et al.

Fig. 11 FFT from the period

between 8th and 16th min of
potential oscillations for <2 mm
fraction anodes

Fig. 12 FFT from the period

between 8th and 16th min of
potential oscillations for <6 mm
fraction anodes
Effect of Coke Properties on the Bubble Formation …
electrolysis time. These phenomena are attributed to the
changes of shape and roughness of the electrode surface.
Anodes with coarser fractions produced higher oscillation
amplitudes due to growth of larger bubbles (coarser surface).
Finer coke fraction promotes the growth of higher number of
smaller bubbles due to more active sites where nucleation of
bubbles occurs.
An increase in current density from 0.7 to 1.15 A cm−2
caused a substantial increase in amplitude (from 79 up to
170%) and frequency and also increase of the anode
potential oscillations.
Correlation between coke sulphur content and bubbles
behaviour is not clear as the observed differences might be
influenced by different permeabilities of the investigated
anodes. Therefore, more profound studies focused on per-
meability influence on bubbles oscillations are required.
Acknowledgements This work was financed by Hydro Aluminium
and the Research Council of Norway. Thanks are due to the NTNU
workshop, especially to Aksel Alstad for manufacturing of experi-
mental parts. Additionally, the contributions of Egil Skybakmoen and
others at SINTEF are gratefully acknowledged.
References
1. W. Haupin, H. Kvande, Thermodynamics of electrochemical
reduction of alumina, in Light Metals (2000), pp. 379–384
1211
2. M.A. Cooksey, M.P. Taylor, J.J.J. Chen, Resistance due to gas
bubbles in aluminum reduction cells. JOM, 60, 51–57 (2008).
doi:10.1007/s11837-008-0019-x
3. F. Hine, K. Murakami, Bubble effects on the solution IR drop in a
vertical electrolyzer underfree and forced convection. J. Elec-
trochem. Soc. 127, 292–297 (1980). doi:10.1149/1.2129658
4. K. Qian, J.J.J. Chen, Visual observation of bubbles at horizontal
electrodes and resistance measurements on vertical electrodes.
J. Appl. Electrochem. 27, 434–440 (1997). doi:10.1023/a:
1018465705058
5. G. Bearne, D. Gadd, S. Lix, et al., The impact of slots on reduction
cell individual anode current variation, in Light Metals (2007),
pp. 305–310
6. K.E. Einarsrud, S.T. Johansen, I. Eick, Anodic bubble behavior in
Hall-Héroult cells. Light Met. 2012, 875–880 (2012). doi:10.1002/
9781118359259.ch151
7. H. Vogt, Contribution to the interpretation of the anode effect.
Electrochim. Acta 42, 2695–2705 (1997). doi:10.1016/S0013-
4686(97)00013-3
8. R.D. Peterson, N.E. Richards, A.T. Tabereaux et al., Results of
100 hour electrolysis test of a cermet anode: operational results and
industry perspective, in Light Metals (1990), pp. 385–393
9. K. Zhang, Y. Feng, P. Schwarz et al., Computational fluid
dynamics (CFD) modeling of bubble dynamics in the aluminum
smelting process. Ind. Eng. Chem. Res. 52, 11378–11390 (2013).
doi:10.1021/ie303464a
10. R.J. Thorne, C. Sommerseth, A.P. Ratvik et al., Bubble evolution
and anode surface properties in aluminium electrolysis. J Elec-
trochem. Soc. 162, E104–E114 (2015). doi:10.1149/2.0321508jes
11. S. Zuca, C. Herdlicka, M. Terzi, On porosity-overvoltage corre-
lation for carbon anodes in cryolite-alumina melts. Electrochim.
Acta 25, 211–216 (1980). doi:10.1016/0013-4686(80)80045-4
 Anode Quality Improvement at Inalum Smelter

S.S. Sijabat, Firman Ashad, Ade Buandra, and Edi Mugiono

Abstract
INALUM has been using high Sulphur and low Sulphur coke with 60:40 ratios since 2004.
Furthermore, some efforts have been done to increase anode quality, such as Blaine
Number Stabilization, Butt Cleaning Improvement, and Cone Crusher Utilization. By
controlling the fine fractions output in green paste mixing, the Blaine number variance was
reduced by 5%. In the other hand, the butt quality also become a serious factor to anode
quality, and to overcome this problem, better butt cleaning process was used to reduce the
impurities. The impurity was reduced and stabilized in the level below 150 ppm from the
specification of 300 ppm. In green paste mixing, coarser material also affected the green
paste product. Coarse material composition should reach at least 5%, nevertheless the
existing hammer mill cannot provide. Hence, INALUM has installed the Cone Crusher
equipment to increase the coarse material up to 10%. Finally, by performing those
improvements have increased the RRO2 by 2.5% and RRCO2 by 0.74%.

Keywords
INALUM Anode quality Blaine number Butt cleaning Cone crusher

Introduction
INALUM transformed to be State Owned Company in
December 19, 2013 after it was founded on January 6, 1976
as Joint Venture Company between the Government of
Indonesia with 12 Japanese Investors incorporated in Nip-
pon Asahan Aluminium Co.Ltd.
Since 1976 INALUM has committed to perform contin-
uous improvement as stated on the company master plan [1].
INALUM consists of four main plants which are Hydro
Electrical Power Plant, Carbon Plant, Reduction Plant, and
Casting Plant. In the previous report, INALUM has made
some improvement regarding the Reduction Plant and
Casting Plant which resulted in good benefit to company
[2, 3]. In line with the previous report, the improvements
shall be continued to reach the vision of the INALUM
to be a global leading company based on integrated
environment-friendly aluminum smelter.
INALUM has planned to increase the production capacity
up to 300 t/year in 2020 [1], and to achieve that plan, some
improvement need to be conducted. In this paper, some
improvements related to Carbon Plant were discussed
including Blaine Number Stabilization, Butt Cleaning
Improvement, and Cone Crusher Utilization. These
Improvements have been applied in INALUM and the result
was used as recommendation to the next improvement.
Improvements

In line with INALUM target to increase production up to

S.S. Sijabat
F. Ashad
A. Buandra (&)
E. Mugiono
PT Indonesia Asahan Aluminium (Persero), P.O. Box 1Kuala
Tanjung, Sumatera Utara 21257, Indonesia
e-mail: ade_buandra@inalum.co.id
300 kt ingot in 2020, Carbon plant should increase anode
quality to meet with pot room requirement. To improve
anode quality some efforts are already done such as.

© The Minerals, Metals & Materials Society 2017 1213

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_145
1214 S.S. Sijabat et al.

Fig. 1 Diagram of a previous design and b Design after improvement [4]

Anode Quality Improvement at Inalum Smelter
Blaine Number Stabilization
In Green Block (GB) anode mixing formula, surface of fine
fraction should be wetted by pitch binder in appropriate with
binder ratio. In the dry aggregate more than 90% of this
surface area occurs in the fine fraction. The broad variance
of surface area will influence the wetted condition which
leads to unstable anode quality.
Stabilization fineness (Blaine number) of fine fraction has
been done by separating fine fraction from ball mill product
with fine fraction from filter dust at different bin. In order to
get the stable combined fine fraction, both of the output fine
fraction were controlled properly.
As shown in Fig. 1, fine fraction from ball mill product
was stored at B-204 and filter dust at B-203 (It has been
modified similar with B-204). The other fractions of coke
were stored at B-201 and B-202.
Result of this improvement as below (Fig. 2 and Table 1):
Fig. 2 Variance of Blaine number fine fraction [5]
1215
After implementation of the new formula some results
were achieved, which follows:
1. Variance of Blaine number fine fraction after stabiliza-
tion program was reduced 32% (Stabilized: 249 BN,
Existing: 364 BN).
2. Variance of anode density after stabilization program was
reduced 5% (Stabilized: 0.00883 g/cc, Existing:
0.00840 g/cc).
Better Butt Cleaning
To produce good anode quality, enhancing of the material
quality such Coke, Coal Tar Pitch (CTP) and Butt will be
required. Appropriate recycling of good anode butts is a
must for producing high quality anodes with better density,
low permeability, high mechanical strength and low resis-
1216 S.S. Sijabat et al.

Table 1 Variance of green Month Standard deviation Remark

anode density
Variance Average Decreasing
1st 0.00910 0.00883 – Before
2nd 0.00958
3rd 0.00852
4th 0.00813
5th 0.00892 0.00840 5% After
6th 0.00804
7th 0.00802
8th 0.00860

Fig. 3 Manual cleaning

tivity. To control butt quality some measurements have been
done such as Butt Hardness and Laboratory check of butt
impurities by sampling and visual check. In result, the cor-
relation between sodium content in butt determined the
quality of butt, which was produced by good cleaning pro-
cess of crust material (Fig. 3). Based on above condition,
decreasing the butt impurities by improving butt cleaning
quality (cleaning manually with tools) was done to reduce
the Sodium content.
Result of improvement as below:
Improvement of butt cleaning: Na content decrease much
<150 ppm (target <300 ppm) (see Fig. 4).
Utilization of Cone Crusher
The most critical component of the anode is the binder
matrix due to it produces carbon foam after placed in
reduction cell that will increase the resistivity of bath. Binder
matrix is a mixture of dust and pitch, where dust came from
fine coke and butt. In order to improve binder matrix quality,
quantity of fine butt should be minimized, because sodium
content of fine coke is better than butt.
Based on typical characteristic of crusher, cone crusher
has a better result to produce much coarser material compare
to impact crusher. Figure 5 shows the characteristic result of
Anode Quality Improvement at Inalum Smelter
Fig. 4 Impurities content in butt coarse
Fig. 5 Cone crusher and impact crusher [4]
output material from both crushers, with resulted the butt
size over 5 mm by 2–10% (target 5%) (see Fig. 6).
In order make sure the influence of coarse butt to the
anode quality especially RRCO2 and RRO2. Small scale test
has been done, where R consist of 45% butt with size over
than 5 mm and T1, T2, T3 were 60, 70, 80% respectively.
The result of this small scale test is shown in Table 2.
1217
Improvements Result
After implementation of all improvements, the better quality
of anode was achieved as shown in Fig. 7. The value of
RRO2 was increased by 2.5% along with RRCO2 by 0.74%.
The increasing of these parameters will lead to the much
better anode after placed in the reduction cell.
1218 S.S. Sijabat et al.

Fig. 6 Result of butt

granulometric

Table 2 Small scale test No. Item Sample (Pcs) Unit Sample
R T1 T2 T3
3
1 Anode baked density 10 g/cm 1555 1635 1617 1569
2 Air permeability 5 nPm 1.50 1.47 1.43 1.30
3 Flexural strength 5 kg/cm2 100.2 106.9 111.3 113.7
4 RRCO2 5 % 96.26 96.33 96.60 96.62
5 RRO2 5 % 92.26 93.38 94.10 95.09
Anode Quality Improvement at Inalum Smelter
Fig. 7 RRCO2 and RRO2 anode
performance
Conclusion
1. Higher Sodium content in but was resulted due to low
quality of butt cleaning process, hence additional clean-
ing process was conducted by correlated tool and result
in decreasing of Sodium content in butt to produce better
anode quality.
2. Anode quality especially RRO2 has strong correlation
with coarser butt, and the optimum value resulting from
small scale test was 80% butt should have over 5 mm
particle size.
3. By implementing Blaine Number Stabilization, Better
Butt Cleaning Process, and Installation of Cone Crusher,
INALUM smelter succeed to increase RRO2 by 2.5%
and RRCO2 by 0.74%.
1219
References
1. Inalum, Company Long-term Plans of INALUM (Rencana Jangka
Panjang Perusahaan, Kuala Tanjung, Indonesia, 2016)
2. D. Sinaga, S. Bice, H. Yunaz, M. Kondo, Technical improvement in
INALUM, in Light Metals (2007), pp. 237–241
3. S.S. Sijabat, I. Ermisyam, M.S. Sunardi, Enhancing production
performance by optimization all resources at PT INALUM
(Persero), in Light Metals (2016), pp. 559–562
4. R&D Carbon, Anode Production and Performance in Pots (Lecture
by R&D Carbon for Inalum, Kuala Tanjung, 2007)
5. Inalum, Stabilization of Fine Fraction Blaine Number at Green
Plant (Inalum Technical Report, Kuala Tanjung, Indonesia, 2011)
 Coke Produced from Lower-Oxygen
Fast-Pyrolysis Oil, A New Approach to Produce
Renewable Anode Raw Materials

Yaseen Elkasabi, Hans Darmstadt, and Akwasi A. Boateng

Abstract
Carbon anodes are presently produced from petroleum-derived coke and coal tar pitch.
Upon consumption of these anodes, some 1.5 t CO2/t Al are generated. This considerable
footprint could be reduced by using biomass-derived coke. It was suggested to manufacture
coke from biomass char. However, the corresponding cokes typically contain undesired
oxidation catalysts (alkali and alkaline earth metals), are high in oxygen (reducing carbon
available for electrolysis), have undesired isotropic textures, and also have low bulk
densities. In order to avoid these shortcomings, a new approach was studied: coking of
biomass-derived oils from a fast pyrolysis process yielding lower-oxygen oil. The
corresponding cokes are very low in undesired impurities (sulphur, vanadium, and nickel).
Levels of oxygen, alkali and alkaline earth metals are acceptable. Using appropriate
conditions, cokes with desired anisotropic textures can be produced.

Keywords
Coke Biomass Texture Pyrolysis Optical microscopy

Introduction growth. Biomass can be transformed by pyrolysis

Biomass Char as Anode Filler
Carbon anodes for the Hall-Héroult process are made from
non-renewable raw materials (petroleum coke and coal tar
pitch). Upon consumption, about 1.5 t CO2/t Al are gener-
ated. For smelters using hydro-generated electricity, this
represents some 37.5% of the total CO2 footprint of alu-
minium production [1]. One option to reduce the CO2
footprint is using renewable, biomass-derived anode raw
materials. In this case, the CO2 generated during electrolysis
would be compensated by the CO2 captured during biomass
Y. Elkasabi
A.A. Boateng
Eastern Regional Research Center, Agricultural Research Service,
U.S. Department of Agriculture, 600 E. Mermaid Lane,
Wyndmoor, PA 19038, USA
H. Darmstadt (&)
Rio Tinto, Arvida Research and Development Centre,
1955 Boulevard Mellon, Jonquière, QC G7S 4K8, Canada
e-mail: hans.darmstadt@riotinto.com
(heat-treatment in an oxygen-poor atmosphere) into a solid
residue (char), oil and gas. With respect to use in anodes,
there are important differences between petroleum coke and
biomass char, which have positive and negative impacts on
smelting (Table 1).
In addition to the lower CO2 footprint, the positive impact
of using char in anodes is based on the composition of
biomass. Biomass, which is transformed into char, contains
very low concentrations of some elements undesired in
anodes (e.g. S, Ni, and V). This advantage does not depend
on the biomass transformation process.
The situation is different for the disadvantages. Here,
biomass transformation has a major impact on coke prop-
erties relevant to anodes. The negative impact of char from
conventional pyrolysis on anode properties was confirmed in
laboratory studies. For example, partial replacement of pet-
roleum coke by char resulted in a considerable decrease of
the anode density, whereas the resistivity and CO2 oxidation
increased [2]. The concentration of undesired alkali and
earth alkali metals and associated CO2 oxidation, can be

© The Minerals, Metals & Materials Society 2017 1221

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_146
1222
Table 1 Properties of biomass Difference
char relative to petroleum coke
with respect to use in anodes Lower CO2 footprint
Lower concentration of S
Lower concentrations of Ni and V
Higher concentration of alkali
and earth alkali metals
Lower bulk density
High concentration of oxygen
Material does not pass through
liquid phase during coking
reduced by acid washing [3]. However, this treatment does
not address the low bulk density. In order to increase the
bulk density of biomass char, it was proposed to perform
pyrolysis under mechanical pressure. By this approach,
indeed chars with bulk densities similar to those of petro-
leum coke were obtained [4]. Nevertheless, apart from the
costs to apply mechanical pressure during pyrolysis on large
scale, there are additional challenges.
During the transformation of biomass to char, the material
always remains solid. It does not pass through a liquid phase,
required for the alignment of the developing carbon layers to
a “graphite-like”, anisotropic texture [5]. Therefore, when
the material remains in solid state, only limited alignment is
possible leading to amorphous or isotropic chars. This tex-
ture is undesired in anodes. Anodes made with an amor-
phous or isotropic filler have a high coefficient of thermal
expansion (CTE) [6], making them susceptible to thermal
shock cracking [7]. Furthermore, their electrical resistivity is
higher, as compared to anodes made with an anisotropic
filler [8]. The authors of the present article therefore believe
that the use of biomass char as an anode filler is not a
promising option.
Biomass Oil-Derived Coke as Anode Filler
Biomass-derived anode filler can also be produced by coking
biomass oil. Use of this biomass coke in anodes would have
the same advantages as char (Table 1). However, the dis-
advantages applying to char could be avoided if an appro-
priate biomass transformation process is used:
• Concentration of alkali and earth alkali metals
– Nearly all inorganic material (including alkali and
earth alkali metals) present in the biomass reports to
the char. As long as during pyrolysis the transfer of
solids containing inorganic compounds to the oils is
avoided, the concentration of alkali and earth alkali
metals in the corresponding coke remains low.
Y. Elkasabi et al.
Impact on smelting
More environmental friendly Positive
Lower SO2 emissions
Higher Al purity, less anode oxidation by air
More anode oxidation by CO2 Negative
Less carbon available for electrolysis
Amorphous or isotropic coke texture, increased
susceptibility towards thermal shock cracking
• Bulk density
– It is envisaged that biomass oil would be transformed
in conventional refineries. Assuming a similar
chemistry of petroleum and bio-oil (discussed below),
the bulk densities of corresponding calcined coke
would be similar. The bulk density would mainly
depend on the green coke volatiles content, which is a
function of the coking conditions [9].
• Oxygen content
– In bio-oil obtained by conventional pyrolysis, the
oxygen content is high [10]. Thus, in the present
work, lower-oxygen boi-oil from a special pyrolysis
process [11] was used as coke feedstock.
• Texture
– Upon coking, the feedstock passes through a liquid
phase. Thus, development of the desired anisotropic
texture is possible. However, the temperature range in
which the viscosity of the reaction mixture is sufficiently
low to allow alignment to an anisotropic texture depends
on the O content. Due to interactions between the oxy-
gen- groups, this range is much smaller for high-O oil
than for low-O oil (Fig. 1). Consequently, coke aniso-
tropy increases with decreasing O content of the corre-
sponding feedstock [12].
Fig. 1 Schematic representation of the relationship between viscosity
and temperature of reaction mixture during coking, adapted from Ref. [13]
Coke Produced From Lower-Oxygen Fast-Pyrolysis Oil …
Fig. 2 Optical microscopy image of coke produced from hydro-treated
heavy biomass-derived oil with less than 1% O
Based on the discussion above, the authors of the present
work consider the bio-oil O content as a major factor
determining if the corresponding coke is suitable or not
suitable for anodes. Its impact on the coke properties can be
evaluated by the coke texture. Thus, in the present work,
cokes produced from different types of biomass at various
conditions were studied by optical microscopy.
Oil produced by conventional pyrolysis typically contains
more than 30% of O [10, 14]. By hydro-treatment, it is
possible to reduce the O content in heavy bio-oils to below
1% [15]. The corresponding coke has an anisotropic texture
desired for anode coke (Fig. 2). Although technically feasi-
ble, hydro-treatment on commercial scale is most probably
not economical. Thus, in the present work, pyrolysis was
performed using a process that produces oil with lower O
content as compared to conventional processes. In this pro-
cess, the pyrolysis (tail) gas is recycled through the reactor.
This tail gas contains CO and H2, which partly deoxygenate
the pyrolysis oil [11]. Use of in situ produced tail gas is much
less expensive as compared to hydrotreatment that requires
H2 from external sources. However, oil deoxygenation is
lower than what can be obtained by conventional hydrogen
deoxygenation. One objective of the present work was
therefore to verify if pyrolysis oil deoxygenation with tail gas
is sufficient to produce anode-grade coke.
Experimental Details
Pyrolysis
Fast pyrolysis of biomass was conducted using the Eastern
Regional Research Center fast pyrolysis tail-gas reactive
pyrolysis process, according to previously published proto-
cols [11]. Briefly, dried biomass was fed through a fluidised
1223
sand bed reactor (temperature: 500 °C, N2 atmosphere) at a
rate of 2 kg/h. Any solid char particulates were separated by
subsequently passing the vapours through a cyclone, after
which compounds with a low boiling point were collected in
a series of cold-water condensers. Any remaining oil
entrained in the non-condensable gases was precipitated by
electrostatic precipitation (ESP). All experiments used the
oil obtained from the ESPs. Using a preheater and gas
blower, the remaining gases were recycled back into the
reactor at a rate of 50–70%.
Coking
Prior to coking, light components of pyrolysis oils were
removed by distillation (conditions not shown for IP pro-
tection). Afterwards, the distillation residues were heated
under argon with a rate of 16 °C/min to a final temperature
of 900 °C. Once this temperature was reached, the samples
were allowed to cool down. In two experiments, the distil-
lation residue was mixed with graphite and petroleum coke,
respectively, prior to coking.
Bio-oil Characterisation
Elemental analysis (CHNS) was conducted using a Thermo
EA1112 CHNS analyser. The O content was calculated by
difference.
Coke Characterisation
For microscopic analysis, coke particles were embedded in
epoxy resin and successively mechanically polished until
usage of colloidal silica (0.05 µm) in the final step. Optical
images were recorded with a LEICA DMI500M reflected
light microscope equipped with a 1/4 quarter lambda
polarizer. The samples were observed in air, and no oil
immersion method was used. Examination of specimens was
done with a magnification between 25 and 500. Addi-
tional details can be found elsewhere [16].
Results and Discussion
Oil Oxygen Content
Although pyrolysis runs of the different biomass feedstocks
were performed in similar conditions, the O content of the
corresponding as-received bio-oil varied considerably
(Table 2). A discussion for the reasons why this is the case is
outside the scope of the present document. Here, it is only
1224 Y. Elkasabi et al.

Table 2 Oxygen content of bio oil and coke Use of Cokes with Different Textures in Anodes
Pyrolysis feedstock Oxygen content [mass%]
Bio-oil Distillation residue, Before the texture of biomass-derived coke is discussed,
coker feed coke textures are briefly reviewed. With increasing order,
A 14 n.d. textures might be classified as amorphous, isotropic, aniso-
B1 15 8.1
tropic sponge, and anisotropic needle (Fig. 3). The CTE and
corresponding susceptibility towards thermal shock cracking
8.0
decreases in the same order. Due to its high CTE, amorphous
7.0
coke cannot be used in anodes. Isotropic coke is acceptable
6.8 in blends with sponge coke. Sponge coke is the most widely
7.0 used texture in the production of anodes. Finally, needle
B2 19 8.0 coke is too expensive for anodes. Its application is usually
C 23 18.3 limited to applications where a low CTE is critical, such as
17.0 in electrodes for electric arc furnaces [18].
16.0
D 23 n.d.
Cokes from High-Oxygen Feed
E 27 20.4
19.8 In cokes made from high-O bio-oil, mostly amorphous
18.2 textures were found. Examples for biomass D (23% O in the
17.1 as-received oil) are presented in Fig. 4. As mentioned above,
15.2 oil from the same pyrolysis run was distilled at different
E 30 n.d. temperatures. In cokes from oils distilled at alternate con-
n.d. Not determined
ditions, traces of isotropic and sponge textures were found
(not shown). Nevertheless, the concentration of sponge
textures was much too low to use that type of coke in
relevant that the tail-gas reactive pyrolysis process yielded anodes.
bio-oil with a lower O content as compared to conventional
fast pyrolysis processes. With some pyrolysis feedstock
materials, the oil O content was less than half that of typical Cokes from Medium High-Oxygen Feed
values found in conventional pyrolysis oil (14 vs. >30% [10,
14]). Distilling off light components further reduced the O The as-received oil from biomass A contained 14% O
content, suggesting that O was concentrated in low-boiling (Table 2) and is here classified as medium high-O oil. The
oil compounds of the bio-oil. corresponding cokes had isotropic textures, which started to
show signs of transition to anisotropic textures (Fig. 5).
There was not sufficient material available to determine the
Cokes Textures CTE of the cokes or of the corresponding laboratory anodes.
It is assumed that the CTE is situated between those of
Coke texture depends on the combined O and S concen- isotropic and sponge coke. Blends of isotropic and sponge
trations of the corresponding feedstock, where anisotropy cokes are already successfully used on commercial scale in
increases with decreasing combined O and S concentrations anodes. It is therefore reasonable to assume that biomass-
[13]. The biomass-derived coker feed contained nearly no derived coke, as shown in Fig. 5, could find applications in
S. Thus, its combined O and S concentrations were only anodes, at least as a blend component. As opposed to other
very slightly higher than the O concentrations listed in types of biomass (see below), the oil distillation conditions
Table 2. In petroleum-derived coker feed, the combined O had no significant impact on the textures of the corre-
and S concentrations are typically in the order of 2–4% sponding cokes.
[17]. This is much lower than the lowest O concentration In the present study, the O concentrations of A and D
found in the biomass-derived coker feed of the present bio-oil represented the extremes. This was also the case for
study. the textures of the corresponding cokes.
Coke Produced From Lower-Oxygen Fast-Pyrolysis Oil … 1225

Fig. 3 Optical microscopy

images of coke with: Amorphous
(a), Isotropic (b), Anisotropic
Sponge (c), and Anisotropic
Needle Texture (d)

Fig. 4 Optical microscopy images of coke produced by coking oils Fig. 5 Optical microscopy image of coke produced by coking of oil
from biomass D from biomass A
1226
Fig. 6 Optical microscopy image of coke produced by coking of oil
from biomass C
Fig. 7 Optical microscopy image of coke produced by coking of oil
from biomass B1
Oil from biomass C and D had similar O contents (23% in
as-received oil). As with D, C cokes were amorphous.
However, C cokes, made from an oil sample distilled at
severe conditions, showed traces of anisotropic texture
(Fig. 6).
In oil from biomass B1, the O content was lower than that
in biomass C oil (15 vs. 23% in as-received oil). As opposed
to biomass C and D-derived coke, no amorphous textures
were found in biomass B1-derived coke. Instead, most bio-
mass B1 cokes had isotropic textures. Again, after distilla-
tion at severe conditions, transition to an anisotropic texture
was observed (Fig. 7).
Coking in the Presence of Solids
In a series of tests, graphite and petroleum coke, respec-
tively, were added to heavy bio-oil prior to coking. One
objective of these tests was to verify if these solids could act
as seeds for the development of anisotropic texture in the
biomass-derived portion of the coke that would otherwise
remain amorphous. The microscopy images of the cokes
made with petroleum coke showed particles which were
either entirely amorphous or anisotropic (Fig. 8). The
Y. Elkasabi et al.
Fig. 8 Optical microscopy image of coke produced by co-coking of
oil from biomass B2 with 75% petroleum coke
Fig. 9 Optical microscopy image of coke produced by co-coking of
oil from biomass B2 with 50% petroleum coke
concentration of the anisotropic particles corresponded to the
concentration of petroleum coke in the coker feed (10, 50,
and 75%, respectively). Furthermore, textures of the aniso-
tropic particles were the same as those found in petroleum
coke alone. This suggests that all anisotropic particles
originated from petroleum coke. In a small portion of the
particles, sections with anisotropic texture were embedded in
sections with amorphous texture. The interface between the
two textures was very well defined. There was no transition
zone (Fig. 9). It can be concluded that addition of petroleum
coke had no influence on the texture of the biomass-derived
coke, even when both materials were in very close contact.
The microscopy images of cokes made from bio-oil and
graphite showed small regions with a highly anisotropic
texture embedded in a matrix with amorphous texture
(Fig. 10). The size and concentration of regions with ani-
sotropic textures reflected the size and amount of added
graphite particles. As for composite cokes made with added
petroleum coke, the interfaces of the two regions were well
defined. There were no indications that the embedded gra-
phite particles influenced the texture of the biomass coke
formed around them. It can be summarised that petroleum
coke and graphite particles do not act as seeds promoting an
anisotropic texture of biomass coke.
Coke Produced From Lower-Oxygen Fast-Pyrolysis Oil …
Fig. 10 Optical microscope image of coke produced by co-coking of
oil from biomass B2 with 10% graphite
Summary and Conclusions
Use of biomass pyrolysis-derived material in anodes would
have significant advantages, including a reduced CO2 foot-
print and very low concentrations of undesired elements (S,
V, and Ni). However, char (solid pyrolysis residue) contains
undesired ash, has a low bulk density and undesired texture.
It is therefore not a suitable anode filler. Cokes made from
oil produced by conventional pyrolysis are high in O, which
results in undesired textures. The oil O content can be
reduced by performing pyrolysis with tail gas recycling. The
biomass type also had an important impact on the oil O
content.
In the present study, several cokes were made from
tail-gas reactive pyrolysis oil. The coker feed with the lowest
O concentration was still much higher as compared to the
combined O and S concentrations in the feedstock for pet-
roleum anode coke. Coke made from the biomass-derived
feed with the lowest O concentration had isotropic textures
with signs of transition to the desired anisotropic textures.
Based on the fact that isotropic coke is already blended in
commercial anodes with anisotropic sponge coke, it is
believed that, by tail-gas reactive pyrolysis of certain bio-
mass materials, anode grade coke can be made.
In addition to the pyrolysis process and the biomass, the
distillation conditions of the coker feed also influence the
coke texture. In the range studied, more severe conditions
favoured a more anisotropic texture, especially when the
texture was not well developed.
1227
Petroleum coke and graphite did not act as seeds for
anisotropic textures in biomass-derived coke.
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Annual Petcoke Conference, San Antonio, TX, USA, 2013
 Part XXVII
Electrode Technology: Electrodes:
Baking/Characterization
 25 Years of Natural Gas Purged Infrared
Pyrometer Temperature Measurement
for the Operation of Open-Top Anodes
Baking Furnaces

Yvon Menard

Abstract
To improve a low flue wall life, a natural gas purged infrared pyrometer system was
implemented to replace original thermocouples based temperature measurement systems on
firing system, in 1991. Flue wall life increased to be over 100 cycles, on Pechiney furnaces,
by preventing flue walls overheating. Anodes baking quality is adequate for two burners
ramps fire technology. Some problems had to be corrected over time as they appeared:
calibration drift, pinched injector tubes, frosted pyrometers lenses, etc. Pyrometers and
thermocouple measurement technologies can both successfully bake anodes to specifica-
tions, but original cost, ease of operation, and maintenance, and effect on refractory may
favour one system over the other, depending on the plant situation.

Keywords
Infrared pyrometer Anode baking Open top baking furnace

Introduction History of the Invention

Anode baking requires measurement of high temperature,
over 1000 °C, for prolonged periods of time. Thermocouple
is the most used temperature measurement technology in the
anode baking process. But this is not the only one. Another
one used, but is not as widespread is the natural gas purged
infrared pyrometer.
Although thermocouple gives good results in normal
situations, it happens that it underestimates temperature of
refractory under burners. This may lead to unacceptable high
temperature and thermal creeping of refractory, leading to
refractory failure.
This paper will review development history of natural gas
purged infrared pyrometer, its performance over 25 years of
continuous use and compare with thermocouple with
emphasis on conditions under which each temperature
measurement system gives best results.
Y. Menard (&)
933 Pierre-Laure, Chicoutimi, QC G7H 7K5, Canada
e-mail: yvonmenard933@mail.com
Natural gas purged infrared pyrometer technology was
invented in Alcan’s Kurri plant in the middle of the 1980,
after conversion from heavy oil to natural gas of their two
Alcoa single baffle open top furnaces. Two problems arose.
• Thermocouples cost was prohibitive and thermocouple
failure rate was high. Platinum thermocouples were used
at that time in this plant.
• Flue wall temperature under burners was too high, even
if flue gas temperature was on target.
When baking anodes are in sections under burners, most
heat transferred to anodes comes from radiation from the
flame to the flue wall. Flue gas temperature in flue walls
under burners, measured by thermocouple, comes from:
• gas temperature resulting from combustion of fuel,
• gas coming from the adjacent flue wall from the previous
section and
• cooling of the flue wall, heated by radiation, by flue gas.

© The Minerals, Metals & Materials Society 2017 1231

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_147
1232
Thermocouple temperature measurement depends heavily
on draft to transport heat from heating sources to thermo-
couple. So any low draft situation results in leaving heat
under burners instead of transporting it to thermocouple.
This results in thermocouple sensing low temperature,
resulting in a demand for more heat, while refractory under
the burners overheats. This results in refractory thermal
creeping. An easily observable symptom of this is glassy flue
walls under burner peepholes.
To solve these two problems, natural gas purged infrared
pyrometers were tried and implemented. So for each ther-
mocouple, an infrared pyrometer was implemented. Princi-
ple was that, by measuring refractory temperature under
burners, temperature measurement was one step closer to the
real heat transfer to anodes, in this step of baking, while
making the baking process less sensitive to low draft in
sections under burners.
Infrared pyrometers were implemented with success in
Kurri. Temperature baking profiles using this technology
were similar to those with thermocouple temperature mea-
surement technology, without recurrent costs of platinum
thermocouples and without refractory overheating. A paper
describing this technology was presented at TMS conference
in 1989 [1]. Technology was protected by a patent issued in
1991 [2].
25 Years of Use Story
Another plant, plant A, had two Pechiney open top triple
baffle furnaces that were converted from heavy oil to natural
gas, in 1985. Furnaces were organized with technology of
that time, one sealing section, three sections under preheat-
ing, two sections under fire and six sections under forced
cooling. Flue life of flue walls was between 50 and 60 fire
cycles. Low draft at that time resulted in overheating of
refractory.
Design
Following Kurri experience, a fire was setup with infrared
pyrometers and tested in 1990. Full implementation fol-
lowed in 1991. There were six fires with two burners ramps
each, each burner ramp had seven thermocouples. They were
retrofitted with 14 pyrometers, one by burner. There were
two spare burner ramps. So a total of about 200 infrared
pyrometers were bought. Such a large order helped to get
low prices. Single wavelength infrared pyrometers were
selected. Double wavelength infrared pyrometers were way
too expensive at that time.
All ramps, including preheating ramps, were equipped
with a standard plant PLC with I/O cards needed for their
Y. Menard
tasks. These pyrometers being very basic, the temperature
curve was not standard. The PLC supplier programmed
thermocouples I/O cards (on cards EEPROM) with a custom
temperature curve for pyrometers. At the time, that was the
simplest way to deal with that pyrometer particularity.
Emissivity correction was made by a calibration screw, that
pushed a steel V shaped spring blade in front of infrared
sensing element, partly obstructing target view by sensing
element. These pyrometers had no programming ability of
any kind, unlike most current infrared pyrometers.
Burners were modified to receive pyrometers (Fig. 1).
The aim tube, 25 mm diameter straight tube, was the injector
for natural gas, so pyrometers had a clear path for temper-
ature measurement. The optics of pyrometers was ordered to
measure a target of a few centimeters in diameter at bottom
of the flue wall, about 4.5 m below pyrometers.
Logic of firing was modified so injection of natural gas
was stopped every two minutes, for a few seconds, to
measure repeatedly bottom of the flue wall without burner
flame interference. A high temperature limit stopped natural
gas injections when this limit was reached. A high temper-
ature limit stopped the entire burner ramps when this tem-
perature was reached. Interruption of the injection was
signaled to fire operators by an alarm indicating which
burner and which ramp was in trouble. High limit and high
limit were established taking into account maximum tem-
perature of flue wall internal sides was, on average, 50 °C
higher than bottom of flue wall interior. An example of this,
Fig. 1 Burner design
25 Years of Natural Gas Purged Infrared Pyrometer …
to avoid going over 1325 °C on refractory, a maximum limit
of 1275 °C was established. Flue wall sides under the
peephole burner stayed with dull new refractory brick tex-
ture, even after 100 fire cycles.
Logic of the injection was to have a fixed natural gas
valve opening, a pulse, at variable intervals, to suit tem-
perature demand. Interval limits, for variable intervals,
maximum and minimum were programmed. Maximum time
interval insured a minimal natural gas purge to protect
pyrometers. Minimum intervals insured that natural gas
quantity was limited, limiting maximum temperature.
Fixed injection time was adjusted to avoid depleting
oxygen level under burners, insuring a total combustion of
fuel. Position and length of flame within flue wall height,
with this fixed quantity of fuel, was adjusted using natural
gas pressure. A low pressure kept flames short near top of
the flue wall height. A high pressure sent a long flame at the
bottom of the flue wall height. Pressure was adjusted for
combustion to happen in middle of the flue wall height, to
distribute heat evenly toward anodes in pits.
Emissivity of pyrometers at start up was adjusted by
measuring bottom of flue wall temperature with a calibrated
portable infrared pyrometer and adjusting emissivity cali-
bration screw to get correct temperature reading. Later, a
calibration furnace was bought to be able to calibrate
pyrometers in a controlled environment.
Problems Arising from Long-Term Use
and Solutions
One of first problem noticed was burner tubes pinching with
time. High temperature softened burner tube so much that
they deformed and red-hot metal partly obstructed the view
of the pyrometer, causing a bias in temperature measure-
ment. Burner tubes were shortened, and burner tube material
was replaced by a higher temperature resistant material.
Single wavelength infrared pyrometer being a relative
measurement (affected by emissivity, dirt on the lens, etc.),
pyrometer has to be calibrated, which is not the case with
thermocouple. It took a while, but, Maintenance Department
used to thermocouples, pyrometers were not calibrated and
eventually temperature measurement drifted. A calibration
schedule was programmed in maintenance management
system. As mentioned before, a temperature calibration
bench was organized, so maintenance workers could cali-
brate pyrometers in their maintenance shop. A few more
pyrometers were bought to have pyrometers available for
calibration.
If a natural gas valve leaks or is blocked open, flame in
front of the pyrometer is still present during temperature
measurement cycle, resulting in an unusually high temper-
ature measured. Analysis of this situation, by comparing
1233
with temperature measured by pyrometers before and after
the pyrometer with a high temperature, gives to fire opera-
tors a hint that natural gas valve has to be maintained.
The same analysis can be performed if a temperature
measurement is unusually low. If a natural gas valve is
closed or natural gas supply is not present (forgotten shutoff
valves) and burners do not inject natural gas, temperature
under this burner will be unusually low and this situation
will be easy to detect, again by comparing with other
pyrometers on the same line of flue walls, on the same fire.
If a burner is not oriented correctly and aims at flue wall
side, flame directly heats one side of the flue wall under the
burner and generally overheats flue walls, if burner orien-
tation problem not detected rapidly. When this problem
happens, pyrometers measure flue walls side temperature
directly where flame heats side and adjust natural gas flow to
get target temperature, avoiding overheating flue wall. This
causes a low temperature locally, which may not be good for
the anode baking, but this protects refractory from over-
heating and prevents refractory failure.
A puzzling problem arose, pyrometer lenses started
frosting, due to chemical attack of lenses by fluorine
evolving from baking. Usually, natural gas purges lenses,
avoiding this kind of chemical attack. It took a while to find
out the cause of this problem. It was finally found that,
before fire advance, fire operators installed a spare burners
ramp at position burner ramp was planned to occupy after
fire advance. When spare burner ramp was in position, fire
operators unhooked burners from burner ramp and dropped
them vertically in packing coke, on last preheated section,
next to peepholes they were planned to occupy at fire
advance time. So burner tubes were fully buried in packing
coke, just on top of very hot anodes, that emitted fluorinated
gases, without any natural gas purge to protect the lens. So
fluorinated gases had opportunity to rise in burner tubes,
attacking pyrometer lenses. Problem was solved by storing
spare burners ramps elsewhere, not on furnaces, this way
they would not be available in normal operation, and still be
available rapidly to replace faulty burners ramps.
An unorthodox use of pyrometers was developed, after
crossover crossing of burners ramps. For safety reason,
natural gas injection stops when temperature measured is too
low, below 760 °C, as required by insurance companies. It
happens that this temperature is not reached when a burner
ramp is on the first section after crossover, depending on
crossover construction, crossover condition or process con-
ditions before crossovers. It requires having burners or
ramps having flame detection or pilot burner to raise tem-
perature, because burner ramps are programmed to stop
natural gas injection if minimal temperature is not reached.
A way to make natural gas injection start safely was devised,
by dropping an ignited fire starter log in peephole under
burner not at minimal temperature. Pyrometer then sees
1234
flames of fire starter log, at temperature measurement time,
flame temperature is over 760 °C, and PLC logic starts
injecting natural gas. If oxygen level is too low, fire starter
log extinguishes, temperature measured drops below
760 °C, natural gas injection stops. If starter log burns
completely before 760 °C at the bottom of the flue wall,
under the burner, is reached and extinguishes, natural gas
injection stops. So pyrometer is used as flame detector and
fire starter log is pilot flame. No modification to PLC logic is
done and baking process stays safe. This procedure is used
only on occasion.
A new problem just arose. Most infrared pyrometers in
operation are still the ones bought in 1990–1991. So they are
25 years old and no longer manufactured. So replacement
pyrometers have to be found to replace the few defective
ones of the older generation. New ones do not have same
mV versus temperature curve, they generally mimic ther-
mocouple output curve. Wiring on new pyrometers may also
differ from two wires of old pyrometers, depending on
pyrometer models and functions, so wiring may have to be
replaced. Plan is to replace all pyrometers on one burner
ramp with newer model pyrometers. This requires thermo-
couples PLC card of this ramp to be replaced by standard
thermocouples PLC card. Doing so, older model pyrometers
and older thermocouples PLC cards programmed for old
pyrometers temperature curve become available as spare
parts for burner ramps remaining with original 1991
technology.
Results on Operation
The main reason for replacing thermocouples with infrared
pyrometers was to avoid refractory overheating. This way
low flue wall life would improve. Did it improved? Figure 2
shows the flue wall live from plant start up. Two milestones
in the graph, natural gas replaced heavy oil in 1985 and
infrared pyrometers replaced thermocouples in 1991. Graph
shows an almost flat zone, where flue walls life rose very
slowly between 1985 and 1997. After 1997 flue wall life
started increasing at a faster rate up to 2013, for internal flue
walls. It was a few years earlier for external flue walls. Better
control on flue walls overheating cannot be credited for all
improvement on flue walls life over the years. Other causes
helped to improve the flue wall life like dedicated refractory
technical maintenance resources, rebuilding anew head
walls, correction of flue walls design to take into account
furnaces changing condition.
Change in flue walls life trend in the 2010s may be partly
attributed to changes in refractory maintenance management
caused by aluminium industry recession that started in 2008.
Y. Menard
Fig. 2 Flue wall life history for plant A
Comparison Between Thermocouples
and Infrared Pyrometers
Temperature distribution among anodes, temperature profile,
depends on many variables:
• Flue wall design;
• Fire cycle length;
• Fire operators knowledge of baking process and how to
act when process in not within specifications;
• Process control adjustment, which goes with knowledge
of technical resources.
Temperature measurement, if representative of real tem-
perature in flue walls, has a neutral effect on temperature
profile. It will neither help nor hamper anodes baking.
Pyrometers, giving two temperature measurements in a flue
wall, instead of one for thermocouple, may help to obtain a
good heat distribution. But this is difficult to prove, because
variables enumerated earlier can obscure the effect. A fast
fire cycle with few sections under burners, conditions under
which infrared pyrometers are used, is usually bad for heat
distribution, because there is little time for heat to reach
steady state.
Physically, when fire operators have to move a burner
ramp, they have to move three equipment by flue walls,
when they use thermocouples. They only move two, with
pyrometers. Pyrometers being a component of burners, they
move with them (Fig. 4). So pyrometers cut by a third safety
risk associated with handling of high temperature parts
during fire advance. Pyrometers being at room temperature,
they are less likely to deteriorate during handling than
thermocouple protection tubes at high temperature, espe-
cially if protection tubes are made out of ceramics.
Thermocouples can be used either with heavy oil or
natural gas. Pyrometers can only be used with natural gas,
because natural gas is used to purge pyrometers.
25 Years of Natural Gas Purged Infrared Pyrometer …
Thermocouple is inexpensive to install, but thermocouple
failure requires frequent changes. Pyrometers are expensive
to install, but last a few decades.
Thermocouple is an absolute measurement, it does not
require to be calibrated. Analogue part of thermocouple
signal transmission to PLC has to be checked, which is
frequently neglected (think about thermocouple simulators
to achieve this verification). Pyrometer is a relative mea-
surement, it requires to be calibrated from time to time, once
every six months, once a year. Again, analogue part of signal
transmission to PLC has to be checked from time to time.
Thermocouples depend on flue gas draft to measure
temperature at burners position. Low draft means underes-
timating temperature under burners. Which translates in
overheating of refractory and excess fuel consumption, to
achieve overheating of refractory. Pyrometers measure
temperature right under burners, so temperature is closer
from real temperature generated by burner. Pyrometers,
while not totally immune to draft effect, is less sensitive.
Temperature measurement at thermocouple position is a
mix of heat generated by both preceding burners. Thermo-
couples cannot know if they give what controller asked them
to give if one of the two preceding burners does not operate
correctly (natural gas valve leak or blockage, etc.). The other
burner is asked to compensate for deficiency of burner in
trouble. With pyrometer, problem is limited to the burner in
trouble, which makes troubleshooting simpler.
On the hardware side, pyrometers have twice as many
inputs, and wires, to PLC than thermocouples, because there
are twice the number of thermocouples. So it is more
expensive to install.
On the control side, each burner having a temperature
controller, difference is on the back burner control. With
thermocouples, back burner controller is the slave of the
front burner controller. It is adjusted to be a fixed proportion
of front burner output. With pyrometers, each burner has a
temperature measurement, so control of each burner is based
on a temperature measurement. If one burner or a pyrometer
of a flue wall has a problem, it does not affect the other one.
Consequently with pyrometers baking quality is less affected
and there is less deviation from flue temperature targets.
Thermocouples require extra equipment if temperature of
flue gas is too low for fuel injection. Pyrometers may be
used as a flame detector of a pilot flame generated by
burning of solid combustible under too low a temperature
burner and pyrometer. This does not require modification to
process logic, so programmed safety protections in process
logic always stay effective.
1235
Domain of Application of Each Technology
Thermocouple works very well in case where time is
available for heat transfer, which means target temperature at
thermocouple position can be rather low, 1080–1100 °C, in
presence of a high enough draft. This implies long fire
sections, three to four sections under fire and slow fire cycle,
24 h and higher.
Pyrometers can be used when there is little time to
complete heat transfer, two or three sections under fire or
short fire cycle, or if the heat transfer to a thermocouple
would be problematic, a low draft situation. Both cases
implies high temperature under burners, 1200–1225 °C, to
insure an ample heat transfer to obtain required anodes
baking level.
An economical study has to be performed to see if it is
more economical to build a longer furnace and added cost to
build burners ramps to use thermocouples or to build a
shorter furnace with fewer but more expensive burner ramps
to use pyrometers.
Conclusion
Natural gas purged infrared pyrometers can be used to
measure temperature in sections under burner ramps. They
are more expensive to install than thermocouples, but last a
lot longer. They require regular calibration. They allow to run
anode baking furnaces at higher temperatures because they
measure directly under burners, protecting refractory from
overheating, which may be useful if the number of sections
under burners is limited or if the fire cycle is very short.
Anodes baking quality is satisfactory for use in electrol-
ysis pots. Anodes baked using this technology are used in
pots operations for 25 years, what amount to about 5.8
million anodes, with only two burners ramps.
Pyrometers temperature measurement offer opportunity,
by running at higher temperature, to build shorter furnaces
and to lower number of burner ramps required. An eco-
nomical study has to be done to compare alternatives.
References
1. C. MacPherson, A new automatic anode baking system using flue
brick temperature control. Light Metals, 575–586 (1989)
2. C.B.P. MacPherson, G.H. Jefferson, Infra-red burner system for
furnaces. United States Patent 5,110,287, 5 May 1992
 Characterization of Prebake Anodes by Micro
X-ray Computed Tomography

Stein Rørvik and Lorentz Petter Lossius

Abstract
As part of the continuous work in improving anode quality at Hydro Aluminium, series of
pilot scale anodes have been manufactured with systematic changes in coke type and green
paste production including recipe. The anodes also support M.Sc., Ph.D. and PostDoc work
in programs supported by Hydro and the Norwegian Research Council. In addition to
regular analysis, the pore, void and grain distribution has been investigated using Micro
X-ray Computed Tomography (µCT). This non-destructive 3D imaging is now
implemented at a cost to allow larger numbers of samples, and a methodology has been
developed by SINTEF that yields surprising sharp detail, suited to interpret important
structural factors for relatively large anode volumes of 10–130 mm diameter. Given a better
cost to information yield than image analysis and mercury porosimetry, Hydro will
continue to support academic work with CT analysis. Examples will be shown of baked
anodes before and after electrolysis testing plus crack patterns after mechanical testing.

Keywords
Carbon anodes Computed Tomography Image analysis Porosity

Background and overhead involved in the sample preparation (setup of

Over several decades, the electrolysis research group at
SINTEF Materials and Chemistry has developed special
competence in characterization of carbon materials by opti-
cal microscopy and image analysis [1–3]. These methods
have been based on embedding the sample in epoxy under
vacuum and making a polished cut through this mount. The
main advantage with this method is the high resolution
(1–2 µm) and speed of automated image acquisition and
analysis (1–2 h). The main disadvantages are the time
S. Rørvik (&)
SINTEF Materials and Chemistry, 7465 Trondheim, Norway
e-mail: stein.rorvik@sintef.no
L.P. Lossius
Hydro Aluminium, 6882 Øvre Årdal, Norway
vacuum embedding device, epoxy curing overnight,
cutting/grinding, polishing and cleaning) and the fact that a
single test piece only represents one slice through the sam-
ple; which may or may not be representative of the entire
sample.
In the recent years, Micro X-ray Computed Tomography
(µCT) has emerged as a good alternative to microscopy
based image analysis. SINTEF/Hydro has found it especially
useful for studies of porosity and mapping of electrolyte
penetration. The main advantage is that the technique can be
used to image large samples non-destructively at a good
resolution within a reasonable time and cost.
In 2013, a µCT instrument was installed at NTNU
(Norwegian University of Science and Technology) as part
of the RECX national centre of X-ray infrastructure (Nor-
wegian Centre for X-ray Diffraction, Scattering and Imag-
ing). This has been directly accessible to the SINTEF
research group, which has gained extensive experience with
this type of imaging and analysis.

© The Minerals, Metals & Materials Society 2017 1237

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_148
1238 S. Rørvik and L.P. Lossius

Previously Published Work
A number of papers has previously been published on CT
imaging of carbon anodes [4–11]. Most of these have pre-
sented quantitative analysis of local density, presenting results
such as gradients and inhomogeneity. As Table 1 shows, a
major difference between the present work and the previously
published work is the resolution (voxel size) and image size.
Because of the limited resolution in the previous work, none of
the referenced papers has presented any pore size distributions
in the traditional sense. Even if the µCT method is still limited
by its resolution, it is the authors’ opinion that the method has
now advanced to a level where anode pore size distributions
can be quantified in a meaningful way.
Investigated Anode Material
The anode test material was produced at the Hydro Alu-
minium test facility in Årdal, Norway, under supervision of
Lorentz Petter Lossius. Regular anode analysis was made by
Hydro Aluminium. The purpose of this study was to
investigate the effect various anode manufacturing parame-
ters had to the resulting porosity. These parameters included
variations in the granulometry (varying Modified Andreasen
Factor), as well as variation in the mixer configuration. The
former and the latter was implemented as two separate series
of pilot scale anodes.
Technique
The instrument (Fig. 1) used for the µCT analysis is an
X-TEK XT H225 ST delivered by the UK company Nikon
Metrology. It has a 225 kV maximum acceleration voltage
and employs a reflection source selectable between four
different targets: Cu, Mo, Ag and W. The usable sample size
is a cylinder from 5 to 150 mm outer edge. The detector has
2000  2000 pixels resolution and the software exports
2000 XY slices, so the resulting resolution (or voxel size) for
the usable sample size range is 2.5  2.5  2.5 µm to
75  75  75 µm.

Table 1 Comparison of data Reference Scan size XY Volume size XY Voxel size
resolution from literature on CT
of carbon anodes 5 – 512  512 0.46  0.46  2 mm
6 – 0.3 mm/0.4 mm
8 50.8 mm Ø 0.13  0.13  0.6 mm
9 50.8 mm Ø 512  512 0.13  0.13  0.6 mm
10 – 0.15  0.15  0.6 mm
11 – 0.7  0.6  0.7 mm
This work 54 mm Ø 2000  2000 0.027  0.027  0.027 mm

Fig. 1 The µCT instrument

(stock photo)
Characterization of Prebake Anodes by Micro X-ray …
Fig. 2 µCT principle (drawing
taken from Wikipedia)
The principle of the method is illustrated in Fig. 2: The
sample is placed on a rotating stage, which is also movable
in the X, Y and Z directions. The sample is illuminated by a
powerful X-ray point source, which emits a cone shaped
beam that penetrates the sample. The image is captured by a
square detector, digitized and stored on a computer. The
sample is rotated in small increments spanning across the
entire 360° rotation. For good results, at least 3142
(p * 1000) images must be acquired. The images are
reconstructed by computer software supplied with the
instrument. Since there are many software options that
affects the result and quality of this reconstruction, the
selection of settings has been automated by a script pro-
cessing the sample metadata. The choice of settings have
been optimized for carbon materials, and give much better
results than the settings recommended by the supplier. This
procedure has also shown to work very well with plastics
and glass materials.
The time needed for such an analysis is reasonable: About
30–45 min for warm-up and calibration of the instrument (at
the start of the day); typically 110 min for the image
acquisition and 30–45 min for the software reconstruction.
The software processing can be done as an automated batch
procedure. This makes the technique cost competitive to
microscopy and image analysis.
1239
Data Processing
The software used to reconstruct the data was the one sup-
plied by the instrument vendor. The analysis software sup-
plied with the instrument was however not found to be
suitable for electrode materials, as the functionality was
focused on machine parts and industrial engineering.
Because of this, a series of custom macros were written for
the public domain software ImageJ [12] for processing and
analysis of the electrode data sets. These macros deal with
the assembly of the sliced XY image stacks (as exported by
the CT software) into one dataset. This dataset is both spatial
and density calibrated. The spatial and density calibrations
are calculated from metadata generated by the CT instru-
ment. The spatial calibration defines the physical voxel size,
while the density calibration translates each voxel’s mea-
sured X-ray attenuation value into a greyscale value
according to a calibration factor. This factor is linear for
carbon materials, as they consist mostly of the one element,
C. The factor was calculated by measuring the average X-ray
attenuation values of a known quality graphite sample, and
then defined as the multiplication factor needed to output
measurement values equal to the geometric density of the
graphite reference. The workflow also includes automati-
cally slicing the dataset in other directions (XZ and YZ), and
1240 S. Rørvik and L.P. Lossius

Fig. 3 XY and XZ slices of a 50 mm prebaked anode sample

generating movies for visualization. This reduces the time

needed for processing of data greatly. The scripts developed
are easy to expand with other functionality. The electrolysis
research group at SINTEF has also worked with character-
ization of other electrode materials, including Søderberg
paste and anodes, cathodes, ramming paste, sidewall mate-
rials and non-carbon electrodes, so the efforts have been
shared between several different research projects.
Figure 3 shows an example of the automated output from
the data processing. The left part of the image shows a slice
of the sample in the horizontal (XY) direction. The right part
shows the centre slice in the vertical (XZ) direction. The line
across the XZ image shows where the XY image is posi-
tioned in the dataset, with an indication of the mm distance
from the top. On the upper left corner, a spatial scalebar is
inserted. This image pair is a single frame from a movie Fig. 4 Pores in a coke grain; carbon is transparent
showing all 2000 slices from the top to the bottom. This
presentation of the data has been found to be one of the most to be seen with red-blue 3D glasses. Carbon is still rendered
intuitive way to visualize the 3D datasets. as transparent here. Figure 6 shows a projected 3D view of
the same coke section, but the pore walls are here shown as a
rendered surface. The disadvantage of using such 3D views
3D Visualization for porous carbon materials is that the view easily gets very
chaotic because of the high number of pores. A 3D view of
It is also possible to extract and visualize features (such as the pores inside the 50 mm anode sample in Fig. 3 would
pores) as a 3D view. Figure 4 shows a projected 3D view of just look as a dense cloud. For carbon materials, our expe-
a 4.35  4.35 mm section of a coke grain. Carbon is here rience is that such 3D views are more useful to visualize
rendered as transparent; pores are semi-transparent white. metal impurities or electrolyte penetration rather than
Figure 5 shows the same view as an anaglyph stereo image, porosity.
Characterization of Prebake Anodes by Micro X-ray …
Fig. 5 Pores in a coke grain shown as an anaglyph image; carbon is
transparent
Fig. 6 Pores in a coke grain shown as a rendered surface; carbon is
transparent
Qualitative Analysis
The CT datasets provide lots of useful qualitative informa-
tion. It is easy to inspect visually how the coke grains are
distributed and packed, how the pores are distributed and
how homogeneous the anode structure is. The method has
also proven to be useful for inspection after mechanical
testing: Fig. 7 shows a 50 mm core from an anode after
mechanical testing (Flattened Brazilian Disk test). The crack
is relatively straight and well defined. The anode is dense
and homogeneous. Figure 8 shows another sample, from an
1241
anode made at a different production facility. Here the crack
is much thinner and more branched; it is hardly visible. This
anode has a more porous structure, with high porosity cokes.
Apparently, the more porous structure of the anode absorbs
the crack growth; the anode is more flexible. These images
illustrates well the thermal cracking problems experienced
when using high amounts of shot coke in prebake anodes.
Quantitative Analysis
The CT images can be analysed quantitatively using similar
image analysis methods as applied to light microscopy
images [1–3]. The main disadvantage is the lower resolution
(tens of microns instead of single microns), but that has been
found to be outweighed by the great advantage of being able
to analyse the entire sample volume instead of just one
polished cut as done with light or electron microscopy. The
quantitative analysis was done using custom written macros
for the public domain software ImageJ [12].
Granulometry Study
Production Porosity
Figure 9 shows an example comparing the total amount of
(large) pores as visible by CT in a series of pilot anodes
(13 cm Ø, 20 cm height). These pilot anodes apply sys-
tematic variations in the granulometry; this work is pub-
lished in another TMS 2017 paper [B. Øye et al.]. The CT
analysis compare the total amount of voids (visible by µCT)
in the green anodes and the very same anodes after baking.
These voids may also be called “production porosity” as
they consist of the voids between coke grains due to
incomplete mixing of the paste, and larger coke pores that
the binder matrix failed to fill. The pilot anodes were scan-
ned full size using two scans covering the upper and lower
half, and the resulting datasets were merged at the overlap-
ping plane.
The key parameters that were changed in the granulom-
etry study are summarized in Table 2. Comparing to the
results in Fig. 9, it is seen that for the green anodes, a
moderate MAF (Modified Andreasen Factor) combined with
the highest amount of fines produces the densest anode. For
the baked anodes, the extra fines increases the porosity.
Here, the highest MAF combined with the highest amount
coarse butts produces the densest anodes. This example
1242
Fig. 7 50 mm Ø prebake anode
sample after mechanical testing
(Flattened Brazilian Disk)
shows how µCT can be applied for structural characteriza-
tion of anodes.
Pore Size Distribution
Figure 10 compares pore size distributions of the baked
anodes shown in Fig. 9. The left grey area in the chart indicates
pore sizes than cannot be reliably measured. These corre-
sponds to pores less than 3 pixels (80 µm) wide; so the size
cannot be properly determined for these. Two cores are anal-
ysed for each anode. The distribution for each of the two cores
from the same anode are similar; while there are clear differ-
ences in the overall pore distribution from anode to anode.
S. Rørvik and L.P. Lossius
Mixing Study
Description of Anodes
The purpose of this study was to examine the effect of
mixing parameters. The mixer is a rotary Eirich type mixer.
Two different types of mixing tools (the rotor blades
mounted inside the mixer) were compared. These are here
just referred as “old” and “new” type. Since the angles of
these rotor blades are different, the paste will be pushed
down or lifted up during mixing, depending on if the rotation
direction is clockwise or counter- clockwise. Table 3 sum-
marizes the mixing parameters that were changed in this
study. The green paste used is the same for all anodes.
Characterization of Prebake Anodes by Micro X-ray … 1243

Fig. 8 50 mm Ø prebake anode

sample after mechanical testing
(Flattened Brazilian Disk)

Fig. 9 Total amount of large

pores (voids) in full size pilot Voids, green vs baked
anodes
4

3.5

3
Voids [volume %]

2.5

1.5

0.5

0
L22G L23G L25G L27G L29G
Voids [%] Voids [%] Voids [%] Voids [%] Voids [%]
Green 2.8335 2.4155 2.3285 1.8645 1.6725
Baked 3.4567 2.944 2.591 1.9562 2.0792
1244 S. Rørvik and L.P. Lossius

Table 2 Production parameters Anode # L22 L23 L25 L27 L29

in the granulometry study
MAF (Modified andreasen factor) 0.26 0.32 0.42 0.42 0.32
Coarse butts amount (%) 12 12 12 16.5 12
Fines amount (%) 24 24 24 24 28

Fig. 10 Pore size distributions

of large pores (voids) in a baked Pilot Anodes L-series Voids [%] L22-045-2c
1 Voids [%] L22-045-2n
anode 50 mm core
Voids [%] L23-047-2c
0.9 Voids [%] L23-047-2n
Voids [%] L25-051-2c
0.8 Voids [%] L25-051-2n
Voids [%] L27-055-2c
0.7 Voids [%] L27-055-2n
..
0.6 ..
..
Voids [%]

0.5 ..

0.4

0.3

0.2

0.1

0
0.001 0.01 0.1 1 10 100
Diameter [mm]

Table 3 Production parameters Anode # M01 M10 M12 M13 M15

in the mixing study
Mixing tool Old type New type New type New type New type
Mass direction Press down Lift up Lift up Press down Lift up
Mixing time (min) 3 6 10 2 4

Pore Size Distribution cracked/non-cracked samples of the same anode; showing

Figure 11 shows pore size distributions of large pores
(voids) in 50 mm anode core samples taken from the dif-
ferent mixing configurations. The differences in pore size
distribution is much higher here than in the case shown in
Fig. 10, where the anodes represent granulometry variations.
The core samples were taken after Flat Brazilian Disk test-
ing; one representing the cracked region (M##-c) and
another representing the non-cracked (M##-n) region. The
pore size distributions are close for each pair of
that the cracking does not affect the overall pore size dis-
tribution, as the crack represents a small fraction of the total
volume of the sample. Sample M15-n was not analysed as it
fell apart during drilling.
Comparing the size distributions in Fig. 11 to the mix-
ing parameters in Table 3, it is clear that the main differ-
ence is in whether the mass is lifted up or pressed down
during mixing. Two minutes mixing in a press-down
configuration gives a denser anode than ten minutes in a
lift-up configuration. The new type of rotor blades gives
Characterization of Prebake Anodes by Micro X-ray … 1245

Fig. 11 Pore size distributions

of large pores (voids) in a baked Pilot Anodes M-series Voids [%] 150417-M01-c
1 Voids [%] 150417-M01-n
anode 50 mm core
Voids [%] 150417-M10-c
0.9 Voids [%] 150417-M10-n
Voids [%] 150417-M12-c
0.8 Voids [%] 150417-M12-n
Voids [%] 150417-M13-c
0.7 Voids [%] 150417-M13-n
Voids [%] 150417-M15-c
0.6 ..
..

Voids [%]
0.5 ..

0.4

0.3

0.2

0.1

0
0.001 0.01 0.1 1 10 100
Diameter [mm]

better results than the old type, comparing the pore size
distribution of M13 to M01.
Conclusion
Micro X-ray Computed Tomography (µCT) has proven to be
an excellent alternative to microscopy based image analysis,
especially for studies of porosity and cracking. The technique
can be used to image large samples non-destructively at a
good resolution within a reasonable time and cost. The anode
structure can be analysed both qualitatively in the form of
visual images and movies, as well as quantitatively in the
form of pore size distributions.
Acknowledgements The present work was carried out in the projects
HAL UP Anodes and SHIFT Method Development, financed by Hydro
Aluminium and the Research Council of Norway. Permission to pub-
lish the method and results is gratefully acknowledged.The work was
carried out in the research programs HAL UP and SHIFT, led by
Nancy J. Holt of Hydro Aluminium. The programs were funded by
Hydro Aluminium and the Research Council of Norway. Permission to
publish the method and results is gratefully acknowledged.
References
1. S. Rørvik, H.A. Øye: A Method for Characterization of Anode
Pore Structure by Image Analysis. The Minerals, Metals and
Materials Society (TMS); Light Metals Proceedings (1996),
pp. 561–568
2. S. Rørvik, H.A. Øye, M. Sørlie, Characterization of porosity in
cokes by image analysis. TMS Light Met. (2001)
3. S. Rørvik, L.P. Lossius, H.A. Øye, Classification of pores in
prebake anodes using automated optical microscopy. TMS Light
Met. (2003)
4. A.N. Adams et al., The non-destructive 3-D characterization of
pre-baked carbon anodes using x-ray computerized tomography.
TMS Light Met. 535–539 (2002)
5. U. Suriyapraphadilok et al., Physical, chemical and x-ray
computed tomography characterization of anode butt cores. TMS
Light Met. 617–621 (2005)
6. U. Suriyapraphadilok et al., Anode butt cores: physical character-
ization and reactivity measurements. JOM. 57(2), 35–41 (2005)
7. D. Picard et al., Characterization of a full-scale prebaked carbon
anode using x-ray computerized tomography. TMS Light Met.
973–978 (2011)
8. D. Picard et al., Characterization of prebaked carbon anode
samples using x-ray computed tomography and porosity estima-
tion. TMS Light Met. 1283–1288 (2012)
9. K. Azari et al., Characterization of homogeneity of green anodes
through x-ray tomography and image analysis. TMS Light Met.
1141–1146 (2014)
10. D. Picard et al., Automated crack detection method applied to CT
images of baked carbon anode. TMS Light Met. 1275–1280
(2014)
11. C. Sommerseth et al., Spatial methods for characterising carbon
anodes for aluminium production. TMS Light Met. 1141–1146
(2015)
12. W.S. Rasband, ImageJ, U.S. National Institutes of Health, Bethesda,
Maryland, USA. web: http://imagej.nih.gov/ij/, (1997–2016)
 Development of Techniques and Tools
for the Determination of Carbon Anode
Quality

Duygu Kocaefe, Yasar Kocaefe, Dipankar Bhattacharyay,

Bazoumana Sanogo, Yao Ahoutou, Hang Sun, and Patrick Coulombe

Abstract
The quality of prebaked carbon anodes, consumed in electrolysis during the primary
aluminum production, has an important impact on the cell performance. The anode quality
depends on the raw material quality and operating conditions in the anode plant.
Development of simple, quick, and inexpensive techniques and tools for anode quality
control will help industry identify the source of problems and take the necessary corrective
actions rapidly. In this article, different quality control tools developed to find the
wettability of coke by pitch, effect of mixing on coke particle size distribution, metallic
impurity content, optimum vibration time, pitch content in green anode, and the
measurement of green and baked anode electrical resistivities are presented. In parallel,
data analysis using the artificial neural network (ANN), a powerful statistical tool for such
applications, provides complementary information on quality and process. This article also
presents the potential utilization of ANN in quality control.

Keywords
Coke Pitch Image analysis Vibro-compactor Sound analysis Impurities
Colorimetry Resistivity

Introduction the exposed anode surface to produce CO2. These reactions

Primary aluminum is produced by the electrolysis of alumina
in the Hall-Héroult process. The anodes are the source of
carbon required for the reduction process. Carbon anodes
constitute an important part of the aluminum production cost
[1, 2]. During the production of aluminum, carbon anodes
are consumed and CO2 is produced [3]. CO2 further reacts
with the anode carbon to produce CO. Air also reacts with
D. Kocaefe (&)
Y. Kocaefe
D. Bhattacharyay
B. Sanogo
Y. Ahoutou
H. Sun
Centre Universitaire de recherche sur l’aluminium (CURAL),
University of Quebec at Chicoutimi, 555, boul. de l’Université,
G7H 2B1 Chicoutimi, QC, Canada
e-mail: dkocaefe@uqac.ca
P. Coulombe
Aluminerie Alouette inc., 400, Chemin de la Pointe-Noire,
C.P. 1650, Sept-Îles, QC G4R 5M9, Canada
increase anode consumption and add to the cost of aluminum
production. One of the key industrial goals is to minimize
this excess consumption of anodes. The energy consumption
increases with increase in electrical resistivity of anodes. In
general, high density, low specific electrical resistivity, low
permeability, low reactivity, high mechanical strength, and
high thermal shock resistance are the basic requirements of
good quality anodes [1]. The anode quality depends on the
raw material quality and operating conditions in the anode
plant. Improvement in anode quality can reduce the pro-
duction cost, energy consumption, and the emission of
greenhouse gases.
Anodes are produced using a mixture of dry aggregates
(calcined petroleum coke, recycled green and baked anodes,
and butts) and coal tar pitch. Petroleum coke constitutes
about 2% of the overall production of an oil refinery [4].
Thus, its quality is not necessarily a major concern for the
petroleum industry. Coal tar pitch, which is a binder for the

© The Minerals, Metals & Materials Society 2017 1247

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_149
1248
dry aggregate, is a residue produced by the distillation or
heat treatment of coal tar. Similar to coke, the quality of this
by-product is crucial for the anode quality. Variations in raw
material properties and quality create challenges for pro-
ducing of good quality anodes and maintaining the quality in
the aluminum industry.
Anode paste is produced by mixing dry aggregate with
molten pitch [3]. The interaction of dry aggregates with pitch
controls the mixing characteristics and the properties of
paste [5, 6]. The measurement of wettability for different
components of dry aggregate by pitch gives an indication of
the paste quality. Under good forming and baking conditions
[7, 8], a good quality paste will result in good quality
anodes. Thus, the measurement of wettability of a dry
aggregate by pitch is an important tool to control the final
anode quality. Also, the measurement of the granulometry of
particles before and after mixing indicates the efficiency of
mixing [9]. Currently, toxic solvents such as xylene are used
to remove pitch from paste to measure the granulometry of
the clean particles.
The paste is compacted by a press or a vibro-compactor
to produce green anodes. Nowadays, the industry usually
uses vibro-compactors. The green anodes are then baked at
high temperature during which pitch is carbonized [10]. This
helps bind the particles together and, consequently, decrea-
ses the electrical resistivity.
The vibration time used to vibro-compact the anode paste
is one of the key parameters that influence the properties of
carbon anodes. If the anode is compacted for a short time
(under-compaction), the green anode density will be low
giving high porosity. If the anode is compacted for a period
longer than necessary (over-compaction), the green anode
density will be high resulting in the formation of cracks in
the anode during baking [8]. Thus, under-compaction or
over-compaction of anodes leads to poor anode quality.
Variation in raw material quality, recipe, and other param-
eters can influence the optimum compaction time. Com-
paction for an optimum time helps produce good quality
green anodes, which is likely to produce good quality baked
anodes. Jonathan et al. [11] used the acceleration of the
vibro-compactor table to determine the optimum compaction
time. Gao et al. [12] used the movement of a bar fixed to the
cover of the compactor to determine this time. Such tools
were difficult to implement in the plant. Thus, a tool indi-
cating the optimum compaction time of the paste during the
compaction process is important to control anode quality.
The level and the distribution of pitch influence the
homogeneity of an anode. Non-homogeneity in anodes
results in non-uniform consumption in the electrolytic cell.
Also, baking is a costly process as it involves significant
amount of time and fuel. Presently, the quality of industrial
green anodes is judged by visual inspection [13] which may
lead to problems as the perceptions of different human
D. Kocaefe et al.
beings are different. A tool is necessary to evaluate the pitch
distribution in a green anode without damaging the anode.
This would help eliminate the “human factor” from the
quality control of a green anode and reduce the loss incurred
by baking defective anodes.
Additional carbon is lost during the electrolytic process
due to air and carbon dioxide reactivities [14]. Impurity
content in the anode controls the reactivities significantly.
There are different standard methods to quantify the impu-
rities. The American Society for Testing and Materials
(ASTM) developed different test methods using Inductively
Coupled Plasma Atomic Emission Spectrometry (ICP-AES),
Atomic Absorption Spectrometry (AAS), and X-ray Fluo-
rescence Spectroscopy (XRF) [15]. These standard methods
require intensive sample preparation, highly skilled person-
nel, and costly reagents. The methods are usually
time-consuming. Thus, a simple but effective tool is neces-
sary to estimate the level of different impurities in the raw
materials and the anode. This tool can help control the
quality of an anode.
Electrical resistivity is an important property which
shows the quality of an anode. High resistivity values in a
green anode indicate the presence of cracks or high con-
centrations of pitch [16]. High resistivity values in a baked
anode however show the presence of cracks [16].
Over-pitching in a green anode could create high
porosity/cracks in the baked anode due to higher
devolatilization at a particular location. The distribution of
electrical resistivity in an anode shows the level of
non-homogeneity in that anode. The problems in the green
anode will have consequences later on during baking and
electrolysis, resulting in high energy and carbon consump-
tion [16, 17]. Hence, a tool is necessary for the industry to
determine the distribution of electrical resistivity in green
and baked anodes to control quality.
The study of the impact of raw material quality as well as
processing parameters for the production of anodes on baked
anode properties is of great importance. The strength of the
plants is their collection of vast amount of data related to the
quality of raw materials, process conditions and the quality
of baked anodes. However, the data are complex; and it is
hard to analyze using conventional methods. Artificial neural
network (ANN) is a mathematical tool that can analyze these
data and can predict baked anode properties based on the
quality of raw materials and process parameters even before
baking [18]. Models based on ANN can help produce good
quality anodes, minimize rejections, and improve anode
quality. Berezin et al. [1] used ANN to predict problems in
an aluminum reduction cell. Meghlaoui et al. [19] developed
an ANN model for efficient control of alumina feeding in the
electrolytic cell. Bhattacharyay et al. [18, 20, 21] have
studied the effect of different parameters on anode
properties.
Development of Techniques and Tools for the Determination …
Different Tools for the Quality Control
of Anodes
Different tools were developed to monitor and control anode
quality at different stages of production based on industrial needs.
Wettability of a Dry Aggregate by Pitch
The wettability of the different components (coke, butts, etc.)
of a dry aggregate by a pitch drop was characterized with the
contact angle formed between the pitch drop and the solid
particle bed. The wettability was measured by the sessile
drop method at 170 °C under inert nitrogen atmosphere. The
dynamic contact angle was determined by using a video
recorder, and the contact angle was measured from the
images using the FTA 32 software [5, 6, 22]. The higher the
contact angle is, the lower the wettability of the solid particle
by the pitch is.
Granulometry of Paste
An inexpensive, quick, and environmentally-friendly
method was developed to remove pitch from the paste
using a nontoxic solvent [9]. The paste was dipped in the
solvent for a specified time. The clean particles were dried
and sieved, and then the granulometry was measured. Fig-
ure 1 shows the steps of the process.
Measurement of Impurities in Raw Materials
or Anodes
A method was developed to extract metallic impurities
(transition metals iron, vanadium, nickel) from carbon
Fig. 1 Extraction of pitch from anode paste [9]
1249
Fig. 2 A schematic view of the set-up to analyze color
samples by chemical reaction as well as electrophoresis [23].
The extracted metallic impurity was measured by col-
orimetry. The solution of the extracted metal was treated
with a reagent to produce a color. The schematic of the
set-up is shown in Fig. 2. The picture of the colored solution
in a plastic container was taken using a camera, and the color
of the picture was analyzed after a certain time with a
custom-made software. A calibration curve was prepared by
plotting a color component with the known concentration
(measured by XRF) of the impurity. The calibration curve
was later used to determine the concentration of the metallic
impurity in an unknown sample. The method was validated
in the presence of interfering ions.
Determination of Optimum Vibration Time
Using Sound Analysis
A tool was developed to determine the optimum compaction
time based on the analysis of sound of the vibro-compactor.
In this method, the sound of the vibro-compactor was
recorded using a microphone (Audio Technica ATR6550
Condenser Shotgun) and a custom-made software. The
recorded sound during the compaction process was analyzed
using the software. The rates of change in the levels of the
sound of the vibro-compactor were calculated in a certain
frequency range. The optimum time of compaction was
determined based on the rate and some predetermined
threshold values. Figure 3 shows the position of the micro-
phone used for the analysis.
Measurement of Pitch Distribution Using Image
Analysis
An image analysis tool was developed to analyze the level
and the distribution of pitch on the green anode surface.
Figure 4 shows a schematic view of the set-up. The anode
surface was illuminated uniformly. Then, the picture
(mvBlueFOX USB2.0 camera) of the surface of the anode
was taken and different color components were analyzed
1250
Fig. 3 Position of the microphone
Fig. 4 A schematic view of the set-up to analyze the pitch distribution
on a green anode surface
with a custom-made software. The software determines the
value of color component above which there is high level of
pitch on the anode surface. These positions are marked with
pink colors in the picture. It also measures the size distri-
bution of the pink patches. A large-size pink patch means a
significant concentration of pitch at that point, and such
anodes may create problems during baking.
A spectrophotometric method was also developed to
measure the level of pitch in an anode sample. The pitch was
extracted with a solvent and the quantity of pitch was
measured by a UV-visible spectrophotometer at a particular
wavelength of light. The pitch levels in anode samples were
measured by the spectrophotometric method to validate the
image analysis results.
Measurement of Electrical Resistivity Distribution
A simple, fast, and non-intrusive method and equipment,
SERMA (Specific Electrical Resistance Measurement of
Anodes) was developed to measure the distribution of
electrical resistivity in an industrial anode. A current was
passed at multiple points through the anode block from one
surface to the opposite surface, and the corresponding
D. Kocaefe et al.
voltage drops are measured. The electrical resistivities at
different points were calculated across the anode. This
technique could be used for both green and baked anodes.
A low current level is used (in the order of about 10
amperes) to make it easy to implement in the plant. Low
current levels also ensure that any perturbation in the anode
is small.
Four plates were used to carry out the measurements: two
plates between the top and bottom surfaces of the anode and
two plates between the side surfaces. Each pair of plates
contains a certain number of flexible contacts at exactly the
same positions to feed current from one surface and to
receive it from the opposite surface. These contacts were
connected to a power supply and the circuit was completed.
Close to the current contacts, the voltage contacts were
installed on both plates to measure the voltage drop at a
given position. The current and voltage contacts were dis-
tributed over the plate covering the entire anode surface. The
results were plotted to identify the defects in the anode. The
schema of the set-up was published elsewhere [16, 17].
Artificial Neural Network (ANN)
Different custom made feed-forward ANN models were
developed. The models were trained by experimental data.
The model identifies the pattern in the experimental dataset.
The model was then validated with the experimental data
which were not used for training. The validated model was
used to predict different anode properties for which no
experimental data are available. The description of different
ANN models were published elsewhere [18, 20, 21].
Results and Discussion
Wettability of a Dry Aggregate by Pitch
A number of studies were published [5, 6, 9, 22] in the
literature by the research group on the wettability of different
types of coke by different pitches. Figure 5 shows the wet-
tability of a particular coke by different pitches and the
densities of the green anodes produced by the coke-pitch
pairs [22]. The wettability was expressed in terms of contact
angle. A low contact angle indicates high wettability of coke
by pitch. The results show that the green anode density
(GAD) increased when the contact angle was low (good
wetting). Thus, the tool helps identify the suitable coke-pitch
pair. Good wettability of coke by pitch will result in a good
green anode density.
Development of Techniques and Tools for the Determination …
Fig. 5 Comparison of contact angle for a particular coke wetted by
different pitches, and the densities of the green anodes produced by the
coke-pitch pairs [22]
Fig. 6 Coke fraction distribution before and after kneader [9]
Granulometry of Paste
The method was developed to determine the granulometry
before and after mixing with an industrial kneader (Fig. 6)
[9]. In this figure, particle size decreases from 1 to 6. Very
fine particles (ball mill product, filtered dust) were not
included in this analysis because the emphasis was to
investigate if the large particles were crushed during
kneading. Figure 6 shows that there were changes in the
particle size fractions of 1 and 2. Reduction in coarser size
fractions resulted in an increase in smaller size fractions (size
5 and size 6).
Measurement of Impurities in Raw Materials
and Anode Samples
Different coke and butt samples were used for the analysis.
The samples were treated with acid followed by elec-
trophoresis. Measured amount of the clear solution obtained
by electrophoresis was treated with reagents to produce a
1251
Fig. 7 Colors produced by the coke extract containing a iron,
b vanadium, and c nickel
certain color. Figure 7a–c shows the color produced by iron,
vanadium, and nickel, respectively.
Table 1 shows the validation of the colorimetric method
by comparing with the XRF analysis. The results show that
the colorimetric method could estimate the impurity levels in
carbon samples with a reasonable precision. The differences
in the values might be due to the non-homogeneity of the
samples. The analysis time was around 30 min, and no
special sample preparation was necessary. In all cases,
standard laboratory grade reagents were used. Thus, the
method was fast, inexpensive, but reliable. The method
worked for both coke and butt samples.
Determination of Optimum Vibration Time Using
Sound Analysis
During the compaction of paste in a vibro-compactor to form
a green anode, there are three phases: reorganization of the
particles, compaction, and stabilization [24]. Figure 8 shows
a typical analysis of the sound of a vibro-compactor, and
three phases can be clearly identified. Certain criteria were
used to identify the end of each phase. An anode which
passes through all these phases is compacted well. Specific
criteria were used to mark the end of the stabilization phase
to determine the optimum compaction time. Experimental
studies showed that the anodes compacted for optimum time
had high green and baked densities.
Four anodes were fabricated using the same raw material
and under the same conditions for validation. The time of
compaction was maintained the same. The sound of the
compactor was analyzed, and the optimum compaction time
was identified for each anode. The difference between the
actual and the optimum compaction times showed the level
of over-compaction of the green anode. The anodes were
baked and the ratio of the baked anode density (BAD) to the
green anode density (GAD) was plotted as a function of
the over-compaction time (Fig. 9). The results show that the
BAD for the same GAD increased when the over-
compaction time decreased. The anodes compacted close
to the optimum time had relatively higher baked density. The
study also shows that the non-homogeneity of the raw
materials has an influence on the optimum time of
compaction.
1252 D. Kocaefe et al.

Table 1 Comparison of XRF Impurity Sample Concentration, ppm

and colorimetric results for
different impurities Measured by XRF Measured by colorimetry
Iron Coke 100 92
Butt 260 270
Coke 200 210
Vanadium Coke 330 335
Butt 390 390
Coke 320 318
Nickel Coke 170 171
Coke 160 161
Butt 150 149
Coke 200 201

for baking. If this problem is found repeatedly, then the pitch

content of the anode, mixing and forming conditions should
be assessed.
To validate the method developed for the determination
of pitch distribution on a green anode surface using image
analysis, tests were performed using laboratory anodes.
Different sections of a laboratory anode surface (see
Fig. 11a) were analyzed by the image analysis technique
(results are shown in Fig. 11b) and the spectrophotometric
method. The results are summarized in Fig. 12 which shows
that there is a good correlation (R2 = 0.95) between the
Fig. 8 Different phases of compaction obtained from the analysis of
percentages of pink patches with the amount of pitch
the sound of a vibro-compactor
determined by the spectrophotometric method. Thus, the
pink patch on the anode surface can be an indicator of the
distribution of pitch on the anode surface.

Measurement of the Electrical Resistivity

Distribution

The overall resistivities of different industrial green and

Fig. 9 Change in the BAD/GAD ratio as a function of the level of
over-compaction
Measurement of Pitch Distribution Using Image
Analysis
Figure 10a shows the picture of the surface of a rejected
industrial green anode, taken by a digital camera under
certain lighting conditions. Figure 10b shows the locations
with high pitch concentrations (marked in pink). The picture
shows high pitch content on the top right corner of the
anode. It also shows high pitch content at the top of the slots.
The size of the patches shows that the anode is not suitable
baked anodes were measured using SERMA. Then, cylin-
drical core samples were taken from different sections of the
anodes, and the resistivities of these samples were measured
according to the ASTM standard. The resistivities of anodes
measured by SERMA and those of the cores were compared
[17]. Figure 13 shows that a reasonably good correlation
was found between the average resistivity measurements
obtained with the equipment and those of the cores. The
method can be used for both green and baked anodes.
Artificial Neural Network (ANN)
Industrial as well as published data were analyzed using the
ANN model. The ANN model was found to identify the
effect of a particular component better than the linear
Development of Techniques and Tools for the Determination … 1253

Fig. 10 a Picture of the surface of a rejected green anode, b Analysis of the surface (Pink color shows high pitch concentration) (Color figure
online)

Fig. 11 a Different sections of a lab anode, b Results of the image

analysis of the surface

Fig. 13 Comparison of average non-dimensional resistivities mea-

sured using SERMA with those determined from the cores taken from
different positions in the green and baked anodes [17]

Fig. 12 Comparison of the results of the spectrophotometric and

image analysis techniques for different anode sections

multivariable analysis and partial least square methods [21].

For example, it is difficult to determine experimentally the
effect of a particular impurity since it is not possible to change
the concentration of only that impurity while keeping the
others constant. An example for such a case is presented here.
Figure 14 shows that both vanadium and iron could catalyze
the CO2 reactivity of anodes [18, 25–27]. This observation is
supported by different researchers. The ANN study showed
that both elements showed similar effect when their con-
centrations were low. However at high concentrations iron
seems to have more influence on CO2 reactivity [20].
Fig. 14 Effect of vanadium and iron on CO2 reactivities [16]
Conclusions
Techniques and tools were developed to determine the
sources of the anode-quality related problems. Wettability
measurements give an idea on the degree of interaction
between coke and pitch. A method was developed to
1254
measure the particle distribution in paste to see if the kneader
affected the granulometry. The above two methods can help
obtain a good paste, which leads to good quality anodes
provided that the other conditions are suitable as well.
Metallic impurities affect the anode reactivity and conse-
quently carbon consumption. With the methods developed,
metallic impurities in raw materials or anodes can be mea-
sured. If the vibro-compaction time is not well-chosen,
anodes can be under or over-compacted, leading to the
deterioration of the anode quality. The method developed
can determine the best vibration time for each anode.
A method was also developed to measure the surface pitch
distribution of green anodes, which identifies over and
under-pitched anodes. A method and equipment (SERMA)
were developed to measure the electrical resistivity distri-
bution in anodes, which can detect the actual location of a
defect. The last three methods have the potential for on-line
use in plants. The ANN model can be used to analyse the
vast amount of data available in the plants to get information
on the relationship between various parameters, including
the impact on anode quality. Above tools can help industry
apply immediately the necessary corrective action when a
problem is detected.
Acknowledgements The technical and financial support of Alu-
minerie Alouette Inc. as well as the financial support of the Natural
Sciences and Engineering Research Council of Canada (NSERC), the
Développement économique Sept-Îles, the Université du Québec à
Chicoutimi (UQAC), and the Foundation of Université du Québec à
Chicoutimi (FUQAC) are greatly appreciated.
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 Flow Detection Module—A New Model
to Predict the Flow in Open Pit Anode Baking
Furnaces

Detlef Maiwald, Domenico Di Lisa, Florian Krummrich,

and Frank Heinke

Abstract
A continuous measurement of the flow inside the flues of baking furnaces is still a
challenge that has not been solved. As a substitute, the draft is measured in one position of
each flue to determine the existence of a volume or flow. Knowing the real flow would be
of the essence for a more accurate and optimized control of the combustion inside the
furnace. A mathematical model for flow detection, based on fuzzy logics was developed to
determine the actual flow in each flue. With the introduction of this flow detection module,
each flue in a furnace is continuously evaluated. The on-line mathematical model calculates
the actual flow in each flue by correlation of the relevant process data available in the firing
system. As a result, the baking process is further optimized for lowest emissions and best
fuel efficiency. The paper illustrates the mathematical approach and shows the results.

Keywords
Anode baking furnace Firing control system Flow detection

Introduction
The anode baking process is running basically as a double
heat ex-changer with a firing zone in between. These areas
are the preheat, firing and cooling area. The areas are
“connected” by the flue gas. The flue gas is acting as a
cooling fluid in the cooling area, as preheated combustion air
in the heating area, and as a heating fluid and additional
combustion air in the preheat area. The volume and flow for
the flue gas is generated by the exhaust fans of the fume
treatment centre. The furnace is operated under negative
pressure respectively in draft mode as shown in Fig. 1.
A temperature-versus-time function related to the desired
target temperature for the anodes determines the baking
process, where the anodes have to be heated up to 1100 °C.
The flow inside the flue walls—the flue gas—is a key
parameter for the control, quality and safety of the baking
D. Maiwald (&)
D. Di Lisa
F. Krummrich
F. Heinke
Innovatherm, Am Hetgesborn 20, 35510 Butzbach, Germany
e-mail: dmaiwald@innovatherm.de
process. The exact flow is not known, because the direct
measurement inside the flues is not possible.
Past trials and developments of flow detection and mea-
surement devices either in the flue walls or in the boots of
the exhaust ramp have finally failed. This failure was not
because of the measuring device as such—the venturi pipe
was in principal working inside the exhaust boot – but it was
mainly due to the disturbances of the furnace itself. Leak-
ages, air ingress etc. lead to a significant drop in the neg.
pressure without significant drops in flow as shown in
Fig. 2, where a flue blockage was simulated (Ref. [1]).
Currently the flow is determined by the measurement of
the negative pressure inside each flue wall. This is executed
by the TP-measuring ramp in the 2nd section of the fire. For
control of the furnace, the negative pressure is just used as a
“vehicle” in a cascaded control loop in the preheat area,
where the focus and master control is the temperature
development in the preheat area represented by a forced
temperature heat-up setpoint curve.
The requirement to achieve new benchmarks is continu-
ously increasing. Knowing the real flow would be of the
essence for a more accurate and optimized control of the

© The Minerals, Metals & Materials Society 2017 1255

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_150
1256
Fig. 1 Principle of the anode
baking process
Fig. 2 Blockage simulation and
effect on flow
combustion inside the furnace. The control of the flow
would lead to lower energy consumption, higher anode
quality and lower emissions which are forced by new leg-
islations for environmental limits.
The Idea
The direct measurement of the flow is not possible. The idea
is to take the characteristic of the damper inside the exhaust
manifold in correlation to the main draft as a definition of an
ideal and undisturbed flow (Videal), and to detect deviations
of the flow through all measurements and data available on
the furnace. Finally these data are fed into a mathematical
D. Maiwald et al.
model to calculate and determine the disturbances of the
ideal flow (Vdisturbances). This will lead to an estimation of the
real flow (Vreal) inside the flue as per following equation:
Vreal ¼ Videal  Vdisturbances
Following measurements and actuators (Fig. 3) in
state-of-art furnace firing control systems are available in the
preheat area:
1. The main negative pressure (draft) Pmain, measured in
the exhaust manifold
2. The main temperature Tmain, measured in the exhaust
manifold
3. The damper position Dpos (feedback) of each flue
Flow Detection Module—A New Model to Predict …
Fig. 3 Usable preheat area
signals
4. The temperature Tflue and the Temperature gradient
Gflue in the first section of each flue
5. The negative pressure Pflue of each flue
6. The temperature target curve (baking curve) of the pre-
heat section
Research and developments that can detect disturbances
of the flow have been undertaken in the University of Jena
and on an existing production furnace to develop correla-
tions between these parameters, which can detect distur-
bances of the flow that cannot be observed by just the
measurement of the negative pressure. Finally a flow control
model was developed using a fuzzy logic model, described
in detail in the subsequent sections.
Fuzzy modeling was selected to be the most appropriate
approach for this problem. In addition to the basic physics,
the flow in a baking furnace is influenced by many
non-physical parameters. These cannot be described by
equations, but by linguistic methods. Fuzzy modeling forms
a system model using a description language based on fuzzy
Fig. 4 Flow disturbance
detection and control model
1257
logics with fuzzy predicates. It is a qualitative modeling
scheme describing system behaviours using a natural
language.
The Flow Control Model
The new flow control model is shown in the following fig-
ure: (Fig. 4).
As input data for the model, all measurements as described
above are chosen to be a part of the real flow detection and
estimation. But these measurements have to be pre-processed
in order to use them as characteristic input for the model.
The Flue Draft
The flue draft is one of the most important measurements in
the anode baking process. It represents the “undisturbed”
amount of flow inside a flue. The flow for each flue is
1258
adjusted by the damper in the exhaust ramps. Therefore it is
used as an input parameter for the model. But before it can
be used for the model, it has to be corrected by the first
major disturbing factors in the process: disturbances of the
main negative pressure, the damper characteristic and the
temperature.
Main Negative Pressure Correction
The main negative pressure represents the source of flow,
generated by the fans of the FTC. The flow is adjusted by the
damper in the exhaust ramps. Disturbances in the main draft
will have an influence on the flue draft at the same damper
positions. Therefore it contains two correction factors m and
n. They represent a correction between an ideal main draft
and the real main draft as shown in the following equations:
pnorm  pdisturbed DpFlue
mmain ¼ ¼
pmainnorm  pmaindisturbed DpMaindraft
nmain ¼ mmain
pmainnorm
ymaincorrect ¼ mmain
xmain þ nmain ¼ YD
YD will be the correction output and serving as an input for
the model. The parameters m and n will be tuned during
model calibration on the furnace.
Fig. 5 Characteristic damper curve
D. Maiwald et al.
Damper Correction
The ideal damper characteristic for the volume (0…100%)
versus the damper position (0…100%) is another measure-
ment used as model input.
The damper contains a specific characteristic between
degree of opening and flow as shown in Fig. 5.
The damper position is corrected by the damper curve
module as follows:
1. Take the opening—flow characteristic of the used
damper
2. Find a linear equation between damper opening and
resulting negative pressure
3. Adjust the parameters of the linear equation during cal-
ibration phase of the model.
The adjustment is based on the furnace design and is in
proportion to the flow resistances. It is an adaption of the real
measured influence of the damper (red cloud represents real
draft values) as shown in Fig. 6. The equations used for
correction and adaptation can be found below.
xcorrection ¼ es
x þ e0
ycorrection ¼ as
y þ a0
Flow Detection Module—A New Model to Predict … 1259

Fig. 6 Damper curve versus draft (negative pressure)

Finally the output of the damper correction and we can follow:

pre-processing represent an expected flue draft for each
2
V_
damper position. f
A
Rsp
T f
V_ 2
p
Dp ¼ ¼
2 2
R s
T
A2

Temperature Correction f ¼ Rs ¼ A2 ¼ constant

and
The physical relation between flow and pressure is described
in the Bernoulli equation. For p ¼ pgeo þ pdyn þ pstat
q 2
pþ u ¼ p0 pgeo  pdyn þ pstat follows p ¼ constant
2

m_ V_ V_ 2
u¼ ¼ Dp /
q
A A T
The pressure is in a direct quadratic relation to the flow and
and
indirect proportional to the temperature. So the temperature
q has a direct and significant influence on the real flow, that
Dp ¼ f

u2
2 needs to be corrected.
1260 D. Maiwald et al.

Temperature Gradient back to a deterministic output value through a method of

Temperature gradients of each flue of the preheat area are the
final values taken as an input into the fuzzy model. The
temperature behavior, especially the gradient and the dif-
ference between a given set-point versus the actual temper-
ature (shown as YG and YT) is a clear indicator for the
behavior of the flue with regards to the actual and real flow
inside the flue wall.
The Fuzzy Model
The Fuzzy model as shown in Fig. 7, is now fed by the
following 3 pre-processed input variables:
center of gravity.
For each of the variables YG, YD and YT, the fuzzy-
fication variables are set as a trapeze function. The vari-
ables can be parameterized as shown in Fig. 8. The range
of deviations are characterized by 3 variables NB- negative
big deviation, ZO-zero or no deviation and PB-positive big
deviation.
The parameters can be also illustrated in a graphical fuzzy
field as shown in Fig. 9.
The next step in the fuzzy module to be defined is the
Inference, fed by the set of rules between the variables.
The model’s 3 variable structure require 27 rule definitions. The
basic structure of the rules is shown in the following table:

1. YD—pre-processed draft/flow value deviation Variable 1 Variable 2 Variable 3 Status

2. YG—pre-processed temperature gradient deviation If YD = too AND AND THEN
3. YT—pre-processed temperature deviation high YG = negative YT = negative 5
If YD = too AND AND YT = ok THEN
The fuzzy model consists of 3 function blocks, namely high YG = negative 4
If YD = too AND AND THEN
1. Fuzzyfication high YG = negative YT = positive 3
The Fuzzyfication transforms an input variable into a If YD = too AND AND YT = ok THEN
linguistic term, describing the different conditions of this high YG = good 2
variable If YD = good AND AND YT = ok THEN
YG = good 1
2. Inference
The Inference defines the dependencies of the input The status column indicates the result of the specific rule,
variables through a set of linguistic rules (IF…THEN … where status 5 represents the worst and status 1 the best
ELSE) condition. The rules for the inference can also be calculated
dynamically and graphically presented. The 3D table in
3. Defuzzyfication Fig. 10 shows the interdependencies for the whole set of
The Defuzzyfication transforms the processed variables variables.

Fig. 7 The fuzzy model

Flow Detection Module—A New Model to Predict … 1261

The variable a represents now the quality of the flow,

normed to 0 … 100%. 0% means no deviation of the flow.
100% means the flow is disturbed at maximum.

Results

For evaluation of the model in an industrial environment, a

Fig. 8 Parameter field of the fuzzy variables test installation was done in a European Smelter. The model
was implemented into the existing level 2 process control
system.
To prove the model, the following tests were executed:

– Test 1: Simulation of a “leakage” in flue 3 at the exhaust

ramp. This was realized by removing one sealing baffle
behind the exhaust manifold in flue 2 of the fire
– Test 2: Opening of a peephole cover in flue 3 of Sect. 1
– Test 3: Opening of 5% of the headwall cover in flue 2.

Fig. 9 Graphic illustration of fuzzy parameters

Test 1

Removing one baffle allows false air to enter the exhaust

ramp—instead of process gas from the flue. The results of
the model output is shown in Fig. 11.
The blue curve represents the flue draft, the red curve the
flue temperature, the orange curve the damper position, the
white curve the main draft and the bold red curve is the
calculated output “a” of the fuzzy flow model.
The baffle was removed at 11:12. It can be observed, that
the model detects the drop in flow, the value changes from
17% up to 100%. At time 11:19 the baffle was set back into
position. The draft increases, slightly overshoots and finally
stabilizes at a new setpoint. This behavior is also detected
significantly in the output of the model. The behavior at time
11:32 is also interesting because the main draft shows a
Fig. 10 Inference significant drop from 50 to 42%. Also this disturbance is
detected by the model as it was expected to be. Finally at
time 11:45, all disturbances are settled and the model output
Finally the Defuzzyfication is required. This is done by a
shows a value between 0 and 5% of remaining disturbances,
special method of gravity through singletons.
in accordance with the model prediction.
P
n
xi
li
xi ¼ Singletonposition
a ¼ i¼1P
n Test 2 and Test 3
li ¼ Aggregationvalue
li
i¼1
Test no. 2 simulated smaller flow disturbances by opening
In our case with 5 different conditions the output variable a one peephole in flue no. 3 as shown in Fig. 12 and Test no.
can be calculated 3 Test no. 3 opened a headwall cover by 5% in flue no. 2, see
Fig. 13.
l1
0 þ l2
25 þ l3
50 þ l4
75 þ l5
100
a¼ The test started at 10:25 and was stopped at 10:59.
l1 þ l2 þ l3 þ l4 þ l5
1262 D. Maiwald et al.

Fig. 11 Graphic history: output of the flow model

The graphs in Fig. 14 show the results of the model for This output can directly be used to generate an alarm for
Flue 3 with the 5% open headwall cover. the operator for a “disturbed” flow in a specific flue. The
The graphs in Fig. 15 show the results of the model for
Flue 2 with an open peephole cover.
Results indicate that the fuzzy model detects the flow
disturbances very precisely and generates a signal in the red
colored area (80–100% disturbance).

Fig. 12 Peephole opening for false air simulation Fig. 13 Head wall opening by 5%
Flow Detection Module—A New Model to Predict … 1263

Fig. 14 Output of the flow model for 5% open headwall cover

Fig. 15 Output of the flow model with an open peephole cover

output can also be used to generate the “real” flow signal flooding index module, the pitch burn module and burner
Vreal for further processing and optimization of the com- capacity limitation to further fine tune and adapt the process
bustion system. This value will be used now inside the automatically.
1264 D. Maiwald et al.

Conclusion and Summary References

A new mathematical model for flow detection, based on 1. P. Mahieu, A. Pinoncely, J. Peenz, Reliable blocked flue wall
fuzzy logics was introduced. The test results show a good detection for enhanced safety in anode baking furnaces. Light
correlation to any variations of the flow. The flow detection Metals (2009)
2. F. Krummrich, Bachelor Thesis: Entwicklung eines Moduls zur
module will be a robust instrument to detect flow distur-
quantitativen Volumenstromdetektion in Anodenöfen, University of
bances and can react dynamically in the fire regime to: Applied Sciences Jena (2012)
3. D. Maiwald, D. Di Lisa, Innovatherm advanced control modules
– Improve process quality and control philosophy—the success for high quality anode
production in open top ring furnace. Aluminium World (2008)
– Improve energy efficiency
4. D. Di Lisa, H.P. Mnikoleiski, D. Maiwald, Homogenized anode
– Improve flue gas emissions baking quality. Light Metals (2009)
– Improve furnace operational safety
 Formation of Carbon Build-Up on the Flue Wall
of Anode Baking Furnace

Zhaohui Wang, Stein Rørvik, Arne Petter Ratvik, and Tor Grande

Abstract
A hard carbon build-up layer often forms on the flue wall surface in anode baking furnaces.
The layer accumulates over thermal circles and needs to be mechanically removed regularly
to ensure sufficient space for the anodes between flue walls. The underlying mechanisms
are still unknown and the extent of the carbon build-up varies from plant to plant. The
build-up on the flue wall, taken from an autopsy of an open top furnace, has been
examined. Microstructure and phase compositions of the carbon build-up, especially
towards the refractory interface, were studied by optical microscopy, X-ray computed
tomography (CT), SEM/EDS, and XRD. Pyrolytic carbon was found to be the main part of
the carbon build-up layer in addition to packing coke particles. The transport of silicon
from the refractory material, condensating on the flue wall surface, is found as nucleation
sites for the formation of carbon build-up. Formation mechanisms of the carbon build-up
are proposed with reaction schemes supported by thermodynamic calculations.

Keywords
Carbon build-up Anode baking furnace Pyrolytic carbon

Introduction species, mechanical impact and large temperature gradients

Reducing the maintenance cost and/or expanding the lift
span of refractories in anode backing furnace is one way to
reduce the cost of aluminium metal production. Carbon
anodes used in aluminium electrolysis can vary in compo-
sition, but are normally made from around 70% petroleum
coke, 15–20% butts, and 14–15% coal tar pitch as a binder.
The green anodes need to be baked before they can be used
in aluminium metal production. Volatiles will be released
mainly from the pitch during heat treatment of the green
anodes. The soaking temperature in the baking furnace is
between 1200 and 1250 °C. The refractories of the flue walls
are subjected to chemical attack, mainly from gaseous
Z. Wang (&)
S. Rørvik
A.P. Ratvik
SINTEF Materials and Chemistry, 7465 Trondheim, Norway
e-mail: zhaohui.wang@sintef.no
Z. Wang
T. Grande
Department of Materials Science and Engineering, Norwegian
University of Science and Technology, 7491 Trondheim, Norway
resulting from the thermal cycles. The refractories degrade
overtime, especially the surface facing the packing coke
towards the anode pits [1–5]. In addition to the mineralogical
phase transition of the refractory materials, a hard carbon
build-up layer often forms on the flue wall surface in anode
baking furnaces. The layer accumulates over thermal cycles
and regularly needs to be removed mechanically to ensure
sufficient space for the anodes between flue walls. The
underlying mechanisms of the carbon build-up formation are
still not properly understood, and the extent of the carbon
build-up varies from plant to plant.
The carbon build-up on the flue wall, collected during an
autopsy of an open top furnace, was studied in this work.
The investigation was focused on the microstructure evolu-
tion and phase transformation through the build-up layer
and at the refractory interface. The formation mechanisms
and the corresponding reaction schemes were revealed and
supported by thermodynamic calculations using FactSage
[6].

© The Minerals, Metals & Materials Society 2017 1265

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_151
1266
Autopsies of Spent Flue Wall
Refractory bricks together with carbon build-up layer were
collected from a spent flue wall during an autopsy of an open
baking furnace with a lifetime of about 4000 days. The
carbon build-up layer was around 1–2 cm in thickness.
Samples, including the interface between the refractory and
the carbon build-up layer, were collected to investigate
microstructure evolution and mineralogical phase transfor-
mation taking place at the interface. Cross-section samples
and powder samples were prepared for characterisation.
A piece of carbon build-up layer and a polished interface
cross-section sample are shown in Fig. 1. A thin black car-
bon build-up layer could be observed at the refractory
interface. Figure 1 also illustrates a schematic drawing partly
showing an open top furnace structure including the hollow
refractory flue wall, the packing coke and the anode, which
are relevant for the present work. The sampling positions are
marked in the drawing. Pristine packing coke particles were
collected for comparison.
Microstructure and phase analysis has been performed on
the carbon build-up cross-section and at the refractory
interface by scanning electron microscopy (SEM) using
LV-SEM HITACHI S-3400 N equipped with an energy
dispersive spectrometer (EDS) (Hitachi, Japan). Samples
with fractured surfaces were also used for a better view of
the morphology of each phase. Carbon structure was
investigated using optical microscopy with polarizing filter
(POL MET) (REICHERT MeF3A). Powder X-ray diffrac-
tion (XRD) was performed to detect the main phases in
carbon build-up by using a Bruker D8 Focus diffractometer
Fig. 1 Carbon build-up sample (left top), interface sample (left
bottom), and a schematic drawing (right) partly showing an open
anode baking furnace structure which is relevant to the present work. 1
hollow flue wall bricks, 2 gaps in flue walls to exhaust the volatiles, 3
packing coke, 4 green anodes, and 5 carbon build-up on flue wall
surface. Figure only for illustration and not in scale
Z. Wang et al.
with a LynxEye PSD detector (Bruker AXS, Karlsruhe,
Germany).
Non-destructive X-ray Computed Tomography (CT) was
used to inspect the 3-dimensional interior microstructure of
the refractory and the carbon build-up, including the inter-
face, using a Nikon XT H225 ST X-ray CT scanner (Nikon
Metrology, UK). A tungsten reflection target was used
without any filtering. Acceleration voltage was 140 kV with
a current of 130 lm, and the image acquisition was done
with an integration time of 2000 ms and 3142 projections
(p  1000) per revolution. A cylindrical sample (1 cm in
diameter and 1 cm in height) was used for the CT scan. The
scanned volume is 2000  2000  2000 voxels, with a
voxel size of 5.5 lm in all three directions.
Carbon Build-up Layer
The carbon build-up layer was first investigated by SEM/EDS.
Figure 2a shows the electron image of carbon build-up
cross-section, where a coke particle is labelled as number 1
and a white spot is labelled as number 3 while the layered
structures growing outwards from the surface of the coke
particle and the white spot is labelled as number 2. Figure 2b
shows the electron image of carbon build-up sample with a
fracture surface, where the vivid laminar phase are demon-
strated. EDS analysis confirmed that the laminar phase was
carbon and the white spots were silica with a minor Na content.
Polarized optical microscope was used to investigate the
laminar carbon phase. The polarized light micrographs are
presented in Fig. 3, where (a) shows the spherical laminar
structure growing into free space, and (b) shows colourful
ribbons surrounding coke particles. The laminar carbon
phases have crystallised in a planar order. Cleavage planes
are clearly shown in the figures. This high-textured carbon
phase is pyrolytic carbon [7, 8]. The rough Maltese-cross
imply the pyrolytic carbon formed in carbon build-up layer
was “rough laminar pyrocarbon” with very anisotropic
properties.
The thickness of the pyrolytic carbon layers varied along
the carbon build-up cross-section. Thicker layers around
100 µm were observed near the flue wall surface as pre-
sented in Fig. 4a–b, while slightly into the packing coke the
layers were thinner and less than 10 µm as shown in
Fig. 4c–d. Micro-cracks inside the pyrolytic carbon crystals
along the cleavage plane are clearly visible in Fig. 4b.
The main phases detected by powder XRD in the carbon
build-up layer were graphite and cristobalite, which was in
agreement with SEM/EDS results. XRD diffractograms are
shown in Fig. 5. Pristine packing coke is also shown for
comparison. The splitting of the C002 peak is pronounced
compared to pristine coke, which is due to the presence of
pyrolytic carbon with higher crystallinity.
Formation of Carbon Build-Up on the Flue Wall … 1267

Fig. 2 SEM images of carbon build-up. a cross-section, and b fracture surface. 1 packing coke particle; 2 layered carbon structure growing on top
of the coke particle and white spots; 3 white silica spots

Fig. 3 Polarized light micrographs of cross-section of carbon build-up. a spherical laminar structure with cleavage planes, and b ribbon-like
structure surrounding a needle coke particle. The two figures have the same magnification

Fig. 4 Polarized light

micrographs of cross-section of
carbon build-up. a–b position
towards flue wall, and c–
d position towards packing coke
1268
Fig. 5 XRD diffractograms for carbon build-up and pristine packing
coke
Refractory Interface
The polarized light micrographs of the refractory interface
are presented in Fig. 6. The refractory material is purple due
to the low reflectivity under polarized light. The figure
clearly demonstrates that the pyrolytic carbon nucleated on
the refractory surface and grew outwards. Several distinct
layers could be observed which probably resulted from
several thermal cycles. The pyrolytic carbon also infiltrated
into the refractory through pores and deposited on the pore
surface. The infiltration depth varied and was in the average
of several hundred lm in this sample. The carbon infiltration
phenomenon has been confirmed by Loss of Ignition
(LOI) test and reported elsewhere [5].
The dark areas embedded in pyrolytic carbon crystals
shown in Fig. 6 correspond to the white spots in SEM
images shown in Fig. 7. Element mappings demonstrated
that the spots are rich in Si and oxygen content and poor in
Na and Al content. The spherical structures imply that they
were liquid at elevated temperatures corresponding to a
silica-rich glass formed during the anode backing process.
Point analysis confirmed that the Na and Al content in the
Fig. 6 Polarized light
micrographs of cross-section of
carbon build-up and refractory
interface
Z. Wang et al.
silica droplets was less than 1 and 5 at.%, respectively. Silica
droplets solidify when the flue wall cools down, which
seems to serve as nucleation and deposition surface for
pyrolytic carbon to grow during the next firing cycle. Dif-
ferent phases observed in the sample were not necessarily
formed at the same time.
Silica spots were also observed in the vicinity of the
refractory surface. The electron image and element mapping
of C, Si, Al, S and O are presented in Fig. 8. The formation
of the silica phase is proposed to contribute both to the
formation of carbon build-up layer and the degradation of
the refractory materials. The mechanism for transporting
silicon to the deposition sites, where pyrolytic carbon is
formed, needs further studies.
Figure 9 shows an electron image of mullite grains
together with element mappings. A Si depleted region along
the mullite grain surface is evident in the Si element map-
ping, which indicates that the mullite grain has been attacked
with loss of Si. The lost Si from mullite grains is suggested
to contribute to the formation of silica droplets in the carbon
build-up layer. Carbon deposition on pore surfaces was also
evident in the C element mapping. Gaseous degradation of
the mullite is proposed to be the underlying reason, which
will be discussed later.
A cylindrical sample was drill from the spent flue wall
brick with a layer of carbon build-up attached to the
refractory. The sample was analysed using X-ray CT scanner
to see the microstructure evolution in the interior of the
material. Images of CT scan are shown in Fig. 10 where
orthogonal views of the xz plane is shown in (a) while the xy
plane is shown in (b) and (c). The brighter the colour in the
figures are the heavier are the element phases. The darker
colour corresponding to less heavy element phases is
explicitly carbon in this sample. Delamination was observed
at the refractory interface probably due to the thermal his-
tory. Many white sports were found in the carbon build-up
layer, which were silica droplets according to the previously
mentioned SEM/EDS analysis. At the exact interface, in the
gaps, white needles/rods phases were observed as shown in
Fig. 10b. Cylindrical sample was carefully broken along the
Formation of Carbon Build-Up on the Flue Wall …
Fig. 7 Backscatter SEM image
and element mapping of C, Si, Al,
Na and O. The spots on refractory
surface were silica
interface for further SEM/EDS analysis to investigate the
phase composition of the needles/rods.
Figure 11a shows a rich rods area corresponding to the
white needles/rods in the CT scans. The surface of the rods
contains mainly carbon. Figure 11b and c display the broken
particle with the rods. A core-shell structure is evident with a
solid core wrapped in shell layered pyrolytic carbon. The
hexagonal cores are clearly shown in Fig. 11d.
Point analysis was performed to check the elemental
compositions of each phase. Results of points 1–6, high-
lighted in Fig. 11, are summarized in Table 1. The hexagonal
rods (point 1–2) and the smaller grains at the background
(point 4–5) had significantly higher Al content compared to
the previously mentioned silica droplets away from the
refractory surface. They are close to the mullite composition
as listed at the bottom of Table 1. The irregular big grain
(point 6) and the small droplet (point 3) are silica phases. The
sample used for illustration has fractured surface to better
1269
display the morphology. Some uncertainties in the element
analysis must be expected due to the sample topography.
Discussion
Formation Mechanisms of Carbon Build-up
The formation of pyrolytic carbon, resulting from hydrocar-
bon cracking and subsequent nucleation and growth on the hot
surfaces at the flue wall, play an important role in the formation
of the carbon build-up layer on flue wall surfaces. The process
of pyrolytic carbon deposition can be described as CVD
(chemical vapour deposition) on a hot substrate or CVI
(chemical vapour infiltration) on porous materials [7, 9, 10].
Hydrocarbon volatiles are released from the pitch during
heating of the green anodes. Once released, the volatiles are
sucked into the flue cavity through open slits and pores in
1270
Fig. 8 Backscatter SEM image
and element mapping of C, Si, Al,
Na and O showing silica spots on
the refractory surface
the flue wall. The burning of the volatiles from the pitch
contributes around 40 to 50% of the total furnace energy
input. A reduced pressure in the flue is maintained for
sucking the volatiles [4] out of the pits. This also gives
sufficient mass flux for the deposition of pyrolytic carbon by
the CVI route. Sufficient mass flux is necessary for yielding
pyrolytic carbon instead of carbon black, which normally
nucleates in the gas phase and not on a hot surface [7]. The
deposited pyrolytic carbon then gradually fills up the voids
between the flue wall and packing coke, as well as the voids
between packing coke particles. As a result, the packing
coke particles fuse together and bind to the refractory sur-
face. In the course of time, a hard carbon build-up layer
accumulates on the flue walls. Volatiles also infiltrate the
refractory through pores and cracks leading to the observed
pyrolytic carbon deposition in pores. A schematic drawing
illustrating the build-up formation mechanisms is shown in
Fig. 12. In addition to the packing coke particles, solidified
Z. Wang et al.
silica droplets and the mullite like rods at the refractory
interface are also important sources for pyrolytic carbon
deposition and subsequent growth. Na seems to have no or
limited contribution in the formation of build-up.
Transport of Silicon to the Carbon Build-up Layer
Silica particles, covered by layered pyrolytic carbon, were
found not only at the refractory interface but also in the
carbon build-up layer away from the refractory. These silica
particles are produced in situ during the anode backing
process. The transport of silicon to the reaction site is
important to understand. Silicon monoxide gas (SiO) is
proposed to be the silicon carrier. Several reactions may
contribute to SiO (g) formation.
Cristobalite in the refractory wall is unstable in contact
with carbon at high temperatures. Cristobalite can be
Formation of Carbon Build-Up on the Flue Wall … 1271

Fig. 9 Backscatter SEM image

and element mapping of C, Si, Al,
Na and O showing Si depletion
region on the mullite grain
surface

Fig. 10 X-ray computed

tomography images of carbon
build-up at the refractory
interface. a xz cross-section,
b and c xy cross-section along
line number 1 and 2 in a. Needles
or rods were found in the gaps as
shown in b
1272 Z. Wang et al.

Fig. 11 SEM images of rods at

the refractory and carbon build-up
interface. a bunch of rods; b–c
broken particle and rods with
layered pyrolytic carbon shell and
solid cores; and d hexagonal core
structure. Number 1–6 are
positions for point analysis

Table 1 Element compositions Al Si Na O

of point 1–6 in Fig. 11 from EDS
point analysis (unit in at.%). Two Point 1 34.1 8.4 0.5 56.7
mullite compositions are also Point 2 32.1 9.2 0.4 58.1
include for comparison
Point 3 0.5 34.2 0.1 60.2
Point 4 29.4 10.5 0.2 59.1
Point 5 32.3 10.4 0.1 56.2
Point 6 2.7 31.0 0.3 66.1
Mullite (3Al2O3
2SiO2) 28.6 9.5 / 61.9
Mullite (2Al2O3
SiO2) 30.8 7.8 / 61.6

converted into volatile SiO (g) by Reaction 1 with a negative

Fig. 12 Schematic drawing illustrating the carbon build-up mecha-
nisms. Figure not in scale
Gibbs free energy of −643 kJ/mol. The process is sponta-
neous at standard state. Moreover, the “silicon depletion
region” on a mullite particle surface, as shown in Fig. 9,
strongly suggests a mullite decomposition reaction. Mullite
decomposition may occur in a CO or H2 atmosphere or in
contact with carbon at certain oxygen partial pressure [11,
12]. The possible reactions are summarized in Table 2, as
Reaction 2–4, with the corresponding standard Gibbs
energies.
Mullite decomposition Reactions (2–4) are energetically
unfavoured in the standard states. By lowering the partial
pressure of SiO (g), however, the reactions will shift to the
right hand sides and cause decompostion of mullite. The
large pressure drop in the open baking furnace, sucking the
gaseous products from the reaction site into the flue cavity,
will contribute to a low SiO pressure and thereby promote
Formation of Carbon Build-Up on the Flue Wall …
Table 2 Possible reactions and the corresponding standard Gibbs energies, unit in KJ/mol
SiO2 þ C ¼ COðgÞ þ SiOðgÞ
3Al2 O3
2SiO2 ðsÞ þ 2COðgÞ $ 3Al2 O3 ðsÞ þ 2SiOðgÞ þ 2CO2 ðgÞ
3Al2 O3
2SiO2 ðsÞ þ 2C $ 3Al2 O3 ðsÞ þ 2SiOðgÞ þ 2COðgÞ
3Al2 O3
2SiO2 ðsÞ þ 2H2 ðgÞ $ 3Al2 O3 ðsÞ þ 2SiOðgÞ þ 2H2 OðgÞ
the mullite decomposition. A predominance diagram of Al–
Si–C–O system at 1300 °C is shown in Fig. 13. The diagram
presents the stable field of each phase as a function of
chemical potentials. The partial pressure of SiO (g) was fixed
at 1  10−8 atm in the calculation. Under this situation,
mullite is unstable when the oxygen partial pressure is lower
than 1  10−11.4 atm. Corundum and SiO (g) will be the
stable phases at oxygen partial pressure in the region of
1  10−26 to 1  10−11.4 atm.
Corundum grains were not detected by SEM, instead,
mullite-like rods wrapped in laminar pyrolytic carbon were
found at the vicinity of refractory interface. This might be
the so-called secondary mullite, where corundum recom-
bined with SiO (g) and formed mullite grains again. This
phenomenon is also reported in other process [11].
Mullite-like rods are only found at the refractory interface.
Re-oxidation of the volatile SiO (g) occurs upon cooling.
Silica droplets solidify at the fresh build-up surface and
severe as pyrolytic carbon nucleation sites in the next
heating section. Hence, over time, silica droplets will be
observed all over the entire carbon build-up layer.
Fig. 13 Predominant phase diagram of Al–Si–C–O system at 1300 °
C. 0.3333 < Si/(Si + Al) < 0.5, pSiO2 = 1  10−8 atm. 1. Al2O3-SiO
(g); 2. Al(l)-Si(s); 3. Al(l)-SiC(s); 4. Al4C3(s) + SiC(s); 5. Al3C4(s) +
SiO(g); 6. Al(l)-SiO(g); 7. 2Al2O3
2SiO2; and “+” denotes 1.0 atm
isobar. Calculated using FactSage [6]
1273
DGð1300 CÞ
−643.0 (1)
+49.3 (2)
+324.5 (3)
+21.9 (4)
Parameters Influencing the Carbon Build-up
Formation
Large pressure drop between the anode pit and flue cavity is
necessary to give sufficient mass flux for pyrolytic carbon to
form through a CVI route. This large pressure drop is the
nature of the open top baking furnace, but not an issue in a
closed type furnace, therefore the formation of pyrolytic
carbon in a closed furnace is not likely. The mechanisms for
carbon build-up in a closed type furnace will be different and
the corresponding results will be reported elsewhere.
Packing coke particle size distribution is another param-
eter influencing the carbon build-up formation. Fines or
smaller particles partially fill the voids between larger par-
ticles and the space between the coarser coke particles and
the flue wall, as illustrated in Fig. 12. The remaining free
space will be significantly smaller compared to the case with
only large particles, while the surface area will be much
larger. The increased surface area will increase the driving
force of fusing. Therefore, coke particles with fines or small
particles will be easier to fuse together and fixe to the flue
wall to form a solid attached build-up layer when all the free
spaces are filled up by carbon. Logically, the process will be
much faster when the packing coke consists of a finer
fraction due to the less free space. Large surface area,
associated with fines, also provides more nucleation sites for
pyrolytic carbon deposition. Removing the fines in the
packing cokes is recommended for reducing the carbon
build-up.
Conclusion
The formation of pyrolytic carbon, resulting from hydro-
carbon cracking and subsequent nucleation and growth on
hot surfaces, plays an important role on the formation of
carbon build-up layer on flue wall surfaces. The hot surfaces
for pyrolitic carbon deposition can be packing coke parti-
cles, solidified silica droplets or mullite-like rods. The
mullite-like rods were mostly like secondary mullite found
1274
only at the refractory interface, while the silica particles were
found spread all over carbon build-up layer. SiO (g) is the
most likely “silicon” carrier, resulting from the decomposi-
tion of mullite grains under the exposure to CO (g) or H2 (g).
The pressure drop towards the flue wall removes SiO
(g) from reaction site and promotes mullite decomposition.
The pressure drop also provides enough mass flux of vola-
tiles, which is necessary for pyrolytic carbon formation.
Fines in the packing coke also enhance the formation of
carbon build-up.
Acknowledgements The present work was carried out in the project
“Reactivity of Carbon and Refractory Materials used in Metals Pro-
duction Technology” (CARMA), financed by the Research Council of
Norway, Hydro Aluminium, Alcoa Norway, Skamol, and Elkem Car-
bon. Permission to publish the results is gratefully acknowledgement.
References
1. P.R.T. Tiba, et al., Systemic analysis of flue wall bricks used on
anode baking furnaces. Light Metals, 1015–1019 (2010)
Z. Wang et al.
2. P. Prigent et al., The effect of the addition of fine andalusite
particles in refractory bricks on gaseous corrosion. JOM 60(5), 58–
63 (2008)
3. F. Brunk, Corrosion and behaviour of fireclay bricks used in the
flues of open anode baking furnaces. Light Metals, 641–646
(1995)
4. F. Keller, P.O. Sulger, Anode Baking, 2nd edn. (R&D Carbon Ltd.,
Sierre, Switzerland, 2008)
5. T. Brandvik, Z. Wang, T. Grande, Investigations of spent
refractory lining in an anode baking furnace. Light Metals (2017)
6. C.W. Bale et al., FactSage thermochemical software and databases.
Calphad-Comput. Coupling Phase Diagrams Thermochemistry 26
(2), 189–228 (2002)
7. X. Bourrat et al., Low temperature pyrocarbons: a review. J. Braz.
Chem. Soc. 17, 1090–1095 (2006)
8. M. Guellali et al., Textures of pyrolytic carbon formed in the
chemical vapor infiltration of capillaries. Carbon 41(1), 97–104
(2003)
9. G.L. Vignoles et al., CVD and CVI of pyrocarbon from various
precursors. Surf. Coat. Technol. 188–189, 241–249 (2004)
10. P. Delhaes, Chemical vapor deposition and infiltration processes of
carbon materials. Carbon 40(5), 641–657 (2002)
11. R.E. Wright, H.I. Wolff, Refractory problems in production of
hydrogen by pyrolysis natural gas. J. Am. Ceram. Soc. 31(2), 31–
38 (1948)
12. R.F. Davis, I.A. Aksay, J.A. Pask, Decomposition of Mullite.
J. Am. Ceram. Soc. 55(2), 98–101 (1972)
 Identification of the Stress Intensity Factor
of Carbon Cathode by Digital Image
Correlation

Donald Picard, Luca Sorelli, Julien Réthoré, Houshang Alamdari,

Marc-Antoine Baril, and Mario Fafard

Abstract
Crack propagation in carbon cathode used in the aluminium industry has been investigated
through flexural tests on notched specimens. The main parameters of interest were the
geometrical evolution of the crack and the stress intensity factor at the tip ends. The latter,
in the case of interfacial fracture in two-dimensional geometries, can be related to normal
(mode I) and shear (mode II) stresses. In this work, a new methodology has been applied
which optically measures the crack tip displacement field by Digital Image Correlation. The
stress intensity factors derived from the experimental data are consistent with results
available in the literature. Furthermore, the preliminary results showed that characterizing
the mode I (opening) only is somehow challenging due to the heterogeneity of such
carbonaceous materials.

Keywords
Carbon Cathode Crack propagation Digital image correlation Stress intensity factor

Introduction cell lining and is thus considered as a non-consumable

An Hall-Héroult aluminium electrolysis cell is composed of
various structural materials such as refractory concrete, steel
and carbon [1]. Carbon is mainly used in the fabrication of
the electrodes, i.e. anodes and cathodes, since it is able to
maintain good thermo-electromechanical properties at the
operational temperature (960 °C) of a cell [2–6]. While the
carbon anode (consumable electrode) has to be replaced
every 26 days (this number may vary depending of the cell
technology), the cathode, on the other hand, is a part of the
D. Picard (&)
H. Alamdari
M.-A. Baril
M. Fafard
Aluminium Research Centre—REGAL, Université Laval, G1V
0A6 Québec, QC, Canada
e-mail: donald.picard@gci.ulaval.ca
L. Sorelli
Centre de Recherche Sur Les Infrastructures En Béton, Université
Laval, G1V 0A6 Québec, QC, Canada
J. Réthoré
LaMCoS Laboratory, Université de Lyon, F69621 Villeurbanne
Cedex, France
electrode.
The life span of an electrolysis cell is strongly correlated
to the cell lining one. Failures leading to the end of life of the
cell are generally related to a lining failure and can be
classified in two categories. The first one contains failures
related to normal operation such as lining degradation (e.g.
erosion of the cathode and chemical contamination of
refractory by the electrolytic bath) [1]. The second one
includes abnormal early failures of the lining leading to
liquid bath leakage. These are generally correlated to the
quality of the preheating phase of the cell used to slowly
increase the temperature of the materials from room tem-
perature (approximately 25 °C) to the operational one (960 °
C). This is mainly done to avoid thermal shock of lining
materials during the early stage operation of the cell, which
include the pouring of molten cryolithe (bath).
As mentioned, the lining is composed of refractories,
cathode blocks and other materials within a steel potshell
each having different thermal expansion coefficients. Hence,
mechanical stresses are induced in the lining when heated
and failure occurs when stress levels exceed material

© The Minerals, Metals & Materials Society 2017 1275

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_152
1276
strengths. In addition to liquid leakage, the generation of
cracks in the cathode blocks will reduce significantly the cell
electrical efficiency and thus it must be avoided. It is thus
imperative to well understand the behaviour of the carbon
cathode block and, more importantly, when it reaches a
critical state, i.e. cracking.
In this work, the cracking behaviour is characterized
through the stress intensity factors (SIF) which has been
calculated using displacement field obtained with a Digital
Image Correlation method during four-point bending tests of
notched cathode samples.
Materials and Methods
Stress Intensity Factors
Determination of material failure is generally based on
failure criteria such as Mohr-Coulomb or von Mises. The
choice of the criterion is highly dependent of the material
microstructure (metals, ceramics, etc.). Once the material
reaches the failure level, cracks will appear. The evolution of
those cracks may be related to a stress intensity factor [7]
used to predict the stress state near the end of the crack tip.
Three linearly independent cracking modes (Fig. 1) are
used to define the crack state: opening (mode I), jn-plane
shear (mode II) and out-of-plane shear (mode III). In the
present case, i.e. interfacial fracture in two-dimensional
geometry, only the first two modes are of interest. However,
the focus has been set on mode I only, i.e. crack opening.
The relationship between the load and the stress intensity
factor varies with the loading case [9]. However, comparison
between experimental results and analytical solutions will
not be addressed in this paper.
Digital Image Correlation
Digital Image Correlation (DIC) techniques have been
emerging to investigate the damage behaviour of different
materials [10, 11]. In summary, it is a measurement technique
Fig. 1 Cracking modes in fracture mechanics. From [8]
D. Picard et al.
that allows one to retrieve displacement fields “separating”
two digital images of the same sample at different stages of
loading. Because of its remarkable sensitivity, it is not only
possible to detect cracks with sub-pixel opening, which would
not be visible, but also to provide accurate estimates of stress
intensity factors. For instance, in concrete science, DIC has
been successfully applied to study the fracture mechanics of
concrete, especially considering the crack opening [12] and
the internal damage due to the expansive reaction of alkali
reactive aggregates [13]. Recently, DIC analysis has been
applied to study the microcrack process of Ultra High Per-
formance Concrete (UHPC) during bending, which is a key to
the structural ductility [14].
Cathode Samples
Cathode samples used for this study come from a graphitized
carbon cathode. The compressive strength, tensile strength,
Young’s modulus and Poisson’s ratio have been measured in
laboratory according to ISO 18515:2007 [15] /ASTM
C695-91 [16]/ASTM C469 [17]/ASTM C496 [18] standards
and are available in Table 1.
The carbon cathode sample dimensions used for flexural
tests (Fig. 2) were chosen according to ASTM C651 [19]
standard and machined to the following values: 300 mm ×
50 mm × 37.5 mm (Length × Height × Thickness). The
initial notch height is 25 and 3 mm width. Also, as shown on
Fig. 2, paint (black marks on a white background) was used
on cathode samples for DIC purpose.
Flexural Tests
Flexural tests were done accordingly to the ASTM C651
[19] standard with a displacement rate of 0.2 mm/min. The
apparatus used is schematized in Fig. 3 and was mounted on
a MTS 810 loading frame. The distance between the upper
cylindrical bearings was 70 and 210 mm between the bot-
tom ones. The actuator displacement (LVDT) and load
(MTS 5 kN load cell) were both recorded with a MTS FT40
controller. On the other hand, images used for DIC analysis
were recorded with a mvBlueFox 102G camera at a rate of
50 frames/s.
Results and Discussion
Cracking Behavior
As highlighted in several studies (e.g. [2–6]) carbon cathode
materials are highly heterogeneous. Hence, cracking path
will be highly affected by this heterogeneity. In order to get a
Identification of the Stress Intensity Factor … 1277

Table 1 Mechanical properties Compressive strength Tensile strength Young’s modulus Poisson’s
of the graphitized carbon cathode (MPa) (MPa) (GPa) ratio
Value 11 1.8 2.05 0.03a
a
The measurement error was very high on this parameter

Typically, mode I cracking will lead to the fully fractured

Fig. 2 Typical carbon cathode sample used for stress intensity factor
tests
representative behavior of mode I, cracking a large number
of samples is thus required. Indeed, even though samples
and notch geometries were selected in order to activate only
the mode I, also shear behavior (mode II) has happened in
several tests. Typical mode I and mode II cracking under
four-point flexural test are shown in Figs. 4 and 5 respec-
tively. However, as mentioned previously, this study has
focused only on mode I as a first step.
sample shown in Fig. 6, which presents pictures of a sample
at the end of the test. As shown on those pictures, the
cracking pattern through the thickness of the sample is not
the same one as the one observed with the DIC on the
painted front face. This highlighted again the high influence
of sample heterogeneity. In order to get two representative
samples exhibiting mode I cracking behavior at least five
tests have been performed. The two samples discussed in
this paper are called SIF-I-01 and SIF-I-02, which are
already been introduced in Fig. 4.
2D Displacement Field
The displacement results of samples SIF-I-01 and SIF-I-02
being similar, only one of them, sample SIF-I-01, will be
discussed in this section and are presented in Figs. 7 and 8.

Fig. 3 Scheme of the flexural

apparatus: a setup; b dimension
1278 D. Picard et al.

3 mm
(a)

3 mm
(b)

Fig. 4 Mode I crack pattern observed on painted graphitized carbon

cathode: a sample SIF-I-01; b sample SIF-I-02

Fig. 6 Typical mode I cracked sample after a stress intensity factor

test. a front view; b open view; c side by side view; d rear view

As expected for a mode I fracture mechanism, the hori-

zontal and vertical displacements are mostly symmetrical far
from the crack. In this latter region, displacements are of
course affected by the crack propagation. However, as
3 mm mentioned previously, this displacement field may vary
through the width of the sample (see Fig. 6).
Fig. 5 Typical mode II crack pattern observed on painted graphitized The crack length evolution of both samples SIF-I-01 and
carbon cathode SIF-I-02 are shown in Fig. 9. It can be seen that the crack
Identification of the Stress Intensity Factor … 1279

Fig. 9 Crack length evolution of samples SIF-I-01 and SIF-I-02 as a

function of time
Fig. 7 Horizontal displacement field (mm) of sample SIF-I-01 after
245.08 s

Fig. 10 Stress intensity factor K1 evolution of samples SIF-I-01 and

SIF-I-02 with time

Fig. 8 Vertical displacement field (mm) of sample SIF-I-01 after

245.08 s

evolution in this cathode material is not a monotonous one.

Two similar events can be observed after approximately
212 s and 219 s in the crack evolution of sample SIF-I-01.
At these steps, the crack length increase rapidly. A similar
event occurred in sample SIF-I-02 after 210 s. This suggest
that at that moment the crack has gone through a weak zone
probably containing more graphitized aggregates with
planes aligned with the crack direction [3, 20].

Fig. 11 Stress intensity factor K1 evolution of samples SIF-I-01 and

SIF-I-02 as a function of crack length
Stress Intensity Factors

The stress intensity factor evolution with time of both weaker zones Instead, the Stress Intensity Factors seem to
samples SIF-I- 01 and SIF-I- 02 is shown in Fig. 10. Con- increase almost monotonously with time. This is not the case
trary to the observations on crack length evolutions (Fig. 9), when Stress Intensity Factors K1 are compared to crack
there are no clear events related to crack propagation in lengths as shown in Fig. 11. In both samples, K1 is almost
1280
constant up to a crack length of about 35 mm. After that,
Stress Intensity Factors K1 increase almost with a constant
slope up to a crack length of about 40 mm. This seems to
indicate that for those two tests weak zones are located
roughly at the same distance from the initial notch and that
they have almost the same size in both samples. Even though
graphitized carbon cathodes are heterogeneous and the SIF
extraction ignores the presence of these heterogeneities, the
critical stress intensity factor for the weak zones seems to be
pffiffiffiffi
reproducible at SIF  0:3 MPa
m.
Conclusion
Cracking behaviour has been characterized through the
stress intensity factors K1 related to normal (mode I) stress.
This factor has been calculated based on displacement field
obtained with a Digital Image Correlation method during
four-point bending tests of notched cathode samples. Sample
heterogeneity effect on cracking behaviour has been high-
lighted and justified the need to have a large number of tests
in order to identify the mode I fracture behaviour. As
expected, cracking seems to be highly affected by the pres-
ence of carbon aggregates with planes aligned with the
cracking direction. Nevertheless, the evolution of the stress
intensity factor K1 as a function of the crack length indicated
that flexural tests on notched specimen where only mode I is
solicited are reproducible. Finally, critical stress intensity
factor for the weak zones seems to be reproducible at
pffiffiffiffi
SIF  0:3 MPa
m.
Acknowledgements Authors would like to acknowledge the financial
support of Natural Sciences and Engineering Research Council
(NSERC). A part of the research presented in this paper was financed
by the Fonds de Recherche du Québec-Nature et Technologie
(FRQNT) by the intermediary of the Aluminium Research
Centre-REGAL.
References
1. M. Sørlie, H.A. Øye, Cathode in aluminium electrolysis. 3rd edn
(Aluminium-Verlag Marketing & Kommunikation GmbH, Düssel-
dorf, Germany, 2010)
2. B. Allard, J.-M. Dreyfus, M. Lenclud, Evolution of thermal,
electrical and mechanical properties of graphitised cathode blocks
for aluminium electrolysis cells with temperature. Light Metals
(2000)
D. Picard et al.
3. B. Allard et al., High temperature mechanical behaviour of carbon
materials used in aluminium smelters. Light Metals, 783–790
(1995)
4. D. Dumas, P. Lacroix, High temperature measurement of electrical
resistivity and thermal conductivity on carbon materials used in
aluminium smelters. Light Metals, 751–760 (1994)
5. A.A. Mirchi, W. Chen, M. Tremblay, Comparative characterisa-
tion of graphitized and graphitic cathode blocks. Light Metals
(2003)
6. D. Picard et al., Thermo-Mechanical characterisation of graphitic
and graphitized carbon cathode materials used in aluminium
electrolysis cells. Light Metals (2010)
7. T.L. Anderson, Fracture mechanics: fundamentals and applica-
tions, 621 p (2005)
8. Wikipedia. Stress intensity factor. Available from: https://en.
wikipedia.org/wiki/Stress_intensity_factor
9. A.F. Bower, Appl. Mech. Solid. p. xxv, 794 p (2010)
10. P. Leplay et al., Identification of damage and cracking behaviours
based on energy dissipation mode analysis in a quasi-brittle
material using digital image correlation. Int. J. Fract. 171(1), 35–
50 (2011)
11. F. Rajabipour, H. Maraghechi, G. Fischer, Investigating the
Alkali-Silica reaction of recycled glass aggregates in concrete
materials. J. Mater. Civ. Eng. 22(12), 1201–1208 (2010)
12. S.Y. Alam, A. Loukili, F. Grondin, Monitoring size effect on crack
opening in concrete by digital image correlation. Eur. J. Environ.
Civ. Eng. 16(7), 818–836 (2012)
13. D. Corr et al., Digital image correlation analysis of interfacial
debonding properties and fracture behavior in concrete. Eng. Fract.
Mech. 74(1–2), 109–121 (2007)
14. Y. Duhamel-Labrecque et al., Featuring the micro-cracking
process of uhpfrc under bending by digital image correlation.
Am. Concr. Inst. J. Mater. M2016–163 (2016)
15. ISO Standard 18515:2007, Carbonaceous materials for the
production of aluminium—cathode blocks and baked anodes—
determination of compressive strength, ISO International Standard,
Switzerland (2007)
16. ASTM Standard C695—91, 2010, Standard Test Method for
Compressive Strength of Carbon and Graphite, ASTM Interna-
tional, West Conshohocken, PA, 2010. doi:10.1520/C0695-15
17. ASTM Standard C469, 2014, Standard Test Method for Static
Modulus of Elasticity and Poisson’s Ratio of Concrete in
Compression, ASTM International, West Conshohocken, PA,
2014. doi:10.1520/C0469_C0469M
18. ASTM Standard C496/C496 M − 11, 2011, Standard Test
Method for Splitting Tensile Strength of Cylindrical Concrete
Specimens, ASTM International, West Conshohocken, PA, 2011.
doi:10.1520/C0496_C0496M-11
19. ASTM Standard C651, 2015, Standard Test Method for Flexural
Strength of Manufactured Carbon and Graphite Articles Using
Four-Point Loading at Room Temperature, ASTM International,
West Conshohocken, PA, 2015. doi:10.1520/C0651-15
20. F. Durand et al., Characterization of the high temperature
mechanical behavior of carbon materials. Carbon 32(5), 857–865
(1994)
 Investigation of Spent Refractory Lining
in an Anode Baking Furnace

Trond Brandvik, Zhaohui Wang, Arne Petter Ratvik, and Tor Grande

Abstract
The refractory lining in anode baking furnaces is exposed to harsh chemical environment
and thermal cycling. Spent refractory lining from an anode baking furnace after 4000 days in
operation was investigated. Variation in the density and porosity across the bricks revealed
that carbon build up in pores had taken place towards the anode side. The spent refractory
bricks were investigated with respect to chemical and mineralogical composition by X-ray
diffraction and electron microscopy. No significant change in the mineralogical composition
across the brick could be detected by X-ray diffraction. Fluoride was not found in the bricks,
while traces of sodium was shown to accumulate together with other impurities in the bricks.
The changes in the chemical and mineralogical composition across the bricks are discussed
in relation to possible chemical reactions taking place during anode baking.

Keywords
Anode baking furnace Refractory lining Degradation mechanism Chemical reactions

Introduction cover materials during electrolysis, recycled anodes consti-

An important part in the process of aluminum electrolysis
are the production and quality of the pre-baked carbon
anodes, where the main production principle is quite similar
from plant to plant [1–3]. The most significant variation with
respect to furnace design is whether the furnace has an open
or closed top section [4]. A mixture of coke and anode butts
is crushed, mixed with pitch and formed into green anodes,
which are subsequently heat treated in the anode baking
furnace. In the electrolysis cell, as the anodes reaches
20–25% of their original size, they are taken out of operation
and recycled to the production of green anodes. The use of
recycled anodes reduces both anode costs and the use of the
carbon materials. Due to the exposure to cryolite and anode
T. Brandvik (&)
Z. Wang
T. Grande
Department of Material Science and Engineering,
NTNU Norwegian University of Science and Technology,
Trondheim, Norway
e-mail: trond.brandvik@ntnu.no
Z. Wang
A.P. Ratvik
SINTEF Materials and Chemistry, Trondheim, Norway
tute a source of impurities, especially sodium and fluorine
from the bath, that normally is not found in great amounts in
the anode raw materials [1, 5]. In the anode-baking furnace,
aluminosilicate refractory walls are used to separate the
anodes from the hot flue gas. During a baking cycle, typi-
cally lasting 20–30 days, the temperature varies from
ambient to about 1200–1300 °C. Due to the high tempera-
ture, cryolite contaminations in the anodes will evaporate
forming gaseous NaF and NaAlF4. The combination of
thermal cycling and chemically harsh environments results
in refractory degradation and eventually the need for the
refractory wall to be replaced [3, 6].
Investigations of degradation of refractory lining in anode
baking furnaces have been reported in several works [1–3, 6].
These investigations have shown mineralogical changes close
to the anode side of the refractory, in addition to blackening of
the refractory caused by carbon deposition. Gaseous sodium
and fluorides were proposed to react with the lining forming a
liquid phase, which during cooling forms a glass phase with a
lower solidus temperature compared to the original refractory
lining [1–3]. This mechanism causes the thermomechanical

© The Minerals, Metals & Materials Society 2017 1281

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_153
1282 T. Brandvik et al.

properties of the refractory lining to change, which eventually

leads to deformation and degradation of the lining. The
interaction of similar materials with sodium aluminum
fluorides has also been studied in depth in relation to the
refractory lining in electrolysis cells [1–3, 6–16].
Materials from an autopsy of a flue wall after approxi-
mately 4000 days in operation were characterized in this
work. The density and porosity variations in the outer layers
facing the anodes are linked to the deposition of carbon in
the open porosity. Changes in phase composition were
evaluated as a function of distance from the anode and
compared to similar findings from previous investigations on
anode baking furnaces. Reaction mechanisms describing the
degradation are discussed.

Method
Fig. 1 The cross section of a typical sample of the exposed refractory
lining. The anode pit side is to the left and the flue side is to the right of
Materials from a spent refractory lining were collected from the brick. The full width sampling with the associated labels has been
an open top anode baking furnace after approximately the basis for most of the investigations in this work. In addition,
4000 days in operation. Samples were taken from three samples of 3 and 5 mm thickness have been prepared for carbon
content analysis
positions on the refractory wall (high, middle and low) and
named H, M and L, respectively. The uppermost sample is
collected approximately 1 m from the top of the furnace. All
samples were collected approximately 1 m from the pit cross
wall. Figure 1 shows a typical cross section of a refractory
sample. The darker region on the left hand side is facing the
anode pit, and the bright area at the right hand side is facing
the flue. The interface between the dark and bright regions
was observed to vary with sampling position. The samples
were divided into sections, named a–h according to the
sampling presented in Fig. 1. In addition to the full width
sampling, two thinner samples were also collected close to
the anode side as shown in Fig. 1.
Density and porosity measurements were carried out
using the Archimedes’ method in accordance with ISO5017.
Mineralogical analysis through X-ray diffraction was con-
ducted on a Bruker D8 Focus diffractometer with a LynxEye Fig. 2 Micrograph of the pristine unreacted refractory material
SuperSpeed detector. Chemical analysis was carried out with
a Hitachi S-3400 N scanning electron microscope (SEM),
with the associated energy dispersive X-ray spectroscopy
Table 1 Chemical composition and some physical properties for the
(EDS). In addition, X-ray fluorescence analysis were carried pristine material
out with a Bruker S8 Tiger 4 kW X-ray diffractometer.
Specie wt%
Al2O3 51
Results SiO2 46
TiO2 1.5
The refractory material used in the anode baking furnace has Fe2O3 1
a highly heterogeneous microstructure, with dense aggre- K2O 0.2
gates (ranging from micron range to several millimeters in CaO 0.2
size), bonded together by a fine matrix phase as shown in
Density 2.4 gcm−3
Fig. 2. The measured chemical composition and some
Open porosity 15 vol.%
physical data of the pristine material are presented in Table 1.
Investigation of Spent Refractory Lining … 1283

Fig. 3 X-ray patterns for sample

L as a function of distance from
the anode

X-ray diffractograms for sample L with full width sam- The measured density and porosity of sample H is pre-
pling (a–h) are displayed in Fig. 3, where mullite (Al6Si2O13) sented in Fig. 5. These results show less density changes in
and cristobalite (SiO2) are found to be the main phases. The the samples closest to the anodes caused by heat treatment,
overall change in phase composition with respect to distance compared to the results in Fig. 4. The density of the sample
from the anode side is minor according to the X-ray patterns. closest to the anode side is the only sample clearly affected
The same is observed for samples H and M. However, when by the heat treatment, while the others are more or less
focusing on the broad strong reflection highlighted in Fig. 3, unaffected. After heat the treatment, the data show a similar
there are some significant variations worth mentioning. As the trend as observed for samples M and L, with an increased
distance from the anode increases (going from a to h), there is density for samples H–b to H–d. The difference between the
a clear variation in the intensity and the position of the baseline (the density level closest to the flue) and the highest
reflection attributed to cristobalite (located at 2h = 21.9°). It is data point is, however, not as pronounced as for samples M
also most likely that the reflection consists of three reflections and L. It is also observed that the density baseline for sample
where only one can be assigned to cristobalite. The variations H is found around 2.35 gcm−3, which is lower than the
do, however, not proceed as a linear function of the distance pristine density observed for sample M and L.
from the anode. For samples L–a to L–e, the broad middle
reflection decreases in intensity and the reflection assigned to
cristobalite increases, while from L–f to L–h the trend is
reversed. This variation is observed to a similar degree for
sample M, while it is not very pronounced for sample H. The
shift appears at approximately 6–7.5 cm into the wall. Apart
from the minor intensity shift in the highlighted peaks in
Fig. 3, there is no significant variation in the overall phase
composition.
Measurements of the density and the porosity for samples
L, M and H were carried out across the whole brick in
accordance to the sectioning presented in Fig. 1. The samples
were then heat treated in air at 1150 °C for 48 h, before the
measurements were repeated. The results for sample L are
presented in Fig. 4, showing almost no change in density and
porosity due to the heat treatment. The blue dotted line indi-
cates the pristine density, which is in good agreement with the
four measurements closest to the burner side. Closer to the
Fig. 4 Density and open porosity for sample L as a function of
anode, the density increases before it drops for the outermost distance from the anode side is plotted before and after heat treatment.
layer. The same behaviour is observed for sample M. The density of the pristine material is indicated by the blue dotted line
1284
Fig. 5 Density and open porosity for sample H as a function of
distance from the anode side plotted before and after heat treatment.
The density of the pristine material is indicated by the blue dotted line
Sample sectioning shown before and after the heat
treatment procedure is presented in Fig. 6. The blackening of
the samples is almost completely removed due to the heat
treatment. Measurements of the weight loss during heat
treatment showed a weight loss of 4 wt% for the sample
closest to the anode side, while no significant weight loss
during heat treatment was measured for the other samples.
Figure 7 show a comparison of the X-ray patterns of
samples with 3 and 5 mm width, a coke sample and the
pristine, unexposed material. The indicated widths are
measured from the anode-facing surface and into the
refractory wall. The green line in Fig. 7 show the main
reflection related to the coke sample. The pristine material
has naturally no significant coke content, while the exposed
samples do show considerable amounts of coke in the outer
layers of the sample. As the width of the exposed sample
decreases, the amount of coke in the sample becomes more
significant. The carbon content in the 3 mm sample is thus
higher than the sample with 5 mm thickness.
As shown in Figs. 4 and 5, the refractory material has a
substantial amount of open porosity (10–20%). Conse-
quently, gaseous species can diffuse into the material
Fig. 6 Samples before (upper)
and after (lower) heat treatment.
The samples closest to the anode
side were clearly blackened
during operation in the anode
baking furnace
T. Brandvik et al.
increasing the amount of exposed refractory surface. When
investigating the outer layers of the most exposed samples
(H–a, M–a and L–a), there are clear signs of chemical wear
on some of the grain surfaces. The SEM image in Fig. 8
show an overview of sample L–a with the anode-facing
surface pointing upwards.
The sample in Fig. 8 consist mostly of larger grains with
some porosity in between. The outer layers of the grains
facing the anodes are clearly affected by years in operation.
Figure 8 show a 50–100 µm thick layer on the grains where
both the microstructure and the chemical composition of the
structure are changed. A part of the affected region is shown
in greater detail in Fig. 9, where the dense grain is found in
the lower part of the figure, while the affected region consists
of a less dense, rod-like microstructure. The grains of the
dense bulk phase are more or less the same as found in the
pristine material. There is no significant increase in Na
content in the exposed regions, compared to the Na content
in the pristine material. The distribution of Al, Si, O and C is
measured by EDS mapping and presented in Fig. 10.
The EDS analysis show a change in chemical composition
from the dense bulk region to the affected porous areas of the
grains. At the boundary between the dense and porous parts
of the grain, there is an abrupt change in the silicon level.
The reacted region is almost depleted of silicon, while the
aluminum oxide is left in the material. The amount of alu-
minum and oxygen is however more or less constant
throughout the investigated region. The chemical wear is
observed throughout the outer layers of the samples, but
seems to be varying with both sampling position in the
furnace and distance into the refractory away from the anode
side.
There are indications of increased degradation in the
bottom of the pit compared to the upper regions, i.e. sample
L–a is more affected than H–a. The thickness of the affected
porous region is decreasing as the distance from the anodes
is increasing. Chemical degradation is also found at the
inside of pores several millimetres into the refractory.
Figures 11 and 12 present sample H-a with the
anode-facing surface pointing upwards. This sample is
Investigation of Spent Refractory Lining …
Fig. 7 Comparison of the X-ray diffraction patterns of pure carbon
with thin exposed refractory samples and the pristine unexposed
material
Fig. 8 Overview of the exposed sample L-a with the anode-facing
surface pointing upwards. The outer layers of the grains are clearly
affected by years in operation
collected from the top section of the furnace, showing minor
signs of chemical wear. Sphere-like particles of SiO2 are on
the other hand observed in the immediate vicinity of the
refractory at the anode side. These particles are found all
over the refractory surface on sample H-a. The samples
collected further down in the furnace, samples M and L,
show no signs of such particles. From Fig. 12 there are signs
Fig. 9 Detailed micrograph of the region of the materials in Fig. 8
where mineralogical transformations are evident. The anode-facing
surface is pointing upwards
1285
of impurities (Na and K) and Al in the SiO2 rich particles.
This suggests that the particles are not crystalline SiO2, but
rather an amorphous glassy phase where the solubility of
impurities are higher.
Discussion
The density variations presented in Fig. 4 demonstrate that
the macrostructure of the wall has changed towards the
anode side. Close to the burner side, the measured density
equals the pristine density (the baseline), while it increases
closer to the anode. The difference between the maximum
measured density and the baseline is approximately 3–4%
for samples M and L. The same behaviour is observed for
the heat treated H samples presented in Fig. 5, however with
a baseline at around 2.35 gcm−3. The difference between the
maximum measured density and the baseline is found to be
approximately 2%. The density variations are thus found to
be greater in the middle and bottom of the pit, compared to
the top section. The fact that X-ray diffraction analysis does
not detect significant compositional variations, points to the
formation of an amorphous phase or densification of the
refractory.
The chemical wear observed in the middle and bottom
section of the pit show regions with pronounced SiO2
depletion. The chemical wear is, however, only observed at
the surface of the grains closest to the anode. These obser-
vations correspond with the assumption that volatile species
are entering the structure through the open porosity, and
react with the outer layers of the grains. The partial pressure
of the reacting species is decreasing with increasing distance
from the anode, leading to a reduction in chemical wear on
the grains. Brunk [6] reports on SiO2 depletion from
refractory materials in anode baking furnace similar to the
observation in this work. He explained the observation with
the reduction of SiO2 by CO, as presented in Eq. (1).
SiO2 ðsÞ þ COðgÞ ¼ SiOðgÞ þ CO2 ðgÞ ð1Þ
At elevated temperatures, the partial pressure of CO in the
anode baking furnace becomes high enough to favour the
formation of gaseous SiO [6]. Samples collected from
the lower (sample L) and middle (sample M) section of the
furnace show pronounced chemical wear in the outer layers,
while this is not observed to the same extent in the samples
collected from the top section (sample H) of the furnace. The
anode baking furnace investigated in this work has an open
top configuration, and it could be assumed that the partial
pressure of oxygen is higher in the upper parts of the oven,
compared to the bottom. The atmosphere in the top section is
thus less reducing, preventing the reduction of SiO2 to take
place.
1286
Fig. 10 Element distribution in the surface region of sample L-a presented in Fig. 9. The anode-facing surface is pointing upwards
Fig. 11 Surface region of sample H-a with the anode-facing surface
pointing upwards
EDS analysis of the SiO2 depleted regions shows a
chemical composition close to the mullite composition. The
average composition of the dense unreacted regions does on
the other hand correspond to andalusite (Al2SiO5) and SiO2
in a 50/50 atomic ratio. Andalusite is often used as a pre-
cursor in the production of refractory materials [6]. During
heat treatment, the thermodynamically unstable andalusite
decomposes into mullite and SiO2 according to Eq. (2).
T. Brandvik et al.
3Al2 SiO5 ðsÞ ¼ Al6 Si2 O13 ðsÞ þ SiO2 ðsÞ ð2Þ
After decomposition, the material ends up with a matrix of
rod-like mullite particles with SiO2 filling the voids, denoted
mullitised andalusite [3, 17]. The heat treated refractory
material is thus consisting of a combination of mullite and
SiO2, corresponding to the X-ray analysis presented in
Fig. 3. As SiO2 is reduced and removed from the structure,
only the mullite matrix is left, as shown in Fig. 9.
The measured density for sample H shows a significant
variation prior to and after heat treatment for the samples
closest to the anode. This reduction in density is attributed to
the removal of carbon during heat treatment. The X-ray
patterns presented in Fig. 7 demonstrate the presence of
carbon in the outer layers of the lining. The closer to the
surface (thinner samples), the more significant the carbon
content becomes. These investigations demonstrate clearly
that carbon is deposited in the open porosity of the refractory
bricks during operation in the anode baking furnace. During
heating, gaseous CO and volatile hydrocarbons from the
green anodes are transported to the vicinity of the refractory.
Carbon deposition could thus be a result of carbon cracking
at the refractory wall. Another possible source of carbon
deposition is a reaction between gaseous SiO and CO2,
forming SiO2 and carbon according to Eq. (3).
Investigation of Spent Refractory Lining …
Fig. 12 Element distribution in the surface region of sample H-a close to the anode side. The anode-facing surface is pointing upwards
SiOðsÞ þ COðgÞ ¼ SiO2 ðsÞ þ CðsÞ
This reaction is a combination of the Boudouard reaction
and the reversed reaction in Eq. (1). As the temperature
decreases in the last part of the temperature cycle, the
CO/CO2 gas mixture becomes unstable, shifting the Bou-
douard reaction, and the reaction in Eq. (3), towards carbon
deposition [18]. Evidence of carbon deposition has not been
found in the middle and bottom section of the furnace,
demonstrating that the amount of carbon deposition in the
pores are not sufficient to influence the density
measurements.
The fact that carbon is only reduced and deposited in the
upper parts of the furnace corresponds to the observation of
SiO2 deposition in the same sections. The reducing atmo-
sphere is most pronounced in the bottom of the furnace and
becomes less reducing further up. SiO2 is reduced in the
1287
ð3Þ bottom of the furnace forming gaseous SiO, and transported
upwards to the less reducing atmosphere. As the environ-
ment becomes sufficiently oxidizing, SiO is re-oxidized
forming droplets of amorphous SiO2 at the face of the
refractory wall. Impurities like Na and K, in addition to Al,
are observed in the SiO2 particles. The presence of such
impurities reduces the particles’ viscosity, favouring the
formation of spherical particles.
There are no signs of increased sodium or fluorine content
in the exposed regions of the refractory, even though both
NaAlF4 and NaF are expected to be present in the gas phase of
the furnace [18]. A recent thermodynamic study of potential
reactions between volatile fluorides and the refractory wall,
suggests refractory degradation could be caused by several
thermodynamically possible reaction schemes [18]. Most of
these reactions result in the formation of the sodium alumi-
nosilicates; nepheline or albite. The fact that no significant
1288
levels of sodium has been observed in the spent lining, indi-
cate that this is not the domination degradation mechanism in
the present samples. The level of NaF and NaAlF4 in the gas
phase are too low for such reactions to dominate, most likely
due to good cleaning routines of the anode butts, reducing the
amount of bath entering the green anodes.
Conclusion
The present work has demonstrated that the dominating
refractory degradation mechanism observed in open top
anode baking furnaces are the reduction of SiO2 by gaseous
CO. The degradation is more pronounced in the middle and
bottom section of the pit due to increased reducing atmo-
sphere. The open top configuration leads to an increased
partial pressure of oxygen in the top section of the furnace,
where gaseous SiO is re-oxidized, forming spherical SIO2
particles in the immediate vicinity of the refractory surface.
Carbon is deposited at the wall in the upper part of the
furnace. This is due to carbon cracking at the refractory wall,
and a result of the oxidation of SiO. Combined with the
increased density close to the anode side, the deposited
carbon causes the thermomechanical properties of the
refractory to change.
Acknowledgements Financial support from the Norwegian Research
Council and the partners Hydro Aluminium, Alcoa, Elkem Carbon and
Skamol through the project”Reactivity of Carbon and Refractory
Materials used in metal production technology” (CARMA) is
acknowledged. Technical support from Christian Schøning, Julian R.
Tolchard and Stein Rørvik, all at SINTEF Materials and Chemistry, is
also acknowledged.
References
1. P. Prigent, M.L. Bouchetou, Gaseous corrosion of Alumino-
Silicate Refractories in Anode Baking Furnaces used for Alu-
minium Produciton Part 1. Interceram 58, 121–126 (2009)
T. Brandvik et al.
2. P. Prigent, M.L. Bouchetou, Gaseous Corrosion of
Alumino-Silicate Refractories in Anode Baking Furnaces used
for Aluminium Produciton Part 2. Interceram 58, 202–209 (2009)
3. P. Prigent et al., The effect of the addition of fine andalusite
particles in refractory bricks on gaseous corrosion. JOM 60, 58–63
(2008)
4. F.H. Becker, F. Goede, Ring pit furnaces for baking of high quality
anodes—an overview. Aluminium 82, 9 (2006)
5. A. Radjenović, Properties of carbon anode components for
aluminium production. Nafta 63, 111–114 (2012)
6. F. Brunk, orrosion and behavior of Firecal Bricks usen in the flues
of open anode baking furnaces. Light Metals, 641–646 (1995)
7. C. Schøning, T. Grande, O.-J. Siljan, Cathode refractory materials
for aluminium reduction cells. Light Metals, 231–238 (1999)
8. O.-J. Siljan, T. Grande, C. Schøning, Refractories for aluminium
electrolysis cells part 1—Deterioration mechanisms based on
phase equilibria. Aluminium 77, 294–300 (2001)
9. O.-J. Siljan, T. Grande, C. Schøning, Refractories for aluminium
electrolysis cells part 2—physical properties of penerating melt,
reduction by metals and volatile fluorides. Aluminium 77, 385–
390 (2001)
10. O.-J. Siljan, T. Grande, C. Schøning, Refractories for aluminium
electrolysis cells part 3—laboratory test for cryolite resistance.
Aluminium 77, 610–615 (2001)
11. O.-J. Siljan, T. Grande, C. Schøning, Refractories for aluminium
electrolysis cells part 4—comparison of laboratory investigations
and autopsies of pot linings. Aluminium 77, 809–814 (2001)
12. O.-J. Siljan, C. Schoning, T. Grande, State-of-the-art alumino-
silicate refractories for al electrolysis cells. JOM 54, 46–55 (2002)
13. C. Schøning, T. Grande, The stability of refractory oxides in
sodium-rich environments. JOM 58, 58–61 (2006)
14. K. Tschope et al., Chemical degradation of cathode linings in
hall-heroult cells—an autopsy study of three spent pot linings.
Metall. Mater. Trans. B 43B, 290–301 (2012)
15. K. Tschöpe, J. Rutlin, T. Grande, Chemical degradation map for
sodium attack in refractory linings. Light Metals, 871–876 (2010)
16. J. Butter, A. Bongers, Alterations of anode baking furnace bricks
during operation. Light Metals, 633–639 (1995)
17. P. Prigent, M.L. Bouchetou, J. Poirier, Andalusite: an amazing
refractory raw material with excellent corrosion resistance to
sodium vapours. Ceram. Int. 37(7), 2287–2296 (2011)
18. T. Brandvik, A.P. Ratvik, T. Grande, Thermodynamic assessment
of the chemical durability of refractory lining in anode baking
furnaces. ICSOBA (2016)
 Non-Destructive Testing of Baked Anodes
Based on Modal Analysis and Principal
Component Analysis

Moez Ben Boubaker, Donald Picard, Carl Duchesne, Jayson Tessier,

Houshang Alamdari, and Mario Fafard

Abstract
Baked anodes quality control is still mostly based on core sampling and characterization.
Only a small proportion of the production can be tested by this method due to the costly,
time consuming, and destructive nature of the analytical techniques. Furthermore, the core
properties are not necessarily representative of those of the whole block. A rapid and
non-destructive method for anode quality control based on vibration modal analysis is
proposed. A number of baked anodes produced under different conditions at the Alcoa
Deschambault smelter were selected. These were excited mechanically at different locations
and the vibration signals of the blocks were measured by accelerometers. Principal
Component Analysis (PCA) was used to cluster the vibration modes of the anodes. It is
shown that the proposed approach allows detecting and distinguishing different types of
anode internal defects. Some of the tested anodes were cut and imaged in order to confirm
the results visually.

Keywords
Aluminum smelting Baked carbon anode NDT Vibration Modal analysis PCA

Introduction lab characterization currently used in most modern primary

The decreasing quality and increasing variability of the
anode raw materials [1, 2], combined with the frequent
supplier changes made to reduce purchasing costs and meet
specifications, make it increasingly difficult for carbon plant
operators to manufacture anodes with consistent quality.
Since fluctuations in anode properties may affect the per-
formance of reduction cells, it is important that sudden drifts
in anode quality be detected, and that corrective actions be
implemented in a timely fashion. This is difficult to achieve
using the quality control scheme based on core sampling and
M.B. Boubaker
D. Picard
C. Duchesne (&)
H. Alamdari
M. Fafard
Aluminium Research Center-REGAL, Université Laval, Laval,
QC G1V 0A6, Canada
e-mail: carl.duchesne@gch.ulaval.ca
J. Tessier
Alcoa Global Primary Metals, Center of Excellence,
Deschambault, QC G0A 1S0, Canada
aluminum smelters. Only a small proportion of the produc-
tion can be tested by this method due to the costly, time
consuming, and destructive nature of the analytical tech-
niques. In addition, it is known that the core properties are
not necessarily representative of those of the whole block.
Hence, developing rapid and non-destructive methods for
quality control of individual baked anode blocks is highly
desirable.
New devices for measuring the electrical resistivity dis-
tribution in carbon anodes were recently proposed as an
indicator of anode quality [3–5]. These systems target one of
the most important anode properties (electrical resistivity)
and should enable feedback corrective actions to be imple-
mented on the anode manufacturing process (e.g. paste
formulation). Although these instruments have been shown
to detect changes in resistivity distribution, it is not clear at
this point if these measurements could be used to diagnose
the cause of these changes and discriminate between the

© The Minerals, Metals & Materials Society 2017 1289

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_154
1290
Table 1 Anode numbers and Anode numbers
description
1, 4, 5, 6, 10, 11, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27
2, 3, 7
8, 12, 13
14, 15
various types of anode defects occurring in practice (e.g.,
cracks, poorly mixed paste, etc.).
This work investigates an alternative and perhaps com-
plementary approach based on vibrational excitation of the
baked anodes and modal analysis. This non-destructive
testing method can potentially be a more direct approach for
sensing the anode internal structure because physical defects
modify the material vibration response. It should provide
overall information about the quality of an anode block, and
enable defect diagnosis if these have a different impact on
the anode vibration response. Modal techniques are also easy
to implement for online defect detection and quality control.
A similar approach has been applied for various porous
materials [6, 7].
Modal analysis can be implemented in different ways
depending on the application. Most of them use the lower
natural frequencies obtained experimentally from the power
spectrum of the material vibration response signals [8, 9].
Alternative approaches include empirical modelling of the
mode shapes estimated from vibration response data [10–12],
as well as numerical model updating methods [13–15]. The
first approach based on natural vibration frequencies was
selected in this work since it is simple and allowed discrim-
inating the anode defects of interest.
In order to test the proposed approach, a set of full scale
baked anodes were selected from the Alcoa Deschambault
Quebec (ADQ) smelter. Some anodes had known defects
visible from the surface and others not. Anodes free of
visible defects were also included in the set. The anodes
were excited mechanically on different faces and positions
on the block and their vibration responses were also recor-
ded at different locations. The vibration modes of each anode
were obtained from their signal power spectrum. It was
decided to use only the first two fundamental natural fre-
quencies based on numerical modelling. The large set of
vibration mode data was analyzed using Principal Compo-
nent Analysis (PCA) [15–17] in order to cluster the tested
anodes based on their vibration response signature. It is
shown that defect free anodes can be discriminated from
defect anodes. In addition, the latter could be distinguished
based on the type of defect present in their structure. These
results were validated by visual inspection after cutting some
of the anodes.
M.B. Boubaker et al.
Description
Free of external defects
Cracks visible externally
Surface defects
Start-up anodes
Materials and Methods
Selection of Industrial Anodes
A total of 27 full-scale baked anodes manufactured at the
Alcoa Deschambault Quebec (ADQ) smelter were used in
this work. In order to test the proposed approach, good
anodes (defect free) as well as anodes including different
types of defects are required. Since it is difficult to assess
whether an anode contains defects or not without destroying
them (unless defects are visible from the surface), it was
decided to select a variety of anodes produced under dif-
ferent conditions (i.e., normal operation and during paste
plant start-ups) as well as some anodes containing known
defects, visible from the surface (i.e., cracked anodes, sur-
face defects due either to intensive firing or to handling).
Most of the selected anodes had no externally visible
defects. The anodes were numbered from A1 to A27.
Table 1 shows which anodes were assigned to each of the
previously mentioned categories.
Some example anodes are shown in Fig. 1. Anode A1 has
no externally visible defect, A3 and A7 had large cracks
visible from the surface, and A8, A12 and A13 had different
types of surface defects.
Numerical Modeling
A finite elements model of a baked anode was built in order
to guide in the development of the experimental mechanical
vibration set-up. The purpose of the model was to simulate
the vibration response of an anode obtained for different
combinations of excitation points and type and position of
the anode supports as shown in Fig. 2. The objective was to
select the combination allowing to identify the most global
vibration modes with the highest signal-to-noise ratio that
capture the most important defects.
Some of the small geometrical details of the anode, such
as the flutes in the stub hole, were simplified in the model
because they were found to have little impact on the global
vibration modes. The boundary conditions were applied
either at the bottom or at the side of the anode so as to leave
only two translation and one rotation modes to simulate
Non-Destructive Testing of Baked Anodes Based on Modal Analysis …
Fig. 1 Example of anodes
showing different types of defects
Fig. 2 Different tested supports
configurations
different supports as per the tested configurations shown in
Fig. 2 (plan support, three prismatic supports or bars). The
interaction constraints “tie” and “hard contact” allowed good
modeling of the degrees of freedom associated with the
anode supports.
In order to predict the vibration responses of the full-scale
anode, a simple three-dimensional model was constructed. It
is worth mentioning that distributed irregularities such as
1291
pores and cracks generally cause mass and stiffness varia-
tions. Accordingly, the anode model was divided into seven
zones along the anode height (numbered in yellow in Fig. 5),
and different mechanical properties were assigned to each
zone. The ranges were as follows: density 1560–
1610 kg/m3, Young’s modulus 7000–11,000 MPa and
Poisson’s ratio 0.18. The density values were obtained from
X-ray computed tomography images collected in previous
1292
Fig. 3 The first two simulated vibration modes of the anode for the two cross bars configuration and excitation on the top
work [19]. The Young’s modulus and Poisson ratio values
were taken from the work of Eliassen [20] and the CIR
Laboratory [21], respectively. The supports (bars and
prisms) always had the properties of steel. The finite element
model of the anode was developed using the Abaqus/CAE
6.14-1 software and the anode was modelled with 10,000
quadratic solid elements. Some of the simulated modes are
shown in Fig. 3.
After simulating the different support configurations and
excitation positions shown in Fig. 2, the one where the
anode sits on its side on two cross bars was selected (top
right in Fig. 2). This configuration yielded lower frequency
vibration modes, which should help distinguishing the var-
ious types of anode defects.
Excitation and Measurement Set-up
The vibration set-up shown in Fig. 4 was designed to identify
the natural frequencies of the anodes after mechanically
exciting them on four faces. A soft rubber impact hammer
was used for the excitation in order to reduce the induced
resonance and increase the amount of energy transferred by
the mechanical displacement. The anodes were excited at five
Fig. 4 Experimental mechanical vibration set-up
M.B. Boubaker et al.
Fig. 5 Position of the five excitation points (identified by numbers) on
four different anode faces (E1-orange, E2-blue, E3-red, E4-green
circles)
different places on each face as shown in Fig. 5. The
accelerometers were positioned differently when exciting on
different faces as shown in Fig. 6. The colors of the dots in
these two figures identify the excitation face. Note that
excitation faces E2 and E3 (blue and red dots in Fig. 5) are
the same, but the accelerometers were placed differently in
these two cases. Each excitation test was repeated 8 times to
average out inaccuracies caused by manual excitation.
Seven accelerometers (Kristler, model 8310A25A1M11-
SP15M) were distributed across each face and measured the
acceleration resulting from each excitation. They were held in
place using hot glue to ensure good contact, especially for
those mounted vertically which could fall off the anode
during testing.
The acquisition system Vishay 6100 Series was used to
acquire the accelerometer signals by strain gauge cards. Since
high-level reading cards were unavailable, all accelerometers
had to be connected with a line voltage reducer device to
strain gauge reading cards. The system can acquire accurate
signals at a frequency of 10,000 Hz playback channels. In
addition, the system software (Strainsmart, Vishay) can
analyze the raw data of each 16,384 series by mean of Fourier
transform. The longest data acquisition time was 6.4 s, which
includes the time required for excitation and reading the data
of the accelerometers. The data exported from the acquisition
system were the relative amplitudes on a set of frequencies
for each of the accelerometers.
Non-Destructive Testing of Baked Anodes Based on Modal Analysis …
Fig. 6 Position of the seven
accelerometers (identified by
numbers) for measuring the
response of each corresponding
excitation face (R1-orange, R2-
blue, R3-red, and R4-green dots)
Modal Analysis of the Vibration Signals
An algorithm developed in Matlab version R2014a (Math-
Works, Natick, MA, USA) was used to identify the first two
fundamental natural frequencies after transferring the time
signal into frequency domain using Fast Fourier Transform
(FFT). Figure 7 shows the power spectra of the vibration
responses of 11 anodes measured by one accelerometer
located at the same position on the top face (E1-orange dots
in Fig. 5). The power spectra show two dominant peaks at
60 and 300 Hz corresponding to the first two global modes,
so called fundamental modes. The presence of defects in the
anode structure would cause these peaks to shift on the
frequency scale. After some preliminary work, it was deci-
ded to limit the analysis to frequencies lower than 500 Hz
because the modes beyond that frequency did not help
Fig. 7 The first two peaks of the
power spectrum of 11 anodes
obtained from one accelerometer
after excitation on the top face
1293
discriminate the anodes. This also increases the resolution of
the signals and facilitates the identification of the modes.
The first two peaks of each anode vibration response were
selected for the analysis since they are the most accurate and
were found sufficient to detect and discriminate the defects
present in the anodes. Modal tests were thus conducted
initially on a defect free anode to identify the first two
fundamental natural frequencies as shown in Fig. 7. Identi-
cal tests were subsequently performed on all the 27 anodes.
The frequency at which the first two peaks occurred for a
given anode was extracted from each vibration response
collected from that anode (i.e., 5 excitation points  4
faces  7 accelerometers = 140 signals/anode) and these
were stored in a (1  280) row vector. This vector of fre-
quencies contains the vibration signature of one baked
anode. Collecting those vectors for all the tested anodes
1294
Table 2 Percent cumulative sum Component
of squares explained (R2) by the
PCA model built on modal 1 33.2
features collected from anodes 2 53.0
yields a matrix X of dimensions (27  280). This large data
matrix was then analyzed using PCA.
Principal Component Analysis (PCA)
PCA is a multivariate statistical method approximating a
high dimensional dataset X (I  J) by a much lower
dimensional subspace T (I  A), where A << J, explaining
the main variance directions in the data. It performs the
following bilinear decomposition of the data matrix X:
X
A
X¼ ta pTa þ E ð1Þ
a¼1
where the orthogonal score vectors ta (I  1) represent the
projection of each observation (row in X) into the lower
dimensional subspace formed by the corresponding
orthonormal loading vectors pa (J  1). The latter consist of
linear combinations of the original variables (i.e. ta = X pa).
The model residuals are gathered in the residual matrix
E (I  J). The principal components (pairs of t’s and p’s)
are ordered in such a way that the first (t1) captures the
greatest amount of variations in the data, whereas the second
captures the greatest amount of variance orthogonal to the
first, and so on. Scatter plots of the scores ta allow to
visualize the clustering patterns of the observations (i.e.,
tested anodes) in the lower dimensional subspace. Interpre-
tation of the clustering patterns based on the original vari-
ables (columns of X or the vibration modes) is obtained by
using scatter plots of the loading values pa. For more details
on PCA the reader is referred to Wold et al. [18].
Results and Discussions
In this section, the results of the PCA model applied to the
anode vibration data matrix X are presented first. The clus-
tering patterns of the anode vibration response is explained
and interpreted based on the vibration modes. The results are
then further validated by showing images of cuts made on
several of the tested anodes to unveil their internal structure.
Finally, a simplified PCA model is presented based on a
reduced number of accelerometers and excitation points in
order to show that similar conclusions can be reached using
a simpler experimental vibration set-up.
M.B. Boubaker et al.
R2 (%)
The first two PCA components were found sufficient to
discriminate the anodes based on their vibration response.
Only these two are discussed here. The cumulative sum of
squares explained (R2) by the PCA model using the two first
components is provided in Table 2. About half of the vari-
ance contained in the vibration mode data matrix X is cap-
tured using only the first two components. The columns of
X were mean-centered and scaled to unit variance prior to
applying PCA (common practice).
The PCA results are presented in Figs. 8 and 9. Figure 10
supports the discussion by showing images of some of the
anode cuts. The clustering pattern of the 27 anodes is shown
in the t1 − t2 score plot (Fig. 8). Each point in the plot cor-
responds to the vibration response signature of one anode.
They were labelled and colored according to the anode
number and description presented in Table 1. The anodes
containing known defects visible from the surface (red and
blue dots) as well as the start-up anodes (green dots), which
are expected to be different, fall on the left hand side of the
score plot in the negative t1 region. All these anodes clearly
distinguish themselves from most of the other anodes having
no externally visible defects (black dots). At the time of vi-
bration testing, it was unknown whether the latter group of
anodes contained defects within their structure or not. This
explains why cutting the anodes was necessary for validation
purposes. It is also interesting to note that these anodes (black
dots) divide into roughly two groups: anodes A19, A21, A23
and A27 (lower right quadrant), and all the others. It will be
shown later that the former group of anodes had no or very
few internal defects after visual inspection of their cuts. The
others had different types of defects.
Images of the internal structure of some anodes are pro-
vided in Fig. 10 in order to support the observations made on
the anodes clustering pattern (Fig. 8). Note that the size of the
cracks in these images has been virtually enlarged for a clearer
visual appreciation. The anodes containing cracks visible
from the surface (red dots in Fig. 8) all cluster together in the
negative t1 region. The image of anode A2 after cutting shows
large transversal (vertical) cracks at one end. The black
anodes A18 and A24 clustering in the extreme positive t1
region had several longitudinal (horizontal) cracks below the
stubholes. Anodes A14 and A26 (lower left quadrant) had a
mixture of vertical and horizontal cracks also below the
stubhole regions. Finally, the images of anodes A19 and A27
revealed no or very few defects in their structure. These
results clearly show the potential of modal analysis for
Non-Destructive Testing of Baked Anodes Based on Modal Analysis …
Fig. 8 PCA score plot (t1–t2) of
the anode vibration responses
Fig. 9 PCA loadings (p1–p2) of
the anode vibration responses
detecting the presence of defects within baked anodes. It also
demonstrates a good sensitivity to the types of defects.
A clearer diagnosis may help selecting appropriate remedial
actions to implement on the manufacturing process and/or
establishing anode sorting schemes.
The loading plot shown in Fig. 9 is now used to interpret
the clustering pattern observed in Fig. 8 in relation with how
the presence of defects shifted the first two vibration modes.
Each point on this plot is related with the frequency of its
1295
corresponding mode obtained after exciting the anode at a
given position, on a given face and recorded by one of the
seven accelerometers. To facilitate the reading of the plot,
the vibration modes are identified by ellipses.
The loading plot should be interpreted as follows. The
absolute value of a loading indicates the importance of the
corresponding variable (vibration frequency for a given
mode in response to an excitation at one point on one face)
in a given component. The signs of the loading values are
1296
Fig. 10 Images of cuts made on some tested baked anodes
M.B. Boubaker et al.
used to interpret the correlation between pairs of variables.
Modal features having loading values of the same sign for
one component are positively correlated and they are nega-
tively correlated when they have opposite signs. The loading
values can be interpreted independently for each PCA
component since they are orthogonal to each other. Figure 9
shows that most of the first mode features have strong
loadings along the second component (p2) and weak values
along the first (p1). The opposite can be said about the
loading values of the second mode. This suggests that the
separation of the anodes along the first PCA component (t1)
is determined by the second vibration mode and the sepa-
ration along t2 by the first vibration mode. Hence, the second
vibration mode for the anodes having positive t1 score values
shifted towards higher frequencies compared to the average
of the 27 anodes, and vice versa for the anodes having
negative t1 values. Similarly, the first mode of the anodes
clustering in the positive t2 score region shifted towards
higher frequencies and in the opposite direction for those
anodes clustering in the negative t2 region.
Therefore, it seems that the direction of the shifts in the
second vibration mode indicates the orientation of the cracks.
A shift towards lower frequencies is associated with anodes
containing cracks mostly oriented vertically (cluster in the
left hand side of the score plot). A shift towards higher fre-
quencies suggests that the cracks are mostly oriented hori-
zontally (anodes in the right hand side of the plot). Those
clustering around the t1 origin (frequency around average
value) contain a mixture of crack orientations. The first mode
separates anodes A13, A14, A26 and A19, A21, A23, A27
from all the other anodes along the t2 axis. It is speculated that
the shifts in the first mode related with this clustering pattern
may be due to differences in the physical and/or mechanical
properties of the anodes affecting their dynamic vibrational
response. This will be clarified in future work.
Pruning of the PCA Model
Although the proposed approach seems promising, it uses
many excitation points and accelerometers which can
become cumbersome and time consuming for an industrial
implementation. It addition, the loading plot (Fig. 9) has
shown that several of the responses obtained for different
excitation points and accelerometers were redundant (i.e.,
very similar loading values). Pruning of the PCA model was
therefore investigated.
The results shown in Fig. 11 were obtained for a pruned
model based on one single excitation point (instead of 5) on
the four anode faces and vibrations recorded by 4
accelerometers (instead of 7). Hence, the dimensions of the
vibration data matrix X were significantly reduced to
(27  32). Comparing Figs. 8 and 11 reveals only minor
Non-Destructive Testing of Baked Anodes Based on Modal Analysis …
Fig. 11 PCA score plot (t1–t2)
after model pruning
differences in the clustering pattern of the anodes, and do not
change the conclusions obtained using the original model. It
is therefore clear that the experimental set-up for modal
analysis can be optimized to reduce cycle time while pro-
viding useful information for baked anode quality control.
Conclusion
Modal analysis was investigated for rapid and
non-destructive testing of individual baked carbon anodes.
A set of full scale baked anodes were selected from the
Alcoa Deschambault Quebec (ADQ) smelter, including
some high quality anodes and defect anodes (visible from
the surface and not). The anodes were excited mechanically
on different faces and positions on the block and their
vibration response was also recorded by accelerometers at
different locations. The vibration modes of each anode were
obtained from their signal power spectrum in the 0–450 Hz
range. Numerical modelling of the anode was used to sup-
port the experimental set-up design. The large set of vibra-
tion mode data was analyzed using Principal Component
Analysis (PCA) in order to cluster the tested anodes based
on their vibration response signature.
It was shown that defect free anodes can be discriminated
from defect anodes. In addition, the latter could be distin-
guished based on the type of defect present in their structure.
The second vibration modes were found to be sensitive to
the presence and orientation of cracks within the anode
block while the first might be related to changes in the
1297
physical and mechanical properties of the anodes. These
conclusions were supported by images of the internal
structure of the anodes collected after cutting some of them.
Based on these promising results, the modal analysis set-up
will be further refined and optimized in future work.
Acknowledgements The authors would like to acknowledge the
financial support of the Natural Sciences and Engineering Research
Council of Canada (NSERC), Fonds de Recherche du Québec—Nature
et Technologies (FRQNT), Alcoa and the Aluminum Research Centre
—REGAL. The assistance provided by REGAL personnel (Hugues
Ferland and Guillaume Gauvin), and by the Alcoa Deschambault anode
plant technical staff is also greatly acknowledged.
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 3D Automated Anode Stub Inspection System

Jean-Pierre Gagné, Rémi St-Pierre, Pascal Côté, and Harold Frenette

Abstract
During the production of aluminium from conventional prebaked Hall-Héroult electrolysis
cells, anodes have to be replaced on a regular basis. The anode rod assemblies, which are
submitted to multiple heating/cooling cycles, tend to deform over time. Moreover, attacks
from HF gas and liquid bath erode the stubs to a different extent at each cycle. The stubs
thus require regular inspection to determine if they need to be repaired. Repair costs are
often very expensive and difficult to follow and forecast. In 2016, STAS commissioned its
new ASIS3D for the 3D analysis of stubs in any configuration (like hexapods). All anode
rods in the rodding shop are automatically inspected in less than 30 s. A work order is
automatically generated for each anode rod that needs to be repaired, after which it is
registered in the database and printed on the anode rod. This paper describes the industrial
performances of the ASIS3D.

Keywords
Anode stub Inspection Anode rod tracking Process monitoring

Introduction (ABI). This plant is located in Quebec, Canada, and uses the
AP18 technology (hexapod) to integrate the latest features in
The tests to assess the industrial performances of the ASIS3D terms of automation and 3D metrology already proven in
technology (Anode Stub Inspection System) were carried out other industrial sectors. The cycle time of the equipment is
on an industrial installation at Aluminerie de Bécancour Inc. only 30 s, and the rejection criteria are easy to change. Any
type of stubs can be measured: hexapod, bipod, tripod, etc.
J.-P. Gagné (&) In the present article, we will use the term “hexapod” to refer
Electrolysis & Carbon Products, STAS Inc.1846, Rue Des to any kind of stub arrangement. The validation method is
Outardes, Chicoutimi, QC G7K 1H1, Canada
presented, as well as some examples of measurement.
e-mail: gagne.jp@stas.com
R. St-Pierre
STAS Inc. 1846, Rue Des Outardes, Chicoutimi,
QC G7K 1H1, Canada Why Automated Anode Rod Inspection
e-mail: stpierre.remi@stas.com
P. Côté Anode rod inspection is essential to ensure the proper operation of
Development and Innovation, STAS Inc, 1846, the rodding shop. On one hand, most rodding shops still use
Rue Des Outardes, Chicoutimi, QC G7K 1H1, Canada manual inspection, which is well described in reference [1].
e-mail: cote.pascal@stas.com
In addition to being expensive in terms of manpower, manual
H. Frenette inspection is non-consistent and also generates non-optimal and
Alcoa Smelting Center of Excellence, Alcoa Canada,
non-controlled efforts in terms of repairs. Moreover, no infor-
Aluminerie Deschambault, 1 Boulevard Des Sources,
Deschambault, QC G0A 1S0, Canada mation is recorded about the state of the stub fleet in the plant. On
e-mail: harold.frenette@alcoa.com the other hand, automated inspection allows huge business cases.

© The Minerals, Metals & Materials Society 2017 1299

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_155
1300 J.-P. Gagné et al.

The reasons to justify the implementation of the ASIS3D

system are threefold. First of all, the optimal control of repair
costs which, for most plants, can certainly justify the
implementation of an ASIS3D. A medium-sized smelter may
have about 10,000 hexapods in inventory (anode rods),
which means very expensive costs in terms of repairs on an
annual basis. Most of the time, stubs are repaired outside of
the plant by subcontractors. How does the ASIS3D help
optimize the repair effort? In fact, the ASIS3D keeps the
history of all measured hexapods in the database. So, after
about 30 days, the whole picture of the plant stub fleet is
very well known: stub minimum diameter, stubs length, etc.
The ASIS3D allows modifying the rejection criteria very
easily. So, the supervisor can set the rejection criteria based
on the targeted repair effort, and a tight follow-up can be
Fig. 1 ASIS3D installed at ABI
performed. Indeed, for each hexapod rejected further to
inspection, a work order is automatically generated in the
database and printed on the bottom of the anode stem. The orders on the stems, is installed at the exit (Fig. 2). It is
work order includes a tracking number, so that the hexapods worth noting that the location of the maintenance areas and
can be routed to the appropriate location to be repaired. The the size of the equipment can be adapted to the rodding shop
repairs to make are perfectly clear (printed on the stems), and and the stub technology.
the costs are known to all parties involved. Three (3) stops are installed on the overhead conveyer:
A second argument for the business case translates into one at the entry (Stop 1), a second in the middle (Stop 2),
manpower restructuring or optimization. Depending on the and a third one at the exit (Stop 3), just prior to the printer
plant, up to four (4) operators can be required for manual head. The ASIS3D is quite easy to implement under the
inspection (if the rodding shop operates 24/7). overhead conveyer, and the travelling path of the hexapod is
A third argument, but not the least, is the optimization of always free of mechanical interferences (even during the
the rodding operation. The typical loss of voltage of an scanning process). The control panel, which includes an
anode is 300 mV [2]. About 120 mV is related to industrial computer, a graphical operation interface
carbon/cast iron/stub interfaces. According to studies [2, 3], (HMI) and a safety relay, is linked to the PLC of the rodding
50–70 mV can be added to this 120 mV interface if the shop and the plant database. In continuous operating mode,
stubs are not in good condition for rodding. The ASIS3D only 30 s (cycle time) are necessary to inspect one hexapod.
gives the necessary tools to optimize the rodding. Actually,
the virtual rodding performed for each hexapod allows
controlling the minimum and the maximum space between
each stub and the corresponding internal side wall of anode
block holes. The free space under each stub for the rodding
is also available for the optimization (this free space is filled
with cast iron during the rodding). However, this segment of
the business case is less tangible and has not been considered
to justify the project.

Industrial Unit

Figure 1 shows an ASIS3D installed at ABI, after the last

cleaning process of the anode rod and prior to the repair loop
on the overhead conveyer. The required floor surface is
about 4.25 m long by 2.6 m wide, centered on the overhead
conveyer. The base of the unit is installed at about 2 m
above the floor to fit with the position of the height of the
hexapods, and walkways are installed to allow access for
maintenance. The industrial printer, used to write the work Fig. 2 Exit of ASIS3D where printer is installed
3D Automated Anode Stub Inspection System 1301

The system uses class 3 lasers installed in an enclosure

(Fig. 1). Access to the scanning area is restricted by inter-
locked doors that prevent the operators from entering the
machine when in operation. With this security system in
operation, the equipment becomes a class 1 laser product,
which means it is safe under all conditions.

Measurements Performed by the ASIS3D

The ASIS3D acquires a point cloud of about 1 million points

(x, y, z) to digitally reproduce each hexapod and uses a
Fig. 5 Erosion of stub tip
powerful world-class industrial 3D metrology software to
perform its measurements. This means that additional mea-
surements can easily be added if needed. The standard
measurements already implemented in the ASIS3D are
illustrated in Figs. 3, 4, 5, 6, 7 and 8, which are examples of
point cloud files digitalized with the ASIS3D. Here is a
description of the measurements:

• Length of each stub (Fig. 3). The top of the spider is used
as a reference plane for the measurements. The system
considers a minimum value and a maximum value to

Fig. 6 Cast iron

Fig. 3 Stub length

Fig. 7 Fitness for rodding

accept or reject the hexapod. It would be easy to also

consider the maximum difference between stub lengths in
order to optimize the cast iron thickness under stubs
during the rodding.
• Minimum diameter of each stub (beaver effect) (Fig. 4).
The results can be displayed in terms of minimum
diameter or the maximum deepness of the notch. This
default is located just above the rodding section. The
criterion could be the minimum diameter of the maxi-
Fig. 4 Beaver effect or minimum diameter mum deepness allowed.
1302
Fig. 8 Toe in
• Erosion of stub tip (Fig. 5). This measurement reflects
the quantity of material that remains on the stub tip
(mainly the section corresponding to the rodding). The
result is given in percentage. The 100% value corre-
sponds to a new stub, while the 70% value relates to a
stub with 30% erosion. The reject criterion is the mini-
mum value accepted.
• Presence of cast iron (Fig. 6). The system measures the
thickness of the cast iron pieces that remain on the stubs,
with the maximum thickness allowed as the criterion.
Those measurements can also be used to follow the
efficiency of the process used to remove cast iron.
• Fitness for rodding (Fig. 7). The purpose of this mea-
surement is to validate if the stub tips of the hexapod can
still be entered properly in the next anode block. In order
to perform this measurement, the software simulates a
virtual rodding of the stubs inside 6 tubes corresponding
to the sizes and locations of the holes in an anode block.
The six (6) tubes are positioned with relation to the anode
stem and center stubs. There are two criteria for each
stub: the minimum space and the maximum space
between the wall of the hole and the surface of the stub.
Not only is this measurement a go-no-go gauge, but it
can also be used to optimize the rodding. Indeed, if these
criteria are combined with the lengths of the stubs, the
cast iron thickness under and around the stubs can be
evaluated and used to optimize the rodding [3].
• Toe-in of stubs (Fig. 8). Those measurements are used as
an indicator for the stub straightening process. It replaces
the usual manual method of measurement.
Verification Method
Like with any measuring instrument, there should be a
method to validate the proper operation of the system. The
3D sensors themselves don’t need to be calibrated.
J.-P. Gagné et al.
Fig. 9 Validation target
Mechanisms used to hold the sensors are heavy and very
robust. However, during the initial start-up, or if a sensor has
to be replaced, a new alignment is necessary. The verifica-
tion method is used to make sure that the sensor is aligned
and operates properly. The verification takes only a few
minutes and can be performed by one technician. A good
practice could be to verify the system monthly.
A dummy aluminium stub, including some typical
defaults, is used as a validation target. The verification target
has two stubs of different lengths. Stub 1 presents a beaver
effect and severe erosion on its tip, and stub 6 presents a cast
iron piece and a reduced diameter at a higher position. The
stubs of the hexapod are numbered from 1 to 6 based on the
side where the stem is printed. We use positions 1 and 6 to
obtain the maximum depth of field used by the sensors.
Figure 9 shows a picture of the validation target.
In order to perform the validation, the first step consists in
selecting the maintenance mode on the ASIS3D HMI, after
which the validation target has to be hung by the technician
right in the center of the ASIS3D. Then, using the HMI, the
operator starts the validation process. After the measure-
ments, the HMI shows the results in a comparison table, with
the real dimensions. The validation target measurements are
then stored in the database.
Table 1 shows the result of three different scans, taken
over a period of 2 months at the plant. Only the initial
alignment was performed at the start-up of the equipment at
the plant. The accuracy of the ASIS3D (worst case) has been
estimated at ±2 mm. So, in the HMI, all results are rounded
to the last millimeter. The results of the measurements
(Table 1) are rounded to the last 0.5 mm in order to
accentuate the differences between the results.
It can be observed in Table 1 that the actual accuracy of
the ASIS3D measurements is very good. Indeed, all mea-
surements are inside ±1 mm compared to the actual
dimension of the reference target. The measurements of the
stub tip erosion are inside ±2% of the actual reference
3D Automated Anode Stub Inspection System 1303

Table 1 Measurements on ASIS3D Actual

validation target measurement
Scan 1 Scan 2 Scan 3 Average
Date of the scan 2016-05-04 2016-05-26 2016-07-20
Stub length (1) (mm) 451.5 451.5 451.5 451.5 452.0
Stub length (6) (mm) 476.5 475.5 476.0 476.0 476.5
Distance between stubs (1 and 2) 950.0 950.0 950.0 950.0 950.0
(mm)
Stub tip erosion (1) (%) 79 81 82 81 80
Beaver effect (1) (max depth) 10.5 10.5 10.0 10.3 10.6
(mm)
Cast Iron thickness (stub 6) 31.5 32.5 32.5 32.2 32.6
(mm)

target. Moreover, accuracy of this measurement could be
improved, providing that the computation capacity is adap-
ted in order not to affect the cycle time of 30 s.
At the end of the validation process, the HMI shows the
measurements in a table where a color code is used. Green is
used if the alignment is perfect, red if the alignment has to be
redone, and yellow if the results are close to the limits.
Industrial Results
To verify the repeatability and accuracy of the ASIS3D on
real worn hexapods, four hexapods each presenting a
specific default were selected. Those hexapods were scanned
three times inside the ASIS3D to verify the repeatability of
the system, and hand measurements were to compare the
numerical measurements with the actual hexapod.
The hexapods that were selected are shown in Figs. 10,
11, 12, 13 and 14. Each of these figures presents a point
cloud representation acquired with the ASIS3D and a picture
of the hexapod taken as much as possible with the same
point of view. The first hexapod (hexapod 1), shown in
Fig. 10, was selected for the very short length of the two
first stubs on the left, cut by erosion, just above the rodding
area.
The second hexapod (hexapod 2), shown in Fig. 11, was
selected for the beaver effect on the center front stub.
The third one (hexapod 3), shown in Fig. 12, was chosen
for the erosion of its stub tip (stub 3), on the right.
The fourth hexapod (hexapod 4) was selected for the cast
iron piece on stub 1 located in the rodding area. This hex-
apod was rejected during the virtual rodding. Figure 13
shows the point cloud representation illustrated with the
virtual rodding and a picture of the hexapod with a go-no-go
gauge corresponding to the holes located on the top of the
anode block.
The results of the measurements shown in Figs. 10, 11,
12 and 13 are presented in Table 2. For each measurement,
the results of three different scans were obtained with the
ASIS3D as well as with the corresponding hand measure-
ments, which were taken carefully. We used a caliper or a
measuring tape for the stub length, beaver effect and cast
iron thickness. The precision of the hand measurements is
±0.5 mm for the measuring tape and ±0.0254 mm for the
caliper. Even if the caliper was very precise, the surface
condition led to less accurate measurements. So, all mea-
surements (tape and caliper) were rounded to the nearest
0.5 mm. Regarding the erosion of the stub tips, the volume
was measured with a bucket of water, filled with graduated
beaker up to a reference line indicating the top of the
inspection zone. The same procedure was performed on a
new stub and the quantity of water was compared with the
eroded stub tips one in order to obtain the percentage
missing or eroded.

Fig. 10 Hexapod 1

Point cloud Picture

1304 J.-P. Gagné et al.

Fig. 11 Hexapod 2

Point cloud Picture

Fig. 12 Hexapod 3

Point cloud Picture

Fig. 13 Hexapod 4

Point cloud Picture

Fig. 14 Hexapod 4

Point cloud of hexapod 4 Picture of hexapod 4

Like the measurements on the validation unit, the three
(3) different scans performed with the ASIS3D demonstrate a
very good repeatability. Indeed, the maximum difference
between the minimum and maximum values is one (1) mil-
limeter for the three (3) scans. The accuracy of the mea-
surements is also very good, with results inside ±2 mm
accuracy. In fact, the irregularity in the surface and shape of
the worn hexapod makes it difficult for very precise hand
measurements as well as numerical measurements on the
point cloud. Regarding the erosion of the stub tips, only 2%
difference was obtained between the lowest numerical
measurement and the hand measurement. The measuring
procedure can be improved, but the scan time would be
affected. However, this 2% difference represents a good
3D Automated Anode Stub Inspection System 1305

Table 2 Measurements on actual hexapods

ASIS3D Actual measurement (by hand)
Scan 1 Scan 2 Scan 3 Average
Hexapod 1: length of stub 1 (mm) 358 357 358 357.5 358.5
Hexapod 1: length of stub 2 (mm) 354 353 353 353.5 355.0
Hexapod 2: Beaver effect (mm) (Max depth) 33 33 33 33 33.5
Hexapod 3: Stub tip erosion (3) (%) 53 52 53 53 54
Hexapod 4: Cast Iron thickness stub 1 (mm) 23 23 23 23 23.5
Hexapod 4: Virtual roddind (go-no-go) Rejected Rejected Rejected Rejected Rejected

accuracy considering the highly irregular surface of an ero-
ded stub. The cast iron thickness was evaluated with great
precision as well, with the same value obtained for the three
scans and only 0.5 mm with the hand measurement. The last
measurement is a combination of many measurements inside
the ASIS3D. As illustrated in the picture of hexapod 4
(Fig. 14), the ASIS3D indicates a conflict for the rodding,
and this result is corroborated by the go-no-go gauge.
Conclusion
The industrial ASIS3D has been successfully implemented
by STAS at ABI. This equipment is manufactured with
robust components already proven in other industry sectors,
requires very little maintenance and is very accurate. The
cycle time of the ASIS3D is only 30 s which is fast compared
to most of the other process in the rodding shop. The system
acquires a point clod of about 1 million points (x, y, and z)
for each hexapod. The industrial metrology software allows
additional measurements, if needed. The measurements can
be used to feed other equipment in the rodding shop, such as
the stub straightener, etc.
The business case can be different depending on the plant.
However, the perfect and optimized control of the stub repair
effort can probably be at the first position for most of the
plants. Indeed, the ease in changing the inspection criteria
easily combined with the work orders printed on the anode
stems and saved in the database are elements which allow
very efficiently a close follow-up of the repair costs which,
otherwise, would be very difficult to manage. Another
business case concerns the manpower for stub inspection,
which can be used for higher level tasks. About the mini-volt
savings by the rodding optimization, this business case is
certainly very important but it relies more on hypothesis.
The fleet of anode rods is a very important asset for any
smelter. The direct maintenance costs associated with such a
fleet can represent several million dollars a year. An auto-
mated inspection system can supply all the necessary data to
allow a rodding shop to pinpoint the most critical repairs on
each rod and perform only the required maintenance. After a
few months of operation, the information stored in the
database allows the planners to forecast the workload of their
rod repair shop.
The STAS ASIS3D/ Automated Stub Inspection System is
available for all stub technologies and allows a lot of pos-
sibilities in terms of optimization and automation.
References
1. P. Côté et al., Anode stub 3D inspection system. Light Met.
1165–1168 (2015)
2. H. Fortin et al., Thermo-electro-mechanical characterization of
anode interfaces at operating conditions. Light Met. 1335–1340
(2013)
3. D. Molenaar, B.A. Sadler., Anode rodding basics. Light Met.
1263–1268 (2014)
 Impact of Cast Iron Degradation and Cathode
Block Erosion on the Current Path
in the Cathodic Assembly of Aluminum
Production Cells

Martin Brassard, Marc LeBreux, Martin Désilets, Gervais Soucy,

Martin Forté, and Jean-François Bilodeau

Abstract
Carbon-cast iron electrical contact degradation is still considered as one of the main cause
for the CVD increase over the lifetime of the electrolysis cell. A thermoelectric finite
element model was developed to evaluate the effect of the carbon-cast iron electrical
contact degradation and the cathode erosion on the CVD and the current distribution inside
the cathodic assembly. Chemical degradation data from laboratory and industrial samples
were used to calibrate the cast iron and the contact resistivities. Results demonstrate that the
carbon block erosion and the contact degradation at the cast iron interface have a direct
impact on the current distribution at the carbon block surface. Both factors increase the
CVD when taken separately but the contact degradation outperforms the carbon block wear
when taken together.

Keywords
Aluminum Cathode Carbon Cast iron Degradation Erosion CVD

Introduction relationship between the cast iron electrical contact degra-

The cathode voltage drop (CVD) accounts for about 8% of
the total voltage of the aluminum production cell [1]. This
energy loss needs to be kept as low as possible to optimize
the production cost. The CVD is known to increase over the
cell’s life [2, 3]. One of the identified cause is the degra-
dation of the cast iron surface used to make the connection
between carbon block and the steel collector bars. That being
said, other phenomena at the carbon block surface like
erosion may also have an effect [4].
This study is an extension of the studies on cast iron
degradation mechanisms that have been already conducted
and published [5]. Further investigations about the
M. Brassard
M. LeBreux
M. Désilets
G. Soucy (&)
Université de Sherbrooke, 2500, Boulevard de L’Université,
Sherbrooke, Québec, J1K 2R1, Canada
e-mail: gervais.soucy@usherbrooke.ca
M. Forté
J.-F. Bilodeau
Rio Tinto (Centre de Recherche et Développement D’Arvida),
P.O. Box 1250, Saguenay, Québec, G7S 4K8, Canada
dation and the carbon block wear are carried out using a
finite element thermoelectric model built within ANSYS
software.
Methodology
Collector Bar Autopsy
One complete collector bar was extracted from a 2500 days
old aluminum production cell. The cast iron cylinders were
recovered using a two-steps operation: surface was drilled
using a diamond grit hole saw to cross the surface deposit
and the remaining cast iron was cut using a carbide grit
hole saw. After resin mounting, the extracted cylinders
were cut in half and polished to conduct metallography
analysis.
The optical microscope images of the surface deposit
were transformed into binary images. The white areas were
considered as metallic phases while the black areas were

© The Minerals, Metals & Materials Society 2017 1307

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_156
1308 M. Brassard et al.

Table 1 Metallic fraction and thickness of the cast iron surface deposit
Metallic Deposit thickness
fraction (mm)
Top of the collector bar 0.6 2.1
Side of the collector bar 0.5−0.75 1.1
Outer end section 0.05 2–7.5
Fig. 2 Schematic of the cathode wear profile

interpreted as a mixture of electrolytic bath. Table 1 gives

the consolidated data of the surface of the collector bar.
The deposit was considered as a metal foam in order to
estimate resistivity increase due to the surface deposit as
compared to the cast iron. The calculations were done using
the Eq. 1, xm being the metallic fraction, qmix being the
deposit resistivity and qCI being the cast iron resistivity.
qmix 1 the center of the cell and that of the solid ledge on the side.
¼ ð1Þ
qCI ðxm Þ3=2
taken into account by modifying the cathode geometry,
following the schematic of Fig. 2. The wear pattern is based
on previous published results on a related technology [7]. In
this work, only the wear depth is modified, it varies from 0 to
0.25 m. On the top of the carbon block, a “pseudomaterial”
is used to mimic the behavior of molten aluminum metal in
The governing equations for the electrical potential dis-
tribution and energy conservation may then be stated as [8]:

Thermoelectric Finite Element Model
In order to predict the effect of the cathode wear on the CVD
and the distribution of current density on the cathode block,
a three dimensional coupled thermoelectric finite element
model of the cathode block assembly is built with ANSYS.
In the proposed work the finite element model is solved for
steady-state regime only. Moreover, due to the symmetry
conditions, only a quarter of the geometry is studied.
A schematic of the proposed model is shown in Fig. 1.
The collector bar is made out of carbon steel rodded in
cast iron. An additional layer of cast iron is added to the
model to represent the addition of a reactive layer that forms
due to chemical degradation of the contact area. The shape
of the groove in the carbon block is rectangular and the
contact is considered to be perfect between the carbon and
the cast iron [6]. The cathode block is assumed to be made of
graphitized carbon. The erosion of the carbon block is also
r½rðTÞrV  ¼ 0 ð2Þ
r½kðTÞrT  þ qv ¼ 0 ð3Þ
where r is the electrical conductivity, V is the electrical
potential, k is the thermal conductivity and T the tempera-
ture. As can be seen in Eqs. 2–3, the electric and thermal
conductivities are function of the temperature. Moreover, the
volumetric heat source term qv represents the Joule effect
caused by the electric current flowing into the cathode block
assembly:
qv ¼ rE2 ð4Þ
where the electrical field is obtained from the solution of
Eq. 2 for the electric potential V. The corresponding
boundary conditions are summarized in Table 2.
For a chosen cathode wear profile (Fig. 2), the set of
boundary conditions (Table 2), and the thermoelectric
properties of each material (k, r), the system of Eqs. 2–4 is

Fig. 1 Schematic of the

a cathode block assembly and
b the cast iron layers wrapping
the steel collector bar
Impact of Cast Iron Degradation and Cathode Block Erosion … 1309

Table 2 Boundary conditions of the finite element model finite element model have shown that as the erosion goes
Boundary Boundary conditions deeper in the carbon block, the ledge toe becomes thicker.
X1 Fixed voltage, fixed temperature By being an electric insulator, it pushes the current density
toward the center of the block where the surface is free of
X2, X4, X5, X6, Convection heat transfer
X7 deposit.
X3 Symmetry for heat transfer and electric current
X8 Fixed current
Effect of the Cast Iron Electrical Contact
X9 Fixed electric contact resistance at steel/cast iron
interface
Degradation Combined with the Wear Profile
on the Current Density Distribution

The cast iron resistivity was updated in the model according

solved using ANSYS Mechanical software (release 16.0). In
this case, calculations are performed within the cathode
block assembly using a grid size of 375 000 nodes. Con-
vergence is declared when the sum of residuals for the dis-
tribution of the electrical potential as well the temperature is
inferior to 0.1%.
Results and Discussion
Estimation of the Surface Deposit Electrical
Resistivity
The surface deposit resistivity increase is estimated accord-
ing to the data that are displayed in the Table 1 and in Eq. 1.
The results displayed in Table 3 shows that the resistivity
increases from 1.5 to 2.8 for most of the cast iron surface
except for the outer end section, which presents a much
higher increase with a value of 89. Those results have been
used to calibrate the model.
Effect of the Wear Profile on the Current
Density Distribution
Figure 3 displays the 3D distribution of the current density
at the surface of the cathode block, for each wear profile. It
shows also the current density distribution at the cast iron
upper surface. On top of the cathode, the current density
concentrates at the ledge toe. Temperature results of the
Table 3 Increase of resistivity of the cast iron surface relative to the
virgin cast iron
Resistivity increase estimation
Top of the bar 2.15
Side of the bar 1.5–2.8
Outer end section 89
to the data presented in Table 3. The modified model
parameters are displayed in Table 4. The cast iron layer
thickness in the model is 15 mm, which is by far thicker
than the surface deposit observed in the collector bar
autopsy (1–2 mm). Previously reported results have shown
that the cast iron resistivity increases by two folds causes an
increase of 1% on the CVD [5]. However, in the same
study, calculations have shown that the contact resistivity
increase has a much greater effect on the CVD. The contact
resistivity was increased by 100 folds instead of the cast
iron resistivity to maximize the effect of degradation in the
model.
Figure 4 displays the 3D distribution of the current den-
sity for each wear profile combined with the electrical con-
tact degradation of the cast iron. This figure also presents the
current density distribution at the cast iron upper surface. As
shown in the previous section, the current density distribu-
tion is affected by the wear level of the carbon block.
However, one can see that the current density distribution on
the carbon block is clearly affected by the cast iron degra-
dation. The effect is the most evident for the carbon block
without erosion. In that case, the current density stays below
20,000 A/m2 and there is limited current concentration
where the ledge toe is located.
Figure 5 presents the maximum current density value and
its position along the length of the cathode block for both
scenarios of collector bar degradation. Results show that for
each wear profile, the current density is higher when the cast
iron contact is degraded. In that case, the maximum current
density is located at the cast iron surface, but for a wear
depth greater or equal than 0.2 m, the maximum current
density is now located at the top surface of the cathode.
However, when the cast iron contact is not degraded, the
maximum current density value is located at the top surface
of the cathode for a wear depth greater or equal than 0.05 m.
For a cathode which is not eroded (wear = 0 m), the location
of the maximum current density is moved to the cast iron
surface.
1310 M. Brassard et al.

a) Wear = 0 m d) Wear = 0.15 m

b) Wear = 0.05 m e) Wear = 0.2 m

c) Wear = 0.1 m f) Wear = 0.25 m

Fig. 3 Effect of the wear profile on the current density distribution—No cast iron degradation

Effect of the Wear Profile on the CVD
Figure 6 shows the CVD variation in relation with the wear
level and the degradation of the cast iron. Figure 4 revealed
previously that the current density is pushed toward the
center of the block as the wear goes deeper. This causes the
current path to be longer and to increase the equivalent
resistance according to Ohm’s law.
The CVD behavior is different when the cast iron elec-
trical contact is degraded. In such a case, the CVD does not
Impact of Cast Iron Degradation and Cathode Block Erosion … 1311

Table 4 Cast iron and contact Cast iron outer layer resistivity increasea Cast iron to carbon contact resistivity increase
resistivity modification
Top of the bar 2 2
Side of the bar 2 2
Outer end 2 100
a
The outer layer refer to the cast iron layer in contact with the carbon block. See the model geometry for more
details

a) Wear = 0 m d) Wear = 0.15 m

b) Wear = 0.05 m e) Wear = 0.2 m

c) Wear = 0.1 m f) Wear = 0.25 m

Fig. 4 Effect of the wear profile on the current density distribution—with degradation
1312
Fig. 5 a Maximum current density value and b its position on the block surface from the inner end of the carbon block
Fig. 6 Effect of the wear profile and cast iron degradation on the CVD
change much in relation with the wear level. The current
path is preferentially influenced by the cast iron degradation
and the wear has little effect on the final CVD result.
Conclusion
The thermoelectric finite element model developed for this
analysis has demonstrated that the current density distribu-
tion at the surface of the cathode block is related to the depth
of the wear. As the erosion progresses, the current density is
moved toward the center of the carbon block. This phe-
nomenon is observed no matter what is the cast iron
degradation evolution. However, the maximum current
density is moved from the carbon block surface to the cast
iron when its degradation is taken into account.
Moreover, the thermoelectric model has shown that the
wear by itself can cause an increase on the CVD. Results
M. Brassard et al.
have shown that the CVD increased by about 10% for the
0.25 m deep eroded block compared to the new block. When
the cast iron degradation data were implemented, the CVD
increased by 17%. In that case, the wear profile had no
apparent effect on the CVD result.
Acknowledgements Authors want to thank Dr. Alireza Hekmat’s for
his input on the metallography analysis. They also wish to acknowledge
Rio Tinto, the Natural Sciences and Engineering Council of Canada
and the “Fonds de Recherche du Québec, Nature et Technologies” for
their financial support.
References
1. H. Kvande, W. Haupin, Cell voltage in aluminum electrolysis: a
practical approach. JOM 52(2), 31–37 (2000)
2. W. Haupin, Cathode voltage loss in aluminium smelting cells. Light
Met. 339–349 (1975) (The Metallurgical Society of AIME)
3. C.J. Michel, Evolution of the cathodic ohmic drop during the
electrolysis in the aluminium cell. Light Met. 989–1003 (1985) (ed.
H.O. Bohner, The Minerals, Metals and Materials Society, New
York, NY)
4. D. Lombard et al., Aluminium Pechyney experience with graphi-
tized cathode blocks. Light Met. 653–658 (1998) (ed. by B. Welch,
The Minerals, Metals and Materials Society, San Antonio, TX)
5. M. Brassard, Dégradation chimique de l’interface cathodique
carbone-fonte de cellules de production d’aluminium, Ph.D. Thesis,
Université de Sherbrooke, 2016, pp. 61–92
6. M. Gagnon et al., Optimization of the cathode collector bar with a
copper insert using finite element method. Light Met. 621–626
(2013) (ed. B. Sadler, The Minerals, Metals and Materials Society,
San Antonio, TX)
7. P. Reny, S. Wilkening, Graphite cathode wear study at Alouette.
Light Met. 399–404 (2000) (ed. R.D. Peterson, The Minerals,
Metals and Materials Society, Nashville, TN)
8. ANSYS Inc., ANSYS Mechanical APDL Theory Reference (Canon-
burg, PA, 2013)
 Part XXVIII
Electrode Technology:
Electrode Design and Performance
 Finite Element Analysis of Slot Size Effect
on the Thermal-Electrical Behaviour
of the Anode

H. Chaouki, M. Baiteche, A. Jacques, E. Gosselin, H. Alamdari,

and M. Fafard

Abstract
In the aluminium industry, the anode quality is an important factor that influences the
Hall-Héroult process efficiency. For this purpose, many efforts have been done in order to
optimize the anode design such as the use of slots, which allow gases, generated through
the reduction operation, to escape. The aim of this work is to investigate the effect of the
slots size on the thermo-electrical behaviour of the anode. To this end, a 3D thermoelectric
model taking into account the anode, the bath and the anode connector has been developed
using ANSYS software. Material parameters such as electrical resistivity, thermal
conductivity and electrical contact resistance are temperature dependent. Numerical
simulations were performed for several slots thicknesses. Furthermore, a new design based
on a variable slots thickness is simulated.

Keywords
Hall-Heroult process Slots Thermo-electrical model Ansys

Introduction Depending on smelter technology, slots are made during the

The Hall-Héroult process is characterized by several
complex multi-physics phenomena and its high-energy
consumption [1]. In last decades many efforts have been
done in order to improve the process efficiency. For this
purpose, the anode assembly constitutes a potential candi-
date, which can help to achieve such a goal. One of the
important innovation was the new anode design where slots
are added to allow gas bubbles to escape and therefore to
reduce the voltage drop and the electric cell noise [2].
H. Chaouki (&)
M. Baiteche
H. Alamdari
M. Fafard
NSERC/Alcoa Industrial Research Chair MACE and Aluminum
Research Centre—REGAL, Laval University, 1065 Avenue de La
Médecine, Quebec, QC G1V 0A6, Canada
e-mail: hicham.chaouki@gci.ulaval.ca
A. Jacques
E. Gosselin
SAWNODE, 395 Rue Marconi, Québec, QC G1N 4A5, Canada
H. Alamdari
Department of Mining, Metallurgical and Materials Engineering,
Laval University, 1065 Avenue de La Médecine, Québec, QC
G1V 0A6, Canada
anode vibrocompaction process or by sawing the anode after
the backing process. The first approach of making slots leads
to significant density gradients inside the anode, which affect
the anode quality. Moreover, using this forming technique
can generate some cracks above the slots after backing [3].
The second approach, based on sawing, allows the forming
of more homogeneous anodes. Nowadays, despite its cost, it
seems to be more suitable to improve the process efficiency.
However, the slot size effect on the thermoelectric behaviour
of the anode, especially the slot thickness, remains to be
understood.
The aim of this work is to investigate the slots size effect
on the anode behaviour. To this end, a thermoelectric finite
element model was developed using the APDL language of
ANSYS software. The parametric design enables to take into
account several anode geometries including a new innova-
tive slots design developed by SAWNODE company [4].
This new saw design allows sawing slots with a double
thickness.

© The Minerals, Metals & Materials Society 2017 1315

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_157
1316 H. Chaouki et al.

Thermoelectric Problem Geometry Description

Let X be a continuous medium subjected to thermal and The geometry consists of an assembly containing the anode,
electrical loadings. The medium can be composed of several the bath, the aluminium rod, cast iron thimbles, the crossbar
materials in contact. The electrical problem is governed by (the steel yoke) and steel stubs (Fig. 1). Without loss of
the following equations [5]: generality, an anode similar to those used in the AP30 cell
8 ! technology is presented in this section [6]. Anode dimen-
>
< divð J Þ ¼ 0
! ! sions are 1500  700  650 mm3 with three stub holes
> J ¼ GðTÞ E ; 8 x 2 X ð1Þ
having 210 mm in diameter and 130 mm in depth (Fig. 2).
:!
E ¼ rV The distance between stub holes centers is 500 mm. The
!! generic anode design takes into account slots with single or
where J ; E ; V and GðTÞ represent the electrical current double thickness as shown in Fig. 3. For the sake of sim-
density, the electrical field, the electrical potential and the plicity flutes are not considered in this model.
electrical conductivity which is temperature dependent. The The steel stubs geometry is depicted in Fig. 4. They have
electrical problem is rewritten as follows: 270 mm in height, 180 mm in diameter and are connected to
a transverse bar with 100 mm in height. The depth of a steel
divðGðTÞ rVÞ ¼ 0; 8x 2 X ð2Þ
stub inside the stub hole is 125 mm. The aluminium rod is
with the following boundary conditions: 1500 mm in height. The clad, assuming the steel
 yoke/aluminium rod transition, is made of steel as the tripod.
V ¼ V ; 8 x 2 CV
@V ! ð3Þ
G @ n ¼ J :n ¼ J ; 8 x 2 CJ

CV and CJ denote two parts of the domain boundary @X.

The electrical current flows through a material having an
electrical resistivity, generates heat by the Joule effect. The
amount of the electrical power converted into a heat source
is defined by [5]:
qv ðT; VÞ ¼ rV:ðGðTÞ rVÞ ð4Þ
This heat source energy per unit volume is involved in the
thermal problem, which is defined for the steady-state case
by [5]:
divðK(TÞ rTÞ þ qv ðT; VÞ ¼ 0; 8 x 2 X ð5Þ

T ¼ T ; 8 x 2 CT
ð6Þ
K @@T
n ¼ q:n ¼
q ; 8 x 2 Cq

In Eq. (5) T and K(T) represent the temperature field and Fig. 1 CAD model
the thermal conductivity. Thermal boundary conditions are
given by formula (6) where CT et Cq are two components of
the domain boundary.
In order to solve the thermoelectric problem, the finite
element method is used. For this purpose, the reader is
referred to the following reference [5], which contains all
details dealing with the weak formulation, discretization and
the contact problem formulation.

Model Description

The model was developed using the APDL language from

the commercial finite element software ANSYS. Thus, the
parametric model can deal with several geometries, bound-
ary conditions and constitutive laws. Fig. 2 Geometric properties of the anode (mm)
Finite Element Analysis of Slot Size Effect on the Thermal … 1317

Fig. 3 A new anode design: slots with double thickness Fig. 5 The mesh used in the analysis

8     
>
> TCC ¼ ~a0 þ ~a1  T2  exp ~b0 ~b1  g ½W=m2  C
>
>
< ~a0 ¼ 1100
~a1 ¼ 6  104
>
>
> ~b0 ¼ 250
>
: ~b1 ¼ 106
ð7Þ

where g is the gap between the carbon and the cast iron. In
this work, it is assumed that the contact is well established
and, therefore, the gap is equal to zero.
The electrical contact resistance (ECR) at the same
interface corresponds to the constitutive law developed in
[7]:
8  D
>
> P
> Rc ¼ A  B  exp  C
> ½X:mm2 
>
>
Fig. 4 Geometric properties of the connector (mm) >
>
>
> 10ða0 þ a1 Tc Þ
>
> A ¼ exp ½X:mm2 
>
< 1 þ a2 Tc þ a3 Tc
2
Mesh Details
10ðb0 þ b1 Tc Þ ð8Þ
>
> B ¼ exp ½X:mm2 
1 þ b 2 Tc þ b 3 Tc
2
>
>
In this study, the 3D element SOLID69 for thermoelectric >
>
>
> C ¼ c0 þ c1 T ½MPa
analysis was used. Elements TARGE170 and CONTA174 >
>
>
> D ¼ d 0 þ d 1 T ½
were used in order to take into account contact between >
: T
surfaces. Figure 5 shows the linear tetrahedral mesh used for Tc ¼ 1000 ½ C
analysis.
Parameters ðai Þ3i¼1 ; ðbi Þ3i¼1 ; ðci Þ2i¼1 and ðdi Þ2i¼1 are defined
as follows:
Material and Contact Properties 8 8
> a0 ¼ 0:397646 > b0 ¼ 0:3963
>
> >
The electrical resistivity and thermal conductivity are tem- < a ¼ 0:564012 > <b ¼ 0:5614
1 1
perature dependent and they are defined for each material in ; ;
> a2 ¼ 1:3060
> >
> b2 ¼ 1:3068
Table 1 [6]. For contact properties, the thermal contact >
: >
: ð9Þ
a3 ¼ 0:1452 b3 ¼ 0:1409
conductance (TCC) at the cast iron/anode interface is  
assumed as a function of the temperature and the gap and it c1 ¼ 0:0355 d1 ¼ 1:6883
5
;
is defined by the following expression [5]: c2 ¼ 3:23  10 d2 ¼ 1:08  104
1318
Table 1 Material properties
Material Thermal conductivity (W/m °C)
2
Aluminium 202 þ 0:168  T  ð7:2E  05Þ  T
Steel 50:816 þ 0:009598  T  0:00009787  T2 þ 6:2756  T3
Cast iron 48:3296  0:01522  T
Carbon 3:1111 þ 0:00505  T  ð2:782396E  06Þ  T2
Bath 100
The electrical contact conductance (ECC) is then defined
as: ECC ¼ ðRc Þ1 .
At cast iron/steel and steel/aluminium rod interfaces high
values of TCC were set while small values of RC were
considered to take into account the voltage drop at this
interface.
Loads and Boundary Conditions
In the present study, the case of an anode located at the
center of the cell is considered (Fig. 6). Assuming a peri-
odicity conditions between central and outer anodes in the
cell, heat fluxes on lateral sides of the anode are negligible.
Figure 7 resumes thermal boundary conditions applied on
the anode and Table 2 shows the corresponding heat transfer
coefficients [6, 8].
For electrical boundary conditions, by considering a cell
containing 40 anodes and operating at a total current of
330 kA, an electrical current of 8250 A is applied on the top
aluminium rod. Moreover, at the bottom of the bath an
essential boundary condition, corresponding to a zero
voltage, is applied.
Numerical Simulations
Model Validation
In order to show the model predictive capability, numerical
simulation was carried out without considering the bath. In
this case, the electrical potential was set to zero at the bottom
of the anode (electrical boundary condition). A convective
flux, representing the anode immersion in the bath, was
applied on the bottom of the anode and on a depth of
150 mm. A convection coefficient equal to 500 W/m2 °C
and an ambient temperature of 955 °C were used to take into
H. Chaouki et al.
Electrical resistivity (X m)
ð3:1E  08Þ þ ð0:0096E  08Þ  T  ð5:19E  14Þ  T2
ð1:53E  07Þ þ ð3:75E  10Þ  T þ ð9:86E  13Þ  T2
ð7:4157E  07Þ þ ð4:4149E  10Þ  T þ ð1:114E  12Þ  T2
ð5:3E  05Þ  ð1:67E  08Þ  T
4.3478E–03
account such a flux. The electrical contact conductance
(ECC) at anode/cast iron interface corresponds to a contact
mechanical pressure equal to 10 MPa.
The obtained results for the temperature profile and the
voltage drop are shown in Figs. 8 and 9. In [9] simulation of
the anode thermoelectric behaviour shows that the temper-
ature is about 650 °C around the stub hole and 700 °C on
the top surface of the anode. The voltage drop was about
300 mV. In [6] a thermo-electro-mechanical study leads to
the following results: (i) a temperature about 700 °C near the
stub hole, (ii) a temperature around 740 °C on the anode top
surface and (iii) a voltage drop equal to 317 mV. In the
present study, according to the Fig. 9, the voltage drop is
about 321 mV. The temperature varies from 695 to 740 °C
on the anode top surface (Fig. 10) while for regions sur-
rounding the stub hole the temperature varies from 623 to
710 °C (Fig. 11). These results are in agreement with those
of above mentioned references and show the robustness of
the model.
Slots Size Effect on the Thermal Electrical
Behaviour of the Anode
In order to study the slot size effect on the thermoelectric
behaviour of the anode, three different anode geometries
were considered. For each anode design, the slot thickness
was the main variable. Therefore, three sets of anode were
defined (Table 3). The anode immersion in the bath was
set equal to 150 mm and the bath depth is 40 mm. For
each simulation the voltage drop, the anode volume and
the energy dissipated through the Joule effect were
calculated.
Results Analysis for Set A
Results of this set of anodes are reported in Table 4.
Histograms (12–14) show that by reducing the slot
Finite Element Analysis of Slot Size Effect on the Thermal … 1319

Fig. 6 Periodicity in the cell for thermal boundary conditions

saving of 12.47 W (0.67%). Moreover, the voltage drop is

improved by 1.2 mV. The anode volume increases by 0.8%
(Figs. 12, 13, 14).

Results Analysis for Set B

Table 5 and histograms (15–17) show simulations results
for this set. By decreasing the slot thickness from 12 to
8/6 mm (double thickness) the voltage drop is reduced by
2 mV, the dissipated energy decreases from 1716.27 to
1707.78 W while the anode volume increases by 0.64%
(Figs. 15, 16, 17).

Results Analysis for Set C

Fig. 7 Thermal boundary conditions
thickness from 12 to 8/6 mm (double thickness) the
amount of energy dissipated by Joule effect decreases from
1861.3 to 1848.83 W, which corresponds to an energy
For the last anodes set, results are reported in Table 6 and
histograms (18–20). Results follow the same trends as for
previous sets. Reducing the slot thickness from 11.5 to
8/6 mm improves the voltage drop by 1.9 mV, the dissipated
energy by 11.65 W and increases the anode volume by
0.75% (Figs. 18, 19, 20).

Table 2 Thermal boundary Component Heat transfer coefficient Ambient temperature

conditions (convection) (W/m2 °C) (°C)
Crust 5 600
Alumina powder 2.5 150
Hot gases 60 955
Tripod and the lower half of the 10 150
aluminium rod
The upper half of the aluminium rod 50 60
Bath 1375 955
1320 H. Chaouki et al.

Fig. 8 FEM results: temperature profile (°C)

Fig. 10 Temperature profile at the anode top surface (°C)

Fig. 9 FEM results: electrical potential (V)

Fig. 11 Temperature profile near the stub hole (°C)

Table 3 Dimensions of anodes Anode Label Length Width Height Slot

set (mm) (mm) (mm) Thickness Height
(mm) (mm)
Set A A1 1500 650 600 12 300
A2 1500 650 600 10 300
A3 1500 650 600 8 300
A4 1500 650 600 8/6 150/300
Set B B1 1600 810 650 12 330/350
B2 1600 810 650 10 330/350
B3 1600 810 650 10/8 175/350
B4 1600 810 650 8/6 175/350
Set C C1 1615 705 600 11.5 330/350
C2 1615 705 600 9.2 330/350
C3 1615 705 600 8/6 330/350
Finite Element Analysis of Slot Size Effect on the Thermal … 1321

Table 4 FEM simulation results Anode (Set A) Volume (m3) Voltage drop (V) Joule effect (W)
(Set A)
A1 0.560744 1.5019 1861.30
A2 0.562544 1.5015 1855.17
A3 0.564344 1.5007 1849.56
A4 0.565244 1.5007 1848.83

Table 5 FEM simulation results (Set B)

Anode (Set B) Volume Voltage drop Joule effect
(m3) (V) (W)
B1 0.815888 1.220 1716.27
B2 0.818064 1.2189 1713.12
B3 0.818864 1.2188 1712.02
B4 0.821104 1.2180 1707.78

Fig. 12 Dissipated energy by Joule effect (Set A)

Fig. 15 Dissipated energy by Joule effect (Set B)

Fig. 13 Voltage drop (Set A)

Fig. 16 Voltage drop (Set B)

Fig. 14 Anode volume (Set A)
1322 H. Chaouki et al.

Fig. 17 Anode volume (Set B) Fig. 20 Anode volume (Set C)

Table 6 FEM simulation results (Set C)

Anode (Set C) Volume Voltage drop Joule effect Conclusion
(m3) (V) (W)
C1 0.657060 1.3319 1716.27 In this work a thermoelectric model was developed in order
C2 0.659586 1.331 1710.36 to study the slot size effect on the thermal-electrical beha-
viour of the anode. Using the APDL language of the
C3 0.662002 1.330 1704.62
ANSYS software the parametric model can easily deal with
different anode geometries, constitutive laws, boundary
conditions and loads. Numerical simulations show that the
model provides results in a good agreement with those
found in previous studies. Simulations show that the
reduction of the slot thickness allows a non-negligible:
(i) decreasing of the voltage drop, (ii) saving of the dissi-
pated energy through the Joule effect and (iii) increasing of
the anode volume. It is worth to note that saving
2 mV/anode represents a saving in the electricity cost
corresponding to $ 80,000/year for a plant of 12,000
anodes.
However, more investigations have to be done for a better
characterization of this effect. Especially, simulating the
thermoelectric behaviour of the anode at half-life and end of
Fig. 18 Dissipated energy by Joule effect (Set C) life, studying the effect of small thicknesses on the degassing
phenomena and taking into account the mechanical part and
flutes.

Acknowledgements The authors warmly thank Laval University,

Natural Sciences and Engineering Research Council (Grant number
EPG 491325-15) and SAWNODE for their technical and financial
support.

REFERENCES

1. D. Richard, M. Fafard, R. Lacroix, P. Cléry, Y. Maltais, Aluminum

reduction cell anode stub hole design using weakly coupled
thermo-electro-mechanical finite element models. Finite Elem.
Anal. Des. 37(4), 287–304 (2001)
2. X. Wang, G. Tarcy et al., Development and deployment od slotted
Fig. 19 Voltage drop (Set C) anode technology at Alcoa. TMS Light Met. 2007, 539–544 (2007)
Finite Element Analysis of Slot Size Effect on the Thermal …
3. S. Thibodeau, Caractérisation des propriétés mécaniques de la pâte
de carbone à 150 °C dans le but d’optimiser la mise en forme des
anodes utilisées dans les cuves Hall-Héroult. Ph.D. dissertation,
Université Laval, 2015
4. A. Jacques, Process, apparatus and saw blade for processing anode
blocks, and prebaked anode blocks for aluminum production.
PCT/CA2014/051239 (2015)
5. P. Goulet, Modélisation du comportement thermo-électro-mécanique
des interfaces de contact d’une cuve de Hall-Héroult. Ph.D. disser-
tation, université Laval, Québec, Canada, 2004
6. H. Fortin, Modélisation du comportement thermo-élec-
tro-mécanique de l’anode de carbone utilisée dans la production
1323
primaire de l’aluminium. Master’s thesis, université Laval, Québec,
Canada, 2009
7. D. Richard, M. Fafard, R. Lacroix, P. Cléry, Y. Maltais, Carbon to
cast iron electrical contact resistance constitutive model for finite
element analysis. J. Mater. Process. Technol. 132(1–3), 119–131
(2003)
8. D.R. Gunasegaram, D. Molenaar, Towards improved energy
efficiency in the electrical connections of Hall-Héroult cells through
FEA modeling. J. Clean. Prod. 93, 174–192 (2015)
9. M. Dupuis, in Proceedings of TMS Light Metals. Computation of
aluminium reduction cell energy balance using ANSYS finite
element models, pp. 409–417 (1998)
 Hydrodynamic and Thermoelectric 3D
Mathematical Model of Aluminium Electrolysis
Cell to Investigate Slotted Carbon Anode
Efficiency

Mounir Baiteche, Hicham Chaouki, Edward Gosselin, Alain Jacques,

Houshang Alamdari, and Mario Fafard

Abstract
Carbon anodes in Hall-Héroult electrolytic cell are the main source of carbon to reduce
alumina into aluminium. Carbon dioxide resulting from the reduction reaction is evacuated
through the lateral sides of the anode and through the slots. The shape and size of the slots
is an important parameter for the anodes design. During manufacture, slots are formed in
the anodes before or after baking. However, to avoid the stresses due to the introduction of
slots in green anodes during molding, the solution is to saw the anodes after baking. The
challenge here is to remove minimum carbon from the anodes while having high energy
efficiency during electrolysis process. This study is conducted to test numerically different
sawn slots configurations in the anode using a 3D mathematical model of the electrolytic
cell. The model takes into account the main thermoelectric phenomena and flow dynamics
that govern the operation of the electrolysis cell.

Keywords
Aluminium electrolysis cell Modelling Slotted anodes Sawn slots Energy efficiency

Introduction
The production of aluminium by the Hall-Héroult process
needs a large amount of carbon anodes necessary to reduce
the alumina in the electrolytic cell. In this electrolysis cell,
takes place a large number of transfer phenomena. The
transfer of electrical charges between the electrodes is the
trigger of thermochemical, thermoelectric, magneto-
hydrodynamic and mechanical phenomena combinations
[1]. Control of all these phenomena is necessary for optimal
aluminium production and competitive energy efficiency.
This control is performed by the calibration of a large number
of operation parameters related to the process and design of
facilities and parts of the cell that provide the good func-
tioning of the cells [2]. One of these changes can potentially
M. Baiteche (&)
H. Chaouki
H. Alamdari
M. Fafard
Aluminium Research Center REGAL, University Laval, 1065,
avenue de la Médecine, Quebec, G1V 0A6, Canada
e-mail: mounir.baiteche.1@ulaval.ca
E. Gosselin
A. Jacques
SAWNODE, 395, Rue Marconi, Quebec, G1N 4A5, Canada
affect the carbon anodes [3]. A lot of work is done to improve
the quality of the anodes either by increasing the density, size
and the thermoelectric properties [4].
The role of the slots in the cell is to release the gas from
the electrolysis reactions [5]. Slots can be introduced directly
in the forming process of the anodes. This is very common
in the anodes manufacture. Different studies were carried out
to study the residual stress from compression during the
formation of the slots [6]. It was recommended by Grunspan
[7] that the formation of post-baking slots is adequate to
eliminate the density gradient between the area of the formed
slot and the rest of the anode. This method avoids to alter the
anodes by molding in a the vibro-compactor and reduces the
cracked anode rejection rate after baking. At the same time,
the post baking slots allow to better control their size and
shape.
The anodes slotted after baking are used in the elec-
trolytic cell by several aluminium smelters. And the use of
different forms of slots is becoming increasingly common.
This work aims to develop a hydrodynamic and ther-
moelectric 3D model for a part of an electrolysis cell to see

© The Minerals, Metals & Materials Society 2017 1325

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_158
1326
the impact of different slot sizes and their shapes on the
energy efficiency of the anodes and thermoelectric phe-
nomena in the electrolytic cell. It is very difficult and
expensive to make such a tests practically on the facilities of
the cell. Mathematical modeling is one way which allows to
provide a solid idea on a geometric configuration efficiency
such as the size of the anodes and the dimensions of the
slots. Their size and shape can only be varied in a certain
range to optimize bubble release as well as mechanical
resistance. However, the material discontinuity created by
the slots is a shortfall in terms of carbon mass relative to the
bulk volume of the entire anode. One solution proposed is to
make slots with double thickness. This configuration may be
done very easily by sawing. Various configurations have
been tested using the model with different anode sizes and
slot widths.
Various studies are published in the literature on the
modeling of thermoelectric phenomena and hydrodynamic
that occur in the cell [8]. Mathematical modeling in this area
requires the coupling of several systems of equations gov-
erning the phenomena involved. The transfer of heat in the
anode and the cell is studied mainly in terms of energy
efficiency of the electrolysis process [9]. The electrical
aspects are also of great importance since it is directly related
to the electrolysis process. The magnetic phenomena and
magnetohydrodynamic are also the interest of different
studies [10].
Many of the most important phenomena are considered in
the developed model to see the impact of the size and shape
of the slots and the anode itself on the profiles of current
density field, the voltage drops across the anode and the
Joule effect in the anodes.
3D Single Anode in Bath Model
The developed model considers a simplified anode geo-
metric configuration of the cell. Figure 1 shows a repre-
sentation of the domains considered in the global model that
can be given as an electrolytic cell of a single anode. This
approach facilitates the simulations while keeping all the
principles of cell operation. Different anode configurations
are tested in the same way. Different anode configurations
are tested in the same way, allowing comparison of the
results. The limitation of the model domain to a single anode
provides the desired results in a faster way.
Global Model Description
The 3D global model is built on a multi-domain approach
using ANSYS CFX [11]. Each part of the cell is constructed
separately and the overall model combines all the parts,
M. Baiteche et al.
Fig. 1 Scheme of the cell part considered in the model
taking into account the contact interface between each
domain. The thermo-physical properties of each material
was considered variable with the temperature and specified
for each area separately.
Figure 2 shows the flowchart of the modular structure for
the overall single anode cell 3D model.
The model is developed in steady state. The aim of this
study is to model the distribution of 3D temperature, current
density and voltage drop in the anode to see the impact of
slot shapes on the distribution after start-up. The cell oper-
ation is considered established and it does not seem neces-
sary to focus on the transient phases where the anodes are
just placed in the cell and when the contact resistance
between the bath and the anode is modified by the formation
of a ledge on the anode surface. Consumption of the anode is
not taken into consideration. The geometry of the anodes
does not vary during the simulation.
The equations of heat transfer, electrical transfer and the
equations of motion for the bath are coupled according to the
respective physical properties in each domain. The boundary
conditions were specified such a way that respect the energy
balance of the simulated cell. The heat loss coefficients and
the gas temperature around the anode, the tripod and the bath
were treated in the same manner as Fortin [12, 13]. Cryolite
crusts that form around the anode and depositing layer of
alumina on the anode were taken into account by specifying
an equivalent thermal resistance of each material.
Other phenomena occur in the electrolytic bath during
operation of the cell such as the chemical reactions as well as
the flow of bubbles produced from reactions. The model
presented in this work does not take into account the
Hydrodynamic and Thermoelectric 3D Mathematical Model …
Fig. 2 Flowchart of the modular structure of the global model
movement of the bubbles and reactions in the liquid bath.
The model can be completed in this direction, but for the
verification of different configurations of the anodes on the
energy balance, it is not required if all the tests are conducted
under the same conditions. Further development will be
done to consider the slots size on bubbles movement in the
bath.
Hydrodynamic Model Assumptions
The flow of the bath in the cell is by itself a problem to treat
separately due to its complexity. Although the cell modeled
herein is a cell with a single anode, the flow was considered
similar to that which occurs under an anode in a real
industrial cell. The hydrodynamic phenomenon on which the
boundary layer depends is related to flow in the entire cell.
A parallel study was conducted to simulate the MHD flow in
the electrolytic cell by considering the liquid aluminium and
the bath [14]. The velocity field obtained after the estab-
lishment of the flow under an anode was imposed in the
domain of the bath in the single anode model of this study.
The same velocity field was considered for all slotted anode
cases. Figure 3 shows an overview of the velocity field
applied in the bath domain to consider the hydrodynamic
phenomenon. This velocity field has been obtained by taking
into account a 3D distribution of the current density and
1327
magnetic field for the calculation of the momentum source in
the two fluids in the cell.
The boundary layer at the interface of the anode with the
bath is calculated by the flow model according to the
properties of the flow which is turbulent. Through this
boundary layer, the thermal and electrical contact resistance
between the bath and anode are considered according to its
thickness.
Thermal and Electrical Contact Resistance
Assumptions
At the interfaces, the contact resistance which varies
depending on the temperature were considered according to
the results given by Richard et al. [15]. Numerically, the
interfaces are built with the General Grid Interface
(GGI) scheme that ensures the conservation of the various
fluxes considered in the field. This method is adapted to link
several domains where different types and different phe-
nomena occur [16]. Between the bath and the anode, the
interface is of a fluid-solid type. The flow of bath generates a
boundary layer where the thermal and electric resistance is
calculated according to the thermal and electrical properties
of the bath. It should be noted that the physical properties of
the bath vary during the cell operation. This is due to the
continuously varying the chemical species concentration of
1328 M. Baiteche et al.

Fig. 3 Velocity profile imposed

in the bath domain

the bath. Constant values were taken for the properties of the
bath which are those presented by Solheim [17].

Results and Discussion

Various simulations were performed where the anodes of

different sizes with specific slots were tested. Four groups of
anodes were modeled using ANSYS-WORKBENCH [18];
each group has anode slots’ specific geometrical dimensions.
For each group, two kinds of slots were tested. The first type
of slot has a consistent thickness while the second type has Fig. 4 Configuration of the two types of slots
two-parted thickness over the height. From the bottom of the
anode, the second type of slots begins with a relatively large The results obtained by the simulations for the various
thickness compared to the top. Figure 4 shows a schematic anodes are shown in Fig. 5. Figures are denoted a, b, c, and
view of the two types of slots. Table 1 shows the geometric d and show the contours of the current density distribution in
characteristics of the anodes tested as well as dimensions of the different anodes groups A, B, C and D respectively. It
the slots. can be observed through these contours a slight difference in

Table 1 Descriptions of the Group N° Length Width Height Slot height Slot thickness Volume
various anodes tested by the (m) (m) (m) (m) (mm) (m3)
model
A 1 1.5 0.65 0.6 0.3 8 0.5643
2 1.5 0.65 0.6 0.15/0.3 8/6 0.5652
B 1 1.615 0.75 0.6 0.35 11.5 0.6570
2 1.615 0.75 0.6 0.35 9.2 0.6595
C 1 1.6 0.81 0.65 0.35 12 0.8180
2 1.6 0.81 0.65 0.175/0.35 10/8 0.8191
D 1 1.6 0.711 0.65 0.4 13 0.7093
2 1.6 0.711 0.65 0.2/0.4 12/8 0.7131
Hydrodynamic and Thermoelectric 3D Mathematical Model … 1329

the distribution of the current density caused by variation in

A1 A2
the shape and size of the slots.
Figure 6 shows the variation of electric potential and the
current density on the center line through the rod connector
of the anode, the anode and the bath. These results show the
voltage drop and the distribution of the current density on
the entire assembly considered in the global model. For each
a) sub-field distribution changes depending on its size and its
physical properties. It can be seen that the transition between
B1 B2 each subdomain is due to electrical resistances of each
interface. The interface between the electrolytic bath and the
anode consider the electrical resistance in the boundary
layer. The electrical and thermal balance depend on this
resistance. The distribution of the current density through
this interface is influenced by the boundary layer of the bath
in contact with the bottom of the anode.
b) Figure 7 compares for each group and for each of the
anodes the power generated by the Joule effect and the
C1 C2 potential drop for each of the anodes. The first thing to
notice is that the variation of the slots forms and size gen-
erates a significant gain in terms of generated power. Smaller
slots size decreases heat lost by Joule effect from the anodes.
Respectively, for each group A to D as presented in
Figs. 7a–d, 3.85, 1.54, 12.16, 7.91 W of Joule effect power
is gained. These values seem small, but in wide aluminium
c) smelters scale, this can represent significant gains in terms of
energy saving.
D1 D2 Regarding the voltage drop on the anodes between the top
and base of anodes, significant differences are observed. For
each group of anodes, the potential difference was recorded
and compared between the anodes with a simple slot and the
double thickness slot. Differences of 0.2, 1.6 and 0.7 mV are
observed for the anodes of groups B, C and D respectively as
presented in Figs. 7b, c and d, while for the two anodes of
d) group A, the potential drop increased by a value of 0.1 mV.
Despite the increase of the voltage drop between the anodes
Fig. 5 Contour of the current density in the anode: a Group A, of the group A, it was shown that the power dissipated by
b Group B, c Group C and d Group D Joule effect gain has decreased by 3.85 W. The advantage of

Fig. 6 Profile of the current

density and the potential across
the center line which passes
through the anode rod to the bath
for anode A1
1330
a)
b)
c)
d)
Fig. 7 Comparison of Joule power generated by the anode and
potential drop between the anodes of different groups: a Group A,
b Group B, c Group C and d Group D
using double layered slots seems to be profitable for the
energy efficiency of the anodes.
Conclusions
The 3D single anode cell model was constructed by a
multi-domain approach, which represents the thermal, elec-
trical and hydrodynamic phenomena with respect to each
medium constituting the system. The study was conducted to
M. Baiteche et al.
test the energy efficiency of anodes of different sizes and to
see the impact of using slots with double thickness across the
anodes. In addition to the volume of carbon gained as
available quantity in anodes for the electrolysis reaction with
double thickness slots, significant gains were calculated in
terms of power released by Joule effect and in terms of
potential drop through the anodes. The results showed that
for small slots size, more energy gain is obtained and less
voltage drop is observed. The double thickness slots seem to
give better carbon anodes efficiency; more investigations
should be done to see the behavior of bubbles in this slots
shape.
Acknowledgements The authors warmly thank Laval University,
Natural Sciences and Engineering Research Council (Grant number
EPG 491325-15) and SAWNODE for their technical and financial
support.
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18. K.L. Lawrence, ANSYS workbench 14. SDC Publications (2012)
 Gas Anodes Made of Porous Graphite
for Aluminium Electrowinning

Babak Khalaghi, Henrik Gudbrandsen, Ole Sigmund Kjos,

Karen Sende Osen, Ove Bjørn Paulsen, Tommy Mokkelbost,
and Geir Martin Haarberg

Abstract
One of the major downsides of the current aluminium production process is the high CO2
emission. One alternative is to replace the consumable carbon anodes with inert anodes so
that oxygen evolves instead of CO2. Also PFC emissions will be eliminated by using inert
anodes. However, so far a sufficiently inert anode has not been found. Another option is to
utilize natural gas through porous anodes in order to change the anode process. This will
decrease CO2 emission remarkably and also eliminate PFC emissions and anode effect. The
porous anode could be made of carbon or it can be inert. However, the as-mentioned
problem still exists regarding porous inert anodes. Therefore, at the moment porous carbon
anodes seem to be the best practical option. In this study, porous anodes made of different
grades of graphite were used for electrolysis experiments in a laboratory cell. Also, off-gas
analysis was performed to get an insight of the ongoing reactions. Our results show that for
some types of graphite anodes, methane participates effectively in the anodic reaction.

Keywords
Aluminium electrolysis Porous anodes Methane

Introduction
Environmental issues related to Hall-Héroult process is one
of the major concerns of the aluminium industry. A large
amount of CO2 is emitted from electrolysis cells. The overall
reaction is as follows [1]:
Al2 O3 ðdissÞ þ 3=2CðsÞ ¼ 2AlðlÞ þ 3=2CO2 ðgÞ
There has been a lot of research to tackle the problem of
CO2 emissions. An inert anode for the Hall-Héroult process
has been called “The ultimate material challenge” [2]. It
shows the high requirements of such a material. There have
B. Khalaghi (&)
G.M. Haarberg
Department of Materials Science and Engineering, Norwegian
University of Science and Technology (NTNU), 7491 Trondheim,
Norway
e-mail: babak.khalaghi@ntnu.no
H. Gudbrandsen
O.S. Kjos
K.S. Osen
O.B. Paulsen

T. Mokkelbost
SINTEF Materials and Chemistry, 7465 Trondheim, Norway
been only laboratory and bench scales tests to try inert anodes
so far [3]. In conclusion, a prospective industrial inert anode
still seems to be unreachable; at least in the near future.
Another alternative to the current industrial process is to
supply a reducing gas (e.g. CH4) to the anode/electrolyte
interface through a porous anode. Then, the gas participates
in the anodic reaction and the overall reaction changes from
ð1Þ (1) to the following:
Al2 O3 ðdissÞ þ 3=4CH4 ðgÞ
¼ 2AlðlÞ þ 3=4CO2 ðgÞ þ 3=2H2 OðgÞ ð2Þ
For this purpose a porous anode must be used. The porous
anode could be made of carbon or an inert material. Certainly, a
porous anode made of an inert material enables maximum gain
of this concept; i.e. the amount of emitted CO2 can be
decreased to half according to the stoichiometry of reaction (2).
However, as mentioned earlier a sufficiently inert anode
has not been found so far. Therefore, a porous anode made
of carbon seems to be a more practical choice at the present

© The Minerals, Metals & Materials Society 2017 1333

A.P. Ratvik (ed.), Light Metals 2017, The Minerals, Metals & Materials Series,
DOI 10.1007/978-3-319-51541-0_159
1334
time. When the anode is made of porous carbon, reactions
(1) and (2) will be competing anodic reactions. The theo-
retical cell voltage of reaction (2) is 1.1 V while for reaction
(1) it is equal to 1.2 V at 1233 K (960 °C) [4]. This leads to
a small depolarization of the cell voltage when methane is
used in such a way [4, 5]. More importantly, utilizing the
reducing gas, e.g. CH4, results in reduced CO2 emission. The
degree of CO2 emission reduction depends on which of these
competing reactions dominates as the anodic reaction.
The concept of supplying a reducing gas to a porous anode
in aluminium electrolysis has been tried before. In some
studies carbon or graphite anodes were use [6–8]. A 0.3–
0.4 V depolarization effect was detected when methane was
used [6]. In another study porous graphite anodes showed
depolarization when methane and H2 were used. It was
mentioned that due to high temperature of the process,
methane decomposition occurs considerably and methane
can be considered electrochemically equivalent to hydrogen.
On the other hand, when hydrogen-containing fuels such as
methane or hydrogen were used considerable fluoride losses
from electrolyte occurred [7]. In addition, the anode might
become clogged by soot when flushed by methane. When H2
and CO were used some depolarization was observed; though
the carbon consumption increased and the anodes disinte-
grated [8]. Inert porous anodes have also been tested in some
studies. But, none of the inert anodes showed sufficient sta-
bility and were either disintegrated or dissolved to some
extent after long time electrolysis [8–10]. One of the candi-
date inert anodes was a non-consumable gas anode based on
the type used for Solid Oxide Fuel Cells (SOFC). It was
reported that this anode is not suitable for the current alu-
minium electrolysis process, but could be utilized in a
modified Hall-Héroult process [11].
We have reported our studies on this concept using both
inert (e.g. SnO2) and graphitic porous anodes. Aluminium
electrolysis experiments were carried out at 850 °C in a
modified electrolyte where methane and hydrogen, in separate
experiments, were used as reducing gases [5, 12, 13]. In a
recent work different graphites were tested as anode material
and one showed better results [14]. In this paper the continu-
ation of previous studies are presented. Here, other parameters
which might play a role have been studied. Establishment of
the three-phase boundary between the gas, anode and elec-
trolyte is crucial for the accomplishment of this process [5]. In
addition, it was observed earlier that cracking of the methane
during the electrolysis leads to partial or even complete
Table 1 Typical properties of Grade No. Grade name Specific gravity (g/cm3)
different graphites [23, 24]
1 G347 1.85
2 EG-92E 1.75
3 TM 1.82
4 G140 1.7
B. Khalaghi et al.
clogging of the anode which is detrimental for this process [6,
14, 15]. In order to establish the three-phase boundary and to
prevent the clogging of the anode, the flow of the gas from top
and the flow of the electrolyte from the bottom through the
porous structure of the anode must be considered. Also, the
flow properties of the porous graphite such as permeability,
porosity and pore size are of great importance. Usually the
electrolyte in the lab experiments is almost stagnant. The
hydrostatic pressure of the electrolyte is negligible and there-
fore, the main factor causing the electrolyte to penetrate the
anode is the capillary pressure. On the other hand, the fluid flow
through a porous medium is described by Darcy’s equation:
K
V ¼ ðrP  qgÞ ð3Þ
l
where V is the average fluid velocity, K is permeability of the
porous material, l is the fluid viscosity, P is the pressure, q is
the density of the fluid and g is the gravitational acceleration
[16]. The three-phase boundary might be established on the
outer surface of the anode or inside the porous structure of the
graphite. This depends on the properties of the porous gra-
phite as well as the flows of the gas and electrolyte.
In a similar study Namboothiri et al [17] made pressure
calculations and permeability measurements in order to find
the suitable permeability for the porous material to be used
as the gas anode. Between four different carbon materials
which were candidates for anode the one with 30% porosity
and average pore diameter 10 lm gave the best perfor-
mance. The permeability of this sample was equal to
1.30  10−14 ± 0.200  10−14 m2. Recalling that 1 darcy is
equivalent to 9.8692  10−13 m2 [18], then the permeability
was equal to 13.2 md (millidarcys). The air permeability of
industrial carbon anodes typically varies from 2  10−14 to
20  10−14 m2 (20–200 md) [19]. In our previous studies
inert anodes based on tin oxide were used. The porous tin
oxide-based anodes were supplied with methane and hydro-
gen and depolarisation was observed [5, 13]. The porosity
of the inert tin oxide anodes used was approximately 28%.
The gas permeability of anodes was in the range of
3–13  10−13 m2 (300–1300 md). The gas permeability
increased slightly with increasing particle diameter. This was
attributed to enhanced gas transport due to larger pore sizes
[20]. However, a much denser graphite in comparison to these
anodes (see grade 1/G347 in Table 1) was the most efficient in
our previous study [14]. Though, no fluid flow or pressure
balance calculations were made.
Porosity (%) Grain size (lm) Supplier
12 11 Tokai
16 800 Tanso
20 10 POCO
20 1000 Tokai
Gas Anodes Made of Porous Graphite for Aluminium Electrowinning
Experimental
Mercury porosimetry was used to characterize the graphites.
This technique is based on the intrusion of mercury into a
porous structure under stringently controlled pressures [21].
A Micrometrics Autopure IV 9500 Mercury Porosimeter
was used. This instrument can determine a broad pore size
distribution (0.003–360 lm) [21]. The graphite samples
were *2 g. The graphite samples had fractured surfaces in
order to have a more accurate measurement since when
graphite is cut it might end up with smeared surfaces. The
permeability of the graphite samples was measured by
Carbon R&D RDC-145 Air Permeability apparatus. This
apparatus has been designed for measuring baked carbon
electrodes. Therefore, the sensitivity of the detectors, the
maximum possible vacuum and the units of measure has
been selected accordingly. So, the samples having perme-
ability in the range of 0.1–30 nPm (10–300 md) can be
measured [22]. The electrolyte composition was chosen
similar to the modern industrial cells except that it was
saturated with alumina. The electrolyte composition was
9.3 wt% AlF3 (Noralf, Boliden Odda AS), 5.0 wt% CaF2
(Merck, >97%), and 9.0 wt% Al2O3 (Merck, >98%) and the
remaining Na3AlF6 (natural cryolite, Greenland). The cryo-
lite ratio was 2.3. Figure 1 illustrates the schematic of the
experimental set-up. A graphite crucible contained the
electrolyte. The walls of the crucible were lined with alu-
mina and its bottom served as the cathode. A hollow steel
tube screwed to the porous carbon anode was used as current
collector. The anode and cathode were positioned horizon-
tally in respect to each other. The crucible containing the
Fig. 1 Schematic of the electrolysis cell
1335
bath was dried in air at 120 °C overnight. After the crucible
was put inside the furnace, the furnace was dried at 200 °C
in flushing N2 until the next morning when the temperature
was raised to 980 °C. The furnace was continuously flushed
with N2. The inlet gas composition for the anode was con-
trolled using mass flow controllers (Bronkhorst) and the inlet
gas pressure was measured. The whole electrochemical cell
was placed in a vertical tube furnace heated by resistance
wires, and connected to a temperature controller.
Galvanostatic electrolysis experiments were performed
using porous anodes made of different graphite grades
(supplied from different companies). Some of the properties
of grades used for preparing anodes are given in Table 1.
Each experiment was started by applying a constant current
of 2.5 A to the cell while N2 was passed through the porous
anode for the first 40 min of the electrolysis time and
afterwards changing the gas to CH4 and continuation of the
electrolysis for 216 min (total time: 256 min).
With this procedure it is possible to detect if there is any
depolarization upon introduction of the CH4 to the anode.
Also another series of electrolysis experiments were carried
out without using methane for comparison and in order to
have a better insight of the process and for comparison.
Different current densities were set by dipping the anode into
the bath deep enough to have the desired current density
while the current and electrolysis time was same for all
experiments. The weight of the anodes was measured before
and after each experiment to check the consumption of the
anodes and it was compared with the theoretical values.
Table 1 summarizes some of the properties of the gra-
phites used in this study.
Figure 2 illustrates the anode assembly used for elec-
trolysis experiments. Threads were made inside the graphite
and the steel tube was screwed into the graphite. This made a
firm connection between the steel tube and the anode.
Steel tube
CH4
Porous carbon
Fig. 2 Anode assembly. On the right hand side a schematic of the
anode assembly is shown and on left a photo of the real anode
assembly. The arrows show the place where anode gas might escape
from the system
1336
Before running experiment the flow of the gas through
the porous anode was tested inside ethanol at room tem-
perature. In case of some of the graphite anodes there was a
flow of the gas from the connection area. This is shown in
Fig. 2 by red arrows. However, as it will be addressed later
this connection became sealed as the temperature was
increased to electrolysis temperature in most cases.
Results and Discussion
The result of mercury porosimetry is shown in Fig. 3. The
differential intrusion of mercury is plotted vs. pore size
distribution. This method only gives the open porosity which
is of course important considering the fluid flow in the
porous structure of the graphite. Besides, it gives the
“minimum pore size” since it measures the pressure needed
to penetrate into the pore [25]. Therefore, the pore sizes
measured by this method might be underestimated to some
extent. As can be seen the grades with larger grain size such
as number 2 (EG-92E) and 4 (G140) have larger pores as
well. And the pore size distributions are also broad. While in
case of grades G347 and TM the pore size distribution is
quite narrow.
The permeability of grade EG-92E was measured to
0.79 nPm (nanoPerm). This is equal to 0.79  10−13 m2 or
80 md. But, the permeability of grade G347 was not in the
range of the apparatus and the measurement failed. This
grade is denser and considering the range of the apparatus its
permeability must be lower than 10 md.
Table 2 summarizes the consumption of the porous gra-
phite anodes in electrolysis experiments. The anodes were
made of three different grades: grade G347 and grade
EG-92E and grade G140; see Table 1. The theoretical con-
sumption of the graphite anode is 1.2 g. This is based on
reaction (1); i.e. with assumption that CH4 does not take part
0.50
1/G347
Log [differen al intrusion (mL/g)]
0.40
2/EG-92E
0.30
3/TM
4/G140
0.20
0.10
0.00
0.0001 0.001 0.01 0.1 1 10
Pore size diameter (μm)
Fig. 3 Differential intrusion of mercury into pores versus pore size
distribution for different graphites. The graphits are depicted by grade
numbers given in Table 1
B. Khalaghi et al.
in the anodic reaction and therefore, the whole weight loss is
due to reaction (1). Of course, when CH4 is used as anode
gas then, reactions (1) and (2) will be competitive anodic
reactions. Thus, oxygen-containing ions dissolved in the
bath might react with methane which leads to lower con-
sumption of the anode and smaller weight loss.
By comparing the weight loss in experiments with CH4
with those without CH4 the degree of CH4 participation in
the anodic reaction can be identified. As can be seen, the
consumptions of anodes were lower in all experiments when
CH4 was used as the anode gas. This suggests that in all of
these experiments CH4 was involved in the anodic reaction;
at least to some extent. However, the difference in weight
loss and consumption is very small in most cases and it
implies that CH4 involvement in anodic reaction was not
significant. Though, this is in contradiction to some of our
earlier findings [14, 15] where in case of grade G347 the
consumption was much lower; experiment 3 in Table 2.
Figure 4 shows the variation of cell voltage during gal-
vanostatic electrolysis using gas anodes made of grade G347
for experiments 1, 2, 3 and 5; see Table 2. The vertical
dashed line corresponds to anode gas shift from nitrogen to
methane in experiment 1, 2 and 3. In experiment 5 only
nitrogen was used as anode gas and here it is illustrated only
for comparison.
The current density in experiments 1–3 was equal to 0.35,
0.29 and 0.26 A cm−2, respectively. The current was same in
all experiments and different current densities was estab-
lished by dipping the anode in the bath to different depths.
So, the wetted surface area was different. It seems that when
the current density was low enough the cell voltage variation
showed a different behaviour. During experiment 2 and 3 the
cell voltage was almost constant and stable. This cannot be
only due to the supply of methane since in experiment 1 also
the anode was supplied with methane. But, in experiment 1
the cell voltage variations was quite similar to the case where
there was no supply of methane; experiment 5. It implies that
when the anode was dipped sufficiently in the bath and/or
current density was low enough the methane became
involved in the anodic reaction much more efficiently.
However, the weight loss changes in experiment 2 and 3 are
not very close. And there must be other factors influencing
the results. One apparent observation is that in experiment 2
the cell voltage fluctuations were more intense during the
first 100 min of electrolysis.
Figure 5 shows the measured pressure before the anode
upon introduction of N2 to the anodes and during heating up
the furnace; the anode was out of the bath and electrolysis
100
had not started. The data for experiment 1, 2, 3 and 5 are
presented.
Unfortunately the pressure data for experiment 3 was
recorded only after introduction of the gas to anode at high
temperature. So, the data at lower temperatures are not
Gas Anodes Made of Porous Graphite for Aluminium Electrowinning 1337

Table 2 The consumption of Grade Anode gas Gas flow Current density Weight Consp. (%) No.
graphite anodes under different (ml min−1) (A cm−2) loss (g)
experimental conditions
1/G347 N2 ! CH4 20 0.35 1.16 97 1
0.29 1.11 93 2
0.26 0.87 73 3
10 0.35 1.18 98 4
N2 20 0.35 1.23 103 5
0.35 1.28 107 6
No gas – 0.35 1.25 104 7
2/EG-92E N2 ! CH4 20 0.35 1.10 92 8
0.29 1.07 89 9
10 0.31 1.13 94 10
N2 20 0.35 1.22 102 11
No gas – 0.38 1.27 106 12
4/G140 N2 ! CH4 10 0.27 1.12 93 13
0.40 1.21 101 14
Electrolysis was run in cryolite-based electrolyte at 980 °C for 265 min. The theoretical consumption is
1.2 g. Experiments 3 and 6 are some earlier results [14, 15]

2.80 1.9
5 Exp 1 Exp 2
N2 → CH4 1.7 Exp 3 Exp 5
2.55
Cell Voltage /V

1
1.5
P /bar

2.30
2
1.3
2.05
3 1.1

1.80 No gas → N2
0.9
0 45 90 135 180 225
0 100 200 300 400 500 600 700 800 900
t /min
T /°C
Fig. 4 The variations of cell voltage during galvanostatic electrolysis
Fig. 5 Measured pressure before the anode, upon introduction of gas
of aluminium for experiments 1, 2, 3 and 5. In experiment 1, 2 and 3
(N2) to the graphite anode and after increasing the temperature from
anode gas was N2 (for the first 40 min) followed by CH4 (until the end
200 to 950 °C during experiments 1, 2, 3 and 5. The anode was out of
of electrolysis). In experiment 5 the anode gas was N2. Anodes were
the bath and the electrolysis had not started. All anodes had same
identical and were made of grade 1 (G347), i = 2.5 A, T = 980 °C
dimensions and were made of grade 1 (G347). The flow rate of
N2 = 20 ml min−1

shown in Fig. 5. However, based on the following discus-

sion the pressure changes for experiment 3 upon introduc-
tion of gas and during heating can be estimated. At the time
of gas introduction to the anode the temperature was equal to
200 °C. Introduction of the gas into the porous anode
immediately caused an increase in pressure. This is due to
the resistance of the porous structure against the gas flow
which can be identified by Eq. 3. Because grade G347 is not
very porous and has low pore size (see Fig. 3) and low
permeability, the pressure increase was high. Furthermore,
as the temperature inside the furnace was elevated the
pressure also increased. When the temperature increased
both the anode and the steel tube expanded. Since the
thermal coefficient of steel is much larger than the graphite,
the steel expanded more and the connection became firm and
sealed at high temperature. This explains the gradual pres-
sure increase after the initial immediate increase at 200 °C.
However, it is obvious that the porous anodes behaved quite
differently though they had same dimensions and they were
made from same graphite; grade G347. The pressure chan-
ges in experiment 1 were quite different in comparison to the
other experiments. Neither introduction of the gas to the
anode, nor the following heating up made a considerable
change in the pressure of anode 1. This might be due to
leakage from the connection between the anode and the steel
1338 B. Khalaghi et al.

tube or a crack or fracture in anode. In any case, most likely 3

a major part of the gas escaped from the anode assembly (a)
without passing through the porous structure and entering 2.8 11
N2 → CH4
the bath. This explains the cell voltage variations and weight

Cell Voltage /V
loss of this anode. For experiment 2, the pressure increase 2.6
was greater than experiment 1 but perhaps not high enough. 10

In experiment 3 the pressure increased to 1.8 bars while in 2.4 8

experiment 2 it reached 1.55 bars. Although data for
experiment 3 is only shown at high temperature (only prior 2.2
9
to electrolysis) but it is apparent that the anode assembly was
completely tight and the graphite behaved well so the 2
methane became efficiently involved in the anodic reaction. 0 45 90 135 180 225
Besides, the anode was deeper inside the bath which in turn t /min
could facilitate the methane reaction with the bath. 2.8
On the whole, the performance of anodes made of grade (b)
EG-92E was slightly better than those made of grade G347. N2 → CH4
The results of anodes made of grade EG-92E are also pre-
2.5 8

sented in Table 2; experiments 8–12. According to Nam-
boothiri et al. [17] the permeability of grade EG-92E is more
suitable than grade G347 for this process. The variation of
cell voltage during electrolysis for these experiments toge-
ther with the experiment where only nitrogen was used as
gas anode (experiment 11) is presented in Fig. 6a. Note that
here again the vertical dashed line only corresponds to gas
anode shift in experiments 8–10; and not experiment 11. As
can be seen, the variation of cell voltage in experiment 10
(gas flow: 10 ml min−1, I = 0.31 A cm−2) is quite similar to
experiment 11 (no methane). It seems the methane was not
much involved in the anodic reaction. This is in accordance
with weight loss results. However, when the methane flow
rate was higher (experiments 8 and 9; gas flow: 20 ml
min−1) the cell voltage variations became different. These
results can be seen more clearly in Fig. 6b. During these two
experiments cell voltage gradually increased while nitrogen
was being supplied. This gradual increase continued for
almost 1 h after introduction of methane. Then the cell
voltage showed a small decrease and kept almost constant
until the end of electrolysis with much less pronounced
voltage fluctuations. This is similar to cell voltage variations
in experiment 2 and 3; see Fig. 4. Though, it seems the
overall participation of methane in anodic reaction in these
two experiments was not very large. Nevertheless, here
again the effect of larger immersion of the anode in the
bath/lower current density is evident. In experiment 9 the
anode was immersed deeper into the bath, corresponding to
Cell Voltage /V
2.2
9
1.9
0 45 90 135 180 225
t /min
Fig. 6 The variations of cell voltage during galvanostatic electrolysis
of aluminium. a Experiments 8–11. b Experiment 8 and 9. In experiment
8–10 anode gas was N2 (for the first 40 min) followed by CH4 (until the
end of electrolysis). In experiment 11 the anode gas was N2. Anodes
were identical and were made of grade EG-92E, i = 2.5 A, T = 980 °C
porosity, larger grain/pore size and larger air permeability,
the pressure changes were negligible and similar. The
maximum pressure increase was equal to 0.15 bars (the
results are not shown here). Similar results were observed in
a previous study [14].
Two electrolysis experiments were also carried out using
anodes made of grade G140; experiments 13 and 14
(Table 2). Here again the impact of higher current density
and/or depth of the anode in the bath was obvious and it
resulted in noticeable change; see Table 2.
Grade G347 has low permeability and therefore, imposes
high resistance toward the flow of the gas. Consequently, the
anode gas escapes from the anode assembly in case