Progress in Materials Science and Engineering

Innovation and Discovery in Russian Science and Engineering
Carlos Brebbia
Jerome J. Connor Editors
J. W. Newkirk · A. A. Popov
A. S. Zhilin Associate Editors
Progress in
Materials Science
and Engineering
Innovation and Discovery in Russian Science
and Engineering
Series Editors
Carlos Brebbia
Wessex Institute of Technology, Southampton, United Kingdom
Jerome J. Connor
Massachusetts Institute of Technology, Cambridge, MA, USA
More information about this series at http://www.springer.com/series/15790

Carlos Brebbia • Jerome J. Connor
Editors
J. W. Newkirk • A. A. Popov • A. S. Zhilin

Associate Editors
Progress in Materials Science

and Engineering
Editors
Carlos Brebbia Jerome J. Connor
Wessex Institute of Technology Department of Civil and Environmental
Southampton, United Kingdom Engineering
Massachusetts Institute of Technology
Cambridge, MA, USA
Associate Editors
J. W. Newkirk A. A. Popov
Materials Science and Engineering Ural Federal University
Department Yekaterinburg, Russia
Missouri University of Science
and Technology
Rolla, MO, USA
A. S. Zhilin
Institute of New Materials
and Technologies
Ural Federal University
Yekaterinburg, Russia
ISSN 2520-8047 ISSN 2520-8055 (electronic)

Innovation and Discovery in Russian Science and Engineering
ISBN 978-3-319-75339-3 ISBN 978-3-319-75340-9 (eBook)
https://doi.org/10.1007/978-3-319-75340-9
Library of Congress Control Number: 2018938828
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Preface
This book is concerned with current issues related to progress in materials science
and technologies.
Progress in modern materials science determines the necessity for rapid develop-
ment in production methods for new materials. The techniques of production have to
be updated and adjusted for achieving new aims and objectives in materials science.
Specifically, the need for new composite materials determined the application of
innovative approaches.
The mechanisms of structure formation in complicated alloys have been investi-
gated. Interpreting the results of experimental studies into the properties of materials
presents considerable difficulty due to the inherent complexity of their chemical
composition. Nevertheless, the authors suggest multiple solutions to these problems,
for instance, modeling as a way of anticipating the properties of materials.
Novel approaches to multiple factor analysis of processing initial and secondary
raw material including nonferrous metals have been proposed. These new strategies
are aimed to increase the yield of nonferrous metals. Dealing with the problem of
using secondary raw materials will serve to decrease the manufacturing cost and
address the environmental issues.
The dynamically developing field of composite materials creates ample opportu-
nities for their application not only in machine manufacturing, but also in building
engineering. Improvement of some properties of materials often leads to deteriora-
tion of others. In attempts to solve this problem, the authors used not only theoret-
ical, but also experimental approaches. Thus, combining scientific and practical data
has ensured their actual implementation in the field.
New patterns of high-pressure treatment of metals have been identified. The
authors have suggested various ways of treatment for large products such as tubes,
which, undoubtedly, presents both scientific and practical interest. The production of
modern materials is inseparable from the methods of high-pressure treatment;
therefore, the outlined techniques present high significance for manufacturing
high-quality products.
v
vi Preface
The editors would like to express their gratitude to all the authors for their
contribution, and to the Editorial Board and other scientists who reviewed the papers
and thus ensured the quality of this book.
This book has been published with financial support of the key Centre of
Excellence “Industrial mining institute of scientific research and projects” by Act
211 Government of the Russian Federation, contract № 02.A03.21.0006, which is
part of the program aimed at enhancing competitiveness of Ural Federal University
named after the first president of Russia B.N. Yeltsin from 2013 to 2020.
The editors also gratefully acknowledge the support of Vice-Rector in Science of
Ural Federal University V.V. Kruzhaev and Director of Institute of Materials
Science and Metallurgy of Ural Federal University V.A. Maltsev.
Rolla, MO, USA J. W. Newkirk

Yekaterinburg, Russia A. A. Popov
Yekaterinburg, Russia A. S. Zhilin
Contents
Part I Structure Formation Analysis of Complicated Alloys

1 Kinetic Parameters and Activation Energy of Pearlitic
and Bainitic Transformations Calculated by Analyzing
the TTT Diagrams of Undercooled Austenite . . . . . . . . . . . . . . . . . 3
M. Gervasyev, D. Novgorodov, and K. Romanova
2 Alloying Addition Effect on the Structure and Behavior
of a Cu-Ni-Zn Three-Component System Alloy Under
Lost-Wax Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
I. A. Gruzdeva and S. S. Gerasimov
3 Structural Changes in Austenitic-Ferritic Steel
03Kh14N10K5M2Yu2T During Heating and Cooling . . . . . . . . . . . 19
L. Mal’tseva, A. Levina, T. Mal’tseva, and V. Sharapova
4 Correlation of Instrumented Charpy Load-Displacement
Curves with Crack Growth in API 5L Grade X80
Pipeline Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
V. Khotinov, V. Farber, and A. Morozova
5 Damping Behavior of Aluminum Replicated Foam . . . . . . . . . . . . . 33
W. Riehemann, A. Finkelstein, U. Arlic, and D. Husnullin
Part II Non-ferrous Metals Metallurgy due to the Refining

of Secondary Raw Materials
6 Recovery of Lead and Zinc from Fine Dust of the Copper
Smelting Industry Using a Chelating Agent . . . . . . . . . . . . . . . . . . . 43
S. Mamyachenkov, O. Anisimova, and E. Kolmachikhina
vii
viii Contents
7 High-Pressure Leaching Arsenic Containing Polymetallic

Copper Mattes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
K. A. Karimov, S. S. Naboychenko, V. I. Neustroev,
and V. A. Menshchikov
8 Investigation of TSL Furnace Hydrodynamics Using
Cold Modeling Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
B. V. Kolmachikhin, V. A. Menshchikov, V. P. Zhukov,
and N. G. Ageev
9 Physical Simulation of Melt Lancing in a TROF Converter . . . . . . 65
V. A. Menshchikov, B. V. Kolmachikhin, and N. G. Ageev
10 Thermodynamic Features Research of Polymetallic Sulfide
Raw Material Leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
D. Rogozhnikov, S. Mamyachenkov, and O. Anisimova
11 Investigation of Lignosulfonate Adsorption
on Zinc Materials in Acidic Media . . . . . . . . . . . . . . . . . . . . . . . . . 81
E. Kolmachikhina and S. Naboychenko
12 Complex Processing of Refractory Pyrite Copper,
Copper-Zinc and Polymetallic Ores on the Basis
of Flotation and Combined Technologies . . . . . . . . . . . . . . . . . . . . . 89
V. Bocharov, V. Ignatkina, A. Kayumov, M. Viduetsky,
and V. Maltsev
Part III Composite Compound Materials Science in Building

Engineering
13 Impact of Waterproofing Permeable Capillary Mixtures
on Cement Stone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
F. Kapustin, E. Pomazkin, A. Spiridonova, and V. Oleinik
14 Composite Cement with a Polymer Addition . . . . . . . . . . . . . . . . . . 107
E. Gerasimova
15 The Manufacture of Concretes Based on Unburnt
Ash Gravel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
F. Kapustin, I. Fomina, and V. Oleinik
16 Physical–Chemical Bases of a Glass Batch
Preparation Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
V. Deryabin, O. Paramonova, and E. Farafontova
17 Influence of Ion-Electron Interaction at the Metal-Oxide Melt
Boundary on the Protective Properties of Enamel Coatings . . . . . . 131
O. Lazutkina, E. Farafontova, and I. Voroshilova
Contents ix
18 Study of Enamel Slip Particles Interaction Using

Model Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
V. Deryabin and I. Tochilova
19 Peculiarities of Formation of Phase Structure and the Hydraulic
Activity of High-Calcium Fly Ash . . . . . . . . . . . . . . . . . . . . . . . . . . 149
I. Domanskaya and V. Oleinik
Part IV High-Pressure Treatment of Metals and Alloys

20 Modernisation of the Method of Rolling of Hot-Rolled Tubes . . . . . 157
A. Bogatov, D. Pavlov, and E. Pavlova
21 New Engineering Solutions in the Production of Laminated
Composite Pipes for the Oil Industry . . . . . . . . . . . . . . . . . . . . . . . 163
N. A. Bogatov, A. Bogatov, and D. R. Salikhyanov
22 Precision of the Tubes Produced by Drawing and Cold Rolling . . . 171
G. Orlov
23 Features of Multihole Stamping of Platinum Glass Melting
Apparatus Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
Yu. Loginov and A. Fomin
24 Research on Metal Forming in the Pipe Ends
Upsetting Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
M. Erpalov and A. Bogatov
25 The Study of Residual Stresses and Surface Hardening
in Tubes After Finishing Processes . . . . . . . . . . . . . . . . . . . . . . . . . 195
M. Rozenbaum, An. Serebryakov, I. Bazhukov, and G. Shimov
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
Part I
Structure Formation Analysis of
Complicated Alloys
Chapter 1
Kinetic Parameters and Activation Energy
of Pearlitic and Bainitic Transformations
Calculated by Analyzing the TTT Diagrams
of Undercooled Austenite
M. Gervasyev, D. Novgorodov, and K. Romanova
1.1 Introduction
There has been a great body of research work (e.g., [1–4]), which, based on some
physical conceptions, provides numerous equations to describe the kinetics of
undercooled austenite decomposition occurring by pearlitic and bainitic transforma-
tion mechanisms. In the majority of cases, these equations provide a rather inaccu-
rate description of the processes actually running in steels. That can be explained by
the multicomponent compositions of steels, featuring a diversity of shapes and sizes
of their constituent phases. On the other hand, an enormous pool of experimental
data has been accumulated on the kinetics of processes in steel upon cooling
[5, 6]. These data are typically reported in the form of various TTT diagrams of
undercooled austenite. The TTT diagrams plotted under isothermal conditions allow
a distinction to be made between pearlitic and bainitic transformations and explicitly
describe the undercooled austenite stability for a specific steel grade. However, such
isothermal TTT diagrams in their graphic representations are difficult to use for
quantitative calculations of temperature fields and structures occurring in the heat
treatment processes.
The present study proposes a phenomenological approach that, based on the
experimental TTT diagrams, makes it possible to determine a set of parameters
that are explicitly described with the kinetic curves.
M. Gervasyev (*) · K. Romanova

Institute of Materials Science and Metallurgy, Ural Federal University, Yekaterinburg, Russia
D. Novgorodov
M.N. Mikheev Institute of Metal Physics of the Ural Branch of the Russian Academy
of Sciences, Yekaterinburg, Russia
© Springer International Publishing AG, part of Springer Nature 2018 3

C. Brebbia, J. J. Connor (eds.), Progress in Materials Science and Engineering,
Innovation and Discovery in Russian Science and Engineering,
https://doi.org/10.1007/978-3-319-75340-9_1
4 M. Gervasyev et al.
1.2 Calculation Technique Development for Kinetic

Parameters and Activation Energy of Pearlitic
and Bainitic Transformations
Any phase transformation can be represented as a function of two basic parameters,

namely, temperature and time.
For the time dependence of a transformation, the Avrami equation has been used:
f ¼ 1 expðAτn Þ: ð1:1Þ
where
f is the volume fraction of the transformed austenite
A and n are called A and n parameters
τ is the transformation time.
The temperature dependence of the A parameter is suggested to be described with
the Arrhenius equation as follows:

Q
A ¼ A0 exp : ð1:2Þ
RT
where
A0 is the preexponential factor
Q is the process activation energy
R is universal gas constant
T is the absolute temperature.
The process activation energy Q includes a thermodynamic factor (ΔG being the
energy for critical nucleation) and a kinetic factor (Qdif being the diffusion activation
factor):
Q ¼ ΔG þ Qdif : ð1:3Þ
While the latter factor is undoubtedly the constant value, the former factor
depends heavily on temperature. However, this dependence is of a complicated
nature as it comprises the processes of nucleation and growth of a new phase. To
describe this temperature dependence of the thermodynamic factor, phase equilib-
rium diagrams are used, and thermodynamic models are calculated. [7–9]. All these
instruments yield rather complicated expressions, which appear difficult to be
applied to real systems; however, all the referenced studies have demonstrated that
altering the free energy with a new phase formation is accomplished with a degree of
supercooling ΔT from the phase equilibrium temperature.
The present study reports about the process activation energy Q determined
through analyzing the TTT diagrams, and an effort is made to describe the temper-
ature dependence thereof.
1 Kinetic Parameters and Activation Energy of Pearlitic and Bainitic. . . 5
1.2.1 Digitization of the Existing TTT Diagrams
The existing TTT diagrams were digitized using standard programs. Figure 1.1
displays TTT diagrams plotted for the steels of the grades 90Kh2N2 M (content of
major alloying elements: C-0.93; Mn-0.71; Cr-1.70; Ni-2.10; Mo-0.20) and U10G
(content of major alloying elements: C-0.96; Si-0.32; Mn-0.55; Cr-0.11; Ni-0.08).
1.2.2 Establishing the Time Dependence of Transformation

Development
For each steel, the dependence of the degree of transformation f on τ was determined
for as a great number of temperatures as possible. Figure 1.2 displays the dependence
of f on ln τ.
1.2.3 Determining A and n Parameters in the Avrami

Equation
From the curves describing the dependence of ln (1/1-f) on ln τ (Fig. 1.3), A and
n parameters were determined in the Avrami equation.
The values of n were averaged and are presented in Table 1.1; and the curves of
ln А are displayed in Fig. 1.4.
Apparently, the temperature dependence of ln А is to a great degree retracing the
С-curve diagrams.
1.2.4 Activation Energy Calculation
Analyzing the curves in Fig. 1.4, the activation energy was determined for the
processes. To this end, a dependence of ln A on 1/T (where Т is the absolute
temperature) was established. For each temperature range in the curve, the value
of Q/R was determined by the curve’s slope. The calculated values as a function of
temperature are shown in Fig. 1.5.
It can be seen that, for a bainitic transformation, regardless of whether it is
distinguished from the pearlitic transformation on the C-curve or not, the activation
energy shows little dependence on temperature for both the 90Kh2N2 M steel and
the U10G steel, and in the first approximation, the activation energy can be assumed
constant. For the pearlitic transformation, the activation energy changes dramatically
Fig. 1.1 TTT diagrams and

major alloying element
contents for steels (a)
90Kh2N2 M and (b) U10G
Fig. 1.2 Time dependence a 120 150

of the degree of
transformation for the steels 100 200
(а) 90Kh2N2 M and 80
300
f, %
(b) U10G 60
40 400
20 550
0 600
0 5 10 15
Ln τ 650
b 120 190
100 200
80
300
f, %
60
40 400
20 500
0 600
0 2 4 6 8 10
Ln τ 650
Fig. 1.3 Dependence of ln a 4 150

ln (1/1–f) on ln τ for the
steels of the grades (а) 2 200
90Kh2N2 M and (b) U10G 300
LnLn(1 /(1 -f))
0
0 5 10 15 400
-2
550
-4
600
-6
650
-8
Ln τ
b 4 190
2 200
300
LnLn(1 /(1 -f))
0
0 2 4 6 8 10 400
-2
-4 500
600
-6
650
-8
Ln τ
Table 1.1 Parameter n in the Bainite Perlite

Avrami equation
90Kh2N2М 3.0 1.9
U10G 3.9 3.9
Fig. 1.4 ln А as a function a 0

of temperature for the steels
0 200 400 600 800
(a) 90Kh2N2 M and
-10
(b) U10G
Ln A
-20
-30
-40
temperature, °C
b 0
0 200 400 600 800
-10
Ln A
-20
-30
-40
temperature, °C
Fig. 1.5 The value of Q/R a

as a function of temperature 40
for the steels (a)
90Kh2N2 M and (b) U10G 30
20
Q /R
10
0
0 200 400 600 800
-10
temperature,ᵒC
b
60
40
Q /R
20
0
0 200 400 600 800
-20
temperature,ᵒC
perlite bainite
with temperature, growing in the absolute value as approaching the equilibrium

temperature of the γ and α phases.
1.2.5 Discussion of Results
The approach suggested in this study makes it possible to analyze the kinetics of
pearlitic and bainitic transformations.
In the pearlitic transformation, the effective activation energy of the process
changes dramatically (see Fig. 1.5). The shape of this curve approaches the shape
of a hyperbola as in the dependence on the supercooling, i.e.:
K perl
ΔG ¼ : ð1:4Þ
ΔT m
where
Kperl is constant for the pearlitic transformation
ΔTm ¼ A1– T (A1 is the temperature of the onset of the pearlitic transformation).
The study demonstrates that the exponent m for the pearlitic transformation is
approaching 2, which is in agreement with the data known from the reference
literature [1].
The bainitic transformation, unlike the pearlitic transformation, is not developing
to its completion; therefore, the Avrami equation was used in this study to describe
the kinetics up to the maximum possible degree of the bainitic transformation
development fbmax, i.e.:
f b ¼ f bmax ð1 expðAτn ÞÞ: ð1:5Þ
where fbmax depends on the supercooling. Similar to the martensitic transformation

[8], we can assume that:
f bmax ¼ 1 expðK b ΔT b Þ: ð1:6Þ
where
Kb is the bainitic transformation constant
ΔТb ¼ Bs – T (Bs is the onset temperature of the bainitic transformation)
A1 and Bs were determined from the ТТТ diagrams.
The activation energy calculated with A parameter under the bainitic transforma-
tion is practically constant, i.e., Q ¼ Qdif. The parameters calculated for the specific
steels can be used in quantitative calculations for the structure formed through the
sections of a workpiece under various heat treatment regimes.
References
1. Christian, J. W. (1975). The theory of transformations in metals and alloys, part 1, equilibrium
and general kinetic theory. Oxford-New York-Toronto-Sydney-Paris-Braunschweig: Pergamon
Press.
2. Lyubov, B. Y. (1981). Diffusion processes in heterogeneous solid medium (p. 296). Moscow:
Nauka. (in Russian).
3. Hillert, M. (1975). Diffusion and interface control of reaction in alloys. Metallurgical Trans-
actions, 6A, 5–13.
4. Umemoto, M., Komatsubara, N., & Tamura, I. (1980). Prediction of hardenability effects from
isothermal transformation kinetics. Journal of Heat Treating, 1(3), 57–64.
5. Atkins, M. (1977). Atlas of continuous cooling transformation diagrams for engineering steels
(p. 260). Rotherham (Yorkshire): BSC.
6. Popova, L. A., & Popov, A. A. (1991). Diagrams for austenite transformation in steels and for
β-solution transformation in titanium alloys (p. 502). Moscow: Metallurgia. (in Russian).
7. Hillert, M. (1982). An improved model for discontinuous precipitation. Acta Metallurgica, 30,
1689–1696.
8. Bhadeshia, H. K. D. H. (2001). Bainite in steels. Transformations, microstructure and properties
(p. 454). London: IOM Communication Ltd.
9. Mirzaev, D. A., Schastlivcev, V. M., Yakovleva, I. L., & Okishev, K. Y. (2000). The kinetics of
isothermal ferrite formation in Fe-9%Cr alloys of different purity. Materialovedeniye, 1, 39–42.
(in Russian).
Chapter 2
Alloying Addition Effect on the Structure
and Behavior of a Cu-Ni-Zn Three-
Component System Alloy Under Lost-Wax
Casting
I. A. Gruzdeva and S. S. Gerasimov
2.1 Introduction
Due to high corrosion resistance and endurance, nickel silver is generally used for
the production of molded pieces for precision instruments and medical equipment
[1]. Moreover, Cu-Ni-Zn ternary alloy is of an attractive silver color, which is the
reason why nickel silver is frequently used for manufacturing metal artwork such as
commemorative coins, medals, and award pins. The strength and wear resistance of
nickel silver (copper 65%, nickel 15%, zinc 20%) are higher than those of alloys
(silver 92.5%, copper 7.5%) [2].
Mechanical and technical properties of nickel silver are determined in sufficient
detail, as Cu-Ni-Zn alloys are most commonly used as wrought metals. Moderniza-
tion of precision instruments has determined the necessity of applying figurine-
shaped details, which are produced by lost-wax process. However, thin-walled
nickel silver casting can sometimes lead to short-run casting (Fig. 2.1). Therefore,
studying the characteristics of Cu-Ni-Zn alloy casting under the lost-wax process is
of particular interest.
2.2 Materials and Methods
The first stage of the research involved studying casting mold fillability by Cu-15Ni-
20Zn alloy depending on casting temperature. For this purpose the method of
estimating casting mold fillability was developed. It consists of the determination
I. A. Gruzdeva (*) · S. S. Gerasimov

e-mail: i.a.gruzdeva@urfu.ru

https://doi.org/10.1007/978-3-319-75340-9_2
12 I. A. Gruzdeva and S. S. Gerasimov
Fig. 2.1 Short-run nickel silver (copper 65%, nickel 15%, zinc 20%) castings
Fig. 2.2 Perforated plate

model for casting mold
fillability estimation
of filled cell fraction in a perforated plate under the lost-wax process [3]. In order to
produce wax models, a perforated plate model was designed by means of Solid Edge
software (Fig. 2.2), and then a master model was constructed by a 3D printer, Objet
Connex 350, using the fast prototyping method. After that the rubber mold was
prepared, and the wax models were obtained and clustered.
Melting and casting were conducted by an INDUTHERM-MUVV700 machine.
Annealing of casting mold was carried out under the same stage heating conditions.
The temperature of all molds before casting was set at 560 C. Nickel silver (copper
65%, nickel 15%, zinc 20%) liquidus temperature is 1112 C; hence, the casting
temperature was set at Tc ¼ 1150 C, 1170 C, 1190 C, and 1210 C. The
perforated plates resulting from the experiments are presented in Fig. 2.3.
The analysis of cast perforated plates revealed that the increase of casting
temperature results in better alloy fillability of molds, which corresponds to the
general notion about the impact of casting temperature on alloy flowability.
The next stage of the research was studying dopant influence on casting mold
fillability, nickel silver (copper 65%, nickel 15%, zinc 20%) castings, surface
2 Alloying Addition Effect on the Structure and Behavior of a Cu-Ni-Zn. . . 13
Fig. 2.3 Nickel silver (copper 65%, nickel 15%, zinc 20%) castings perforated plate
Fig. 2.4 Nickel silver

perforated plate: (a) without
dopant; (b) with 4.0 mass %
Sn and 0.4 mass % Al
dopant
quality, and microstructure. We chose Al and Sn as dopants. The conditions of

investment mold annealing, melting, and casting were the same as noted above. The
casting temperature was set at Tc ¼ 1190 C in each case. The perforated plates
resulting from the experiments are shown in Fig. 2.4.
The analysis of cast perforated plates revealed that alloying 4.0 mass % Sn and
0.4 mass % Al dopant into Cu-15Ni-20Zn ternary alloy improves casting mold
fillability. The apparent reason for that is that aluminum decreases copper alloy
solidification range; as a result, copper alloys show higher flowability. Moreover,
dopant alloyage improves the casting surface condition.
The final stage of the present work was investigating casting temperature (the
possibility of casting temperature decrease) and casting mold fillability of Cu-15Ni-
20Zn-4Al-0.4Sn alloy under the lost-wax process. Conditions of investment mold
annealing, melting, and casting were the same as stated above; casting temperature
was set at Tc ¼ 1130 C, Tc ¼ 1150 C, and Tc ¼ 1170 C. The perforated plates
resulting from the experiments are presented in Fig. 2.5.
The analysis of cast perforated plates revealed that the increase of casting
temperature results in better alloy fillability of molds, which corresponds to the
general notion about the impact of casting temperature on alloy flowability.
Fig. 2.5 Nickel silver

(Cu-15Ni-20Zn-4Al-0.4Sn)
castings perforated plate
Table 2.1 Casting mold fillability depending on casting temperature

Casting Mold Casting Mold
temperature, Filled cell fillability, temperature, Filled cell fillability,

С quantity, pcs. % С quantity, pcs. %
1150 52 50 1190 98 94
1170 70 67 1210 86 83
Table 2.2 Casting mold fillability depending on dopant alloyage

Casting temperature, Filled cell quantity, Mold fillability,

С Alloy chemistry pcs. %
1190 Cu-15Ni-20Zn 98 94
1190 Cu-15Ni-20Zn-4Al- 104 100
0.4Sn
2.3 Results
The results of the first stage of the experiment devoted to casting mold fillability with
Cu-15Ni-20Zn alloy depending on casting temperature are presented in Table 2.1.
As Table 2.1 shows, the best alloy fillability of investment molds is observed
when the casting temperature is 1190 C, i.e., at melting temperature above liquidus
line up to 75–80 C. In this case, fillability is 94%. When the casting temperature is
1210 C, alloy fillability of molds is lower, which is probably due to oxide film
(ZnO) formation on the metal bath surface. Moreover, the high casting temperature
causes intensive zinc evaporation, which prevents ingate mold filling in and leads to
pinhole formation on casting surface.
Alloying 4.0 mass % Sn and 0.4 mass % Al dopant allows reaching 100% casting
mold fillability, which is demonstrated in Table 2.2.
As Table 2.2 shows, the best alloy fillability of investment mold is observed when
the nickel silver is alloyed with aluminum and tin. Moreover, the surface of a casting
sample presented in Fig. 2.4a demonstrates surface irregularity and gritty scale.
More than likely it is also explained by intensive zinc evaporation under at high
Fig. 2.6 Nickel silver sample microstructure: (a) without dopant; (b) with 4.0 mass % Sn and 0.4
mass % Al dopant
casting temperature. The casting sample surface shown in Fig. 2.4b is clean, without
any irregularities. It is probably connected with aluminum deoxidizing power on
copper alloy, as well as the formation of aluminum oxide layer, which prevents zinc
evaporation and decreases zinc loss upon melting.
Furthermore, the dopant alloyage makes it possible to obtain fine-grained micro-
structure of nickel silver casting samples (Fig. 2.6). Grain size of nickel silver sample
alloyed by aluminum and tin is 75–100 μm, which is 2.0–2.5 times smaller than
grain size of nickel silver without alloying.
Table 2.3 Casting mold fillability depending on casting temperature

Casting temperature, С Filled cell quantity, pcs. Mold fillability, %
1130 82 79
1150 101 97
1170 104 100
The nickel silver sample alloyed by aluminum and tin has more compact, close-
grained, and ordered microstructure as opposed to porous and random microstruc-
ture of nickel silver sample without dopant. It can be explained by the capacity of
aluminum to decrease the solidification range of copper-nickel-zinc alloys, and as a
result, the crystallization of liquid nickel silver melt proceeds more regularly.
In the final stage of the study, we attempted to decrease casting temperature of
Cu-15Ni-20Zn-4Al-0.4Sn alloy, since lower temperature means lower loss of fusible
elements and, therefore, less energy consumption. The results of the analysis are
presented in Table 2.3.
As Table 2.3 shows, 100% alloy fillability of molds is observed when the casting
temperature is 1170 С. Most probably, low-melting elements reduce nickel silver
liquidus temperature, which allows decreasing casting temperature. Moreover, cast-
ing at 1150 С provides sufficient quality casting.
2.4 Conclusions
To summarize, a method of estimating mold fillability has been introduced. The

technique involves assessing the fraction of filled cells in a perforated plate under
lost-wax process. This method may be used for the estimation of mold fillability of
casting figurine-shaped details and opencast. Nickel silver casting temperature that
ensures the best mold fillability has been determined as 1190 С. Lower casting
temperature is insufficient for good mold fillability, while higher casting temperature
exerts intensive zinc evaporation that has an adverse effect on mold fillability as well
as on the surface quality of nickel silver samples. The best casting mold fillability
(100%) has been reached through changing the alloy chemical composition. It might
not be appropriate for technical figurine-shaped details, but it is quite suitable for art
open or statuary castings. Insignificant addition of aluminum and tin allows reducing
the casting temperature by 20–40 С. It is important in terms of reducing the loss of
tin and zinc as well as energy costs.
Nevertheless, since different process conditions such as investment mold
annealing temperature before casting, roughness of working layer refractory invest-
ment mold, and others also influence casting mold fillability, it is advisable to
continue the research in the field using the suggested estimation method. Further-
more, it is reasonable to study mechanical characteristics of Cu-15Ni-20Zn-4Al-
0.4Sn such as tensile strength, Brinell hardness, and percent elongation determined
using the method of lost-wax process.
References
1. Kurdumov, A. V., Pikunov, M. V., Chursin, V. M., & Bibikov, E. A. (1986). Castings
production from non-ferrous alloys (pp. 217–218). Moscow: Metallurgy.
2. Osintsev, O. E., & Fedorov, V. N. (2004). Copper and copper alloys (pp. 186–187). Moscow:
Mechanical engineering.
3. Gruzdeva I. A. (2013). Casting mold fillability studying by alloy МНЦ15-20 under the lost-wax
process. In S. S. Gerasimov, A.V. Sulitsin, (Eds.), Proceeding of the 13th Conference Russian
Founders, (pp. 254–259), Ekaterinburg.
Chapter 3
Structural Changes in Austenitic-Ferritic
Steel 03Kh14N10K5M2Yu2T During
Heating and Cooling
L. Mal’tseva, A. Levina, T. Mal’tseva, and V. Sharapova
3.1 Introduction
Developed austenitic-ferritic steel has the necessary strength, hardness, high pro-
cessability and high corrosion resistance. It is intended for springs and elastic
elements. Earlier studies [1, 2] have shown solidification through δ-ferrite in the
investigated steel during crystallization. 03Kh14N10K5M2Yu2T steel’s structure
consists of two main phases – austenite and δ-ferrite in approximately equal amounts
(50/50) after hardening at 1000 C. It has been found [2] that δ-ferrite has an
abnormally high hardness ( 500 HV) in the investigated steel. The hardness of
the austenite is low ( 200 HV). A superstructure reflection of δ-ferrite areas is
forbidden to δ-ferrite. The best description of superstructure is type B2 lattice. The
darkfield image of superstructure reflections (001) indicates the presence of round
shape superfine particles. It is distributed in δ-ferrite crystals. The phase ratio of
austenite and δ-ferrite ( 50/50) is stable in the temperature range of 800–1100 C
(Fig. 3.1a, b). The amount of δ-ferrite increases above the temperature 1100 C.
Ferrite grains increase at a temperature of intensive γ ! δ transformation (above
1200 C). This is due to exceeding a recrystallization threshold. Diffusion mobility
of bcc ferrite lattice atoms is more than austenite fcc lattice atoms.
The Chemical composition of the investigated steel (wt.%) is: 0.02 C; 14.2 Cr;
9.8 Ni; 5.1 Co; 2.5 Mo; 2.4 Al; 0.36 Ti; total content of S, P and Cu 0.35; rest
Fe. The melting of investigated steel ingots was carried out by open-type induction
furnaces. A homogenizing annealing was carried out. Ingots were forged to the
necessary diameter. Samples for tensile tests and bars for microsections were
prepared. Microstructural studies were carried out on the microscope OLYMPUS
JX-51, with 500-fold magnification; also, by electron microscopy using the
L. Mal’tseva (*) · A. Levina · T. Mal’tseva · V. Sharapova


https://doi.org/10.1007/978-3-319-75340-9_3
20 L. Mal’tseva et al.
Fig. 3.1 Hardened steel 03Kh14N10K5M2Yu2T microstructure: (a) 1000 C (in water);
(b) 1100 C (water); (c) 1300 C (water); (d–h) laser tempering melting, (d) darkfield image
superstructural reflex (001) in the central part of the specimen; (e), (f) bright-field image;
(g) electron diffraction pattern; (h) scheme of indexing
3 Structural Changes in Austenitic-Ferritic Steel 03Kh14N10K5M2Yu2T. . . 21
microscope JEM-200CX. Phase composition of steel was studied by X-ray diffrac-

tion analysis using K-monochromatic radiation chromium anode. The number of
magnetic phases has been measured by the Faraday magnetic balance.
The steel heat treatment was carried out by SNOL furnaces. The temperature
heating of specimens was to 1250 C. Kinetics of isothermal δ ! γ transformation of
the austenitic-ferritic steel 03Kh14N10K5M2Yu2T was studied at temperatures
1000–700 C, heat time of 5, 10, 20, 30, 40, 50, 60, 90, 120, and 180 min, as well
as the structure and phase composition of the steel prehardened from 1000 to
1200 C by direct heating to temperatures 300–1000 C, heat time of 1 h.
Laser surface treatment was carried out on 10 10 55 mm size samples.
Operation mode of CW laser “LT1-2” was characterized by 600 watts laser output
power. The velocity of the beam was 100 mm/min. The aim of this work is to
establish mechanisms of precipitation of reversed austenite during quenching and
ageing of overheated steel at 1100–700 C, at its reheating to establish the finish and
start temperatures for hot plastic deformation of this steel.
3.2 Results and Discussion
Table. 3.1 shows the effect of quenching temperature on physical properties of the
investigated steel.
There was a significant increase of magnetic saturation (Ms) in proportion to
δ-ferrite at temperatures above 1100 С. The main phase is δ-ferrite at 1300 С.
Precipitations of reversed austenite formed due to insufficiently high cooling rate
on the ferrite background. Colonies of reversed austenite form Widmanstatten
pattern with characteristic needle (plate) structure (Fig. 3.1c). Such form of the
precipitating phase usually is typical for shear transformation [3]. Suppressing of
reversed austenite precipitation is not possible during cooling at 1300 С to water.
The maximum value of the coercive force Hc can be explained by structural
changes after quenching at 800 C (the features of δ ! γ transformation [3], as well
as the influence of new paramagnetic impurities in the austenite). This is impeding
the process of magnetization reversal. Hc minimum has been observed after hard-
ening at 1200 C and above. The steel structure becomes almost completely ferrite
and grain growth occurs.
Table 3.1 The effect of quenching temperature on physical properties of the investigated steel
T quenching, С (water cooling) Нс, А/сm Br, Tl Ms, kА/m
800 22 0.12 400
900 15 0.10 380
1000 15 0.10 400
1100 7 0.50 950
1200 5 0.70 1000
Fig. 3.2 The microstructure of the steel 03Kh14N10K5M2Yu2T: (a) after laser treatment with a
reflow; (b) after laser treatment with the rehardening at 1000 C
The surface layer of the investigated steel has δ-ferrite single-phase structure
(Figs. 3.1d and 3.2a). The δ-ferrite hardness reaches 600–650 HV. The investigated
steel structure formation after laser treatment has been shown in [1]. However, it
should be noted some of structural features of the transition from δ-ferrite phase to
the ferritic-austenitic structure. Figure 3.1d–g shows that identical orientation frag-
ments of austenite are arranged at the periphery of weakly oriented subgrains of
δ-ferrite with dispersed spherical particles (Fe, Ni, Al) (on the outside of the pictures,
these fragments merge into one γ-grain).
The relative orientation of δ and γ lattices is close to the Kurdjumov-Sachs
orientation relationship, and extensive flat areas of phase boundary correspond to
the trace of the plane {111}δ || {110} γ.
Reheating to 1000 C leads to the formation of a two-phase austenitic-ferritic
structure, with very fine grains of austenite, in the δ-ferrite single-phase zone. This
indicates a high cooling rate and a large number of nucleation centres (Fig. 3.2b).
Reheating does not lead to visible changes in the microstructure in the case of the
equilibrium structure up to temperatures of about 700 C after quenching and can
only note the etch increasing (Fig. 3.3b). The heterogeneous structure of the phases
Fig. 3.3 Microstructure of austenitic-ferritic steel 03Kh14N10K5M2Yu2T hardened (a–d)

1000 C, (e), (f) from 1200 C and aged for 1 h: (a), (e) at 500 C; (b), (f) 650 C; (c) 700 C;
(d) 750 C
is observed during ageing above 650 C. This is due to the disintegration of the solid
solution (δ-ferrite), a partial conversion δ ! γ and intermetallic phase of a complex
composition. The presence of this phase (Fe74Cr12Ni14)2.09 (Mo64.4 Ti35.6) was
confirmed by the physical-chemical analysis of the precipitate of steel hardened at
1200 C and aged at a temperature of 650 C. An austenitic component is increased
(70–80%) to temperatures 700–750 C (Fig. 3.3d).
The differential scanning calorimetry (DSC) heating curves (Fig. 3.4) show two
exothermic peaks. The first (400–530 C) is associated with ageing in δ-ferrite, and
DDSC*10-3/(uv/mg/min)
TG/% DSC/(uv/mg)
Peak 1627 °C exc
0.04
101.2
0
0.03
[1.1]
101.0 Peak 731.4 °C Peak 981.0 °C

0.02 -2
Value 816.0 °C
100.8 Value 6320 °C
0.01
-4
100.6 Peak 468.2 °C
Peak 985.9 °C
Value 618.0 °C 0.00
100.4 Value 5323 °C -6

-0.01
100.2
-8
[1.1]00116_Ai203-H6 Zak [01] -0.02
DSC
100.0
Value 928.0 °C
-0.03 -10
Value 911.0 °C
99.8
200 400 600 800 1000 1200
Temperature/*c
Fig. 3.4 Curves of differential scanning calorimetry of the investigated steel at heating and cooling
the second (620–820 C) is associated with the above-described processes of

δ-ferrite disintegration.
Subsequent heating and holding for 1 h at 500 C and above (Figs. 3.2b and 3.4e,
f) contribute to further precipitation of the austenite phase to the equilibrium ratio
(50/50) in water-quenched (1200 C) austenitic-ferritic steel structure. The Morphol-
ogy of reversed austenite is changed. Widmanstatten pattern (Fig. 3.1c) becomes
almost equiaxial as a result of diffusion processes. The rate of formation of reversed
austenite is large and depends on the temperature of isothermal holding in the
investigated steel. The transfer of overheated (1250 C) steel to temperature
900 C, with time heating of 1–2 min, leads to structure formation like at Fig. 3.1a.
A further increase of time holding does not lead to changes in the quantity of
reversed austenite at these temperatures. The δ ! γ transformation proceeds slowly
(due to lower velocity of diffusion processes) and reaches an equilibrium phase ratio
at 900 C after 5 min, at 800 C after 30 min and at 700 C after 90 min.
The hot metal forming (rolling) generally is carried out at a temperature of
1200–900 С. σ-phase is precipitated at 700–900 C in industrial duplex steels
after slow cooling [4, 5]. However, the investigated 03Kh14N10K5M2Yu2T steel
does not have this shortcoming. It contains no precipitations of embrittling σ-phase.
Mechanical properties of this steel are shown in Table 3.2.
Tensile strength and yield strength are reduced at a temperature above 900 C.
This facilitates hot plastic deformation. Ductility remains almost the same.
Table 3.2 The mechanical properties of the steel at high temperatures

Temperature of testing, С σ0.2, MPa σTS MPa δ, % ψ, %
900 208 230 37.7 69.0
950 162 171 38.3 67.5
1000 134 151 40.0 62.0
The δ-ferrite quantity increases at 1200–1250 C. The process of hot plastic defor-
mation occurs in a temperature range; therefore the forging heating temperature
might be at a temperature of 1200–1250 C, but the finish rolling temperature must
be at a temperature of 900 C.
3.3 Conclusions
The study of the investigated austenitic-ferritic 03Kh14N10K5M2Yu2T steel

establishes:
1. Mechanisms of reversed austenite precipitation: (a) Widmanstatten mechanism
by quenching of reheated steel and (b) the diffusion mechanism by ageing of
overheated steel at 1100–700 C, at its reheating
2. Recommendations for hot plastic deformation of the investigated steel at the
temperature range of 1250–900 C
References
1. Nemirovskii, Y., & Khadyev, M. (2009). Structure of 03Kh14Ni10K5M2Yu2T steel after laser
treatment. Metal Science and Heat Treatment, 51(5–6), 297–300.
2. Mal’tseva, L., & Arkhangel’skaya, A. (2010). Special features of hardening of austenitic-ferritic
steel after thermoplastic treatment. Metal Science and Heat Treatment, 52, 39–45.
3. Apaev, B., & Voronenko, B. (1974). The kinetics of phase transformations in austenitic-ferritic
steels. Iron and Steel, 8, 90–95.
4. Hong, C., & Ding, T. (2011). A new economical sigma-free duplex stainless steel 19Cr-6Mn-
1.0Mo-0.5Ni-0.5W-0.5Cu-0.2N. Journal of Iron and Steel Research International, 18(4), 52–57.
5. Michalska, J., & Sozanska, M. (2006). Qualitative and quantitative analysis of σ and χ phases in
2205 duplex stainless steel. Materials Characterization, 56, 355–362.
Chapter 4
Correlation of Instrumented Charpy Load-
Displacement Curves with Crack Growth
in API 5L Grade X80 Pipeline Steels
V. Khotinov, V. Farber, and A. Morozova
4.1 Introduction
Charpy impact testing is required to provide the necessary pipeline life resource
especially for operation in low-temperature climate regions [1, 2]. X80 grade steels
are used for gas pipelines with 11.8 MPa air pressure. It is known that such steels
have extremely high Charpy energy more than 250 J/cm2 at –40оС. Special cracks
called separations are observed on the fracture surface. A high amount of separations
parallel to rolling plane were found as the main feature of the fracture surface in X80
pipes. Evidently, fewer separations were formed in pipes with similar Charpy energy
but high arrestability. Based on these findings, the question is raised of whether the
Charpy test is suitable for predicting fracture arrest in high strength material.
Through subsequent refinements in testing and certification standards, the Charpy
test has been developed in accordance with the requirements of the engineering
community. Due to its low cost and convenience, there is a growing interest in using
the instrumented Charpy test to obtain a wide range of information about fracture
initiation, crack propagation mechanisms, and impact energy properties [3–6]. Accu-
rate determination of load and/or energy versus displacement behavior during the
instrumented impact test is essential to obtain such information [7, 8].
The following impact strength properties and crack propagation resistance of
low-carbon ultrahigh ductile steel will be further discussed in detail, including the
analysis of both smoothed load-displacement curves and fracture surfaces.
V. Khotinov (*) · V. Farber · A. Morozova


https://doi.org/10.1007/978-3-319-75340-9_4
28 V. Khotinov et al.
4.2 Materials and Experimental Procedure
The material used for the present research was API X80 grade low-carbon (LC) steel
with 0.05 wt.%C – 1.5%Mn – 0.15%Si – 0.04%V chemical composition. After
TMCP and subsequent accelerating, cooling LC steel had ultrafine (~3–5 μm)
ferrite-bainite structure with ultrahigh toughness level.
Charpy specimens were machined from the middle pipe wall. Specimen geomet-
rical dimensions were those of typical full size V-notch, that is, 10x10x55 mm,
according to specification ASTM E23.
Charpy impact tests were carried out in temperature range from +20 to –80 C on
an Instron Ceast 9350 instrumented droptower machine with maximum impact
energy of 757 J supplied by data acquisition system (DAS) Ceast 16000. The data
were acquired using a sampling frequency of 1.0 MHz and a point number of 8000
with the sampling time of 0.001 ms. Load vs. displacement curves were smoothed by
a hardware filter with 2 kHz frequency on the DAS to reduce the effects of proper
oscillations of the specimen-striker elastic system.
The fracture surfaces of Charpy impact specimens were investigated via visual
observation with fivefold magnification and were subjected to identification and
measurement with 0.1 mm accuracy of the next fracture zones [9]:
– Near to notch shear zone Θ
– Homogeneous ductile zone Lh
– Fiber ductile zone Lf
– Brittle zone of Lbr
– Ductile final break zone Lfb
– Shear tips λ
Impact load vs. displacement curves are shown in Fig. 4.1. The impact load behavior
on the elastic displacement stage has been described by the slope angle α1 (tg α1)
named as elastic rebound compliance (RCel) and the level of general yield point Fgy.
It can be seen that RCel is constant and does not depend on test temperature up to the
Fgy level, equal to 18.5 kN, at any test temperature.
It is evident that typical impact load points Fgy, Fm, Fiu, and Fa can be correctly
construed on these traces, but it is surprising that there are two maximums for
ultraductile steel. Appearance of the first peak like yield drop on the tensile test
curve was induced by crack initiation from point Fgy to point Fmax1 and crack
propagation in shear zone Θ from point Fmax1 to point Fmin. Typical for steels at
any test temperature, the shear zone is caused by severe plastic deformation near to
notch (Fig. 4.2). Shear lips λ are plastic deformation products as well, but their width
depends on test temperature – the lower the test temperature, the lower the shear lips’
width.
4 Correlation of Instrumented Charpy Load-Displacement Curves. . . 29
F,kN Fmax2
Fmax1 T= +20°C
T= -40°C
20 T= -60°C
Fgy T= -80°C
Fmin
Fiu Fiu
15 Fgy
α2
Fmax1
Fmin
10 α2 Fa Fa Fmax2
Fiu
α1 Fa
Fa
5
0
0 5 10 15 20 S, mm
Fig. 4.1 Impact load vs. displacement curves of LC steel
Fig. 4.2 Crack propagation

Q
zones on the fracture surface
of LC steel correlated with Lh
characteristic points of “F-s” l
curve Lf
Lf b
The second peak occurrence is a result of the interaction between the crack and
the plastic deformation zones ahead the tip of a crack. This peak disappeared when
the plastic deformation zone could not resist crack propagation at a lower test
temperature. Curve stage size from points Fmin to Fiu is correlated with crack
propagation in homogeneous zone Lh due to a ductile stable fracture.
Valuable information can be obtained from the analysis of an unstable crack
growth stage from point Fiu to point Fa which is correlated with fiber zone Lf,
(Fig. 4.2). Rebound compliance (RCiu ¼ tg α2) of segment FiuFa led to a growing
portion of brittle fracture component at a lower test temperature.
Figure 4.3 shows the temperature dependences of the fracture zone length of API
X80 steel. It can be seen that the lengths of both shear zone Θ and ductile final break
zone Lfb are only slightly sensitive to the change of test temperature, whereas the
lengths of both the homogeneous ductile zone Lh and fiber ductile zone Lf change
noticeably. The decrease in test temperature from 20 to –60 C leads to a decrease
in the length of the Lh zone and to an increase in the length of the Lf zone.
The correlation between Charpy impact toughness and load-displacement curve
characteristic parameters Fmax2 and RCiu is shown in Fig. 4.4. It is well known that
steels that are subjected to a thermomechanical controlled process often show a
30 V. Khotinov et al.
6.0
Fracture zone length, mm 5.0
4.0
Lh
Lf
3.0
2.0
Lfb
1.0
Q
0.0
-100 -80 -60 -40 -20 0
Test temperature, оС
Fig. 4.3 Temperature dependences of the fracture zone lengths
KCV,
500 Fmax2,
25
J/cm2 kN,
RCiu
Fmax2 upper
400 20
plateau
300 15
rising
shelf
200 10
100 – KCV; 5
– Fmax2;
lower
RCiu – RCiu
plateau
0 0
-120 -100 -80 -60 -40 -20 0 20 Т, 40
°С
Fig. 4.4 Correlation of impact toughness KCV and instrumented impact parameters Fmax2 and RCiu
in brittle-ductile temperature transition of LC steel
“rising shelf” behavior when upper plateau, rising shelf, transition stage, and lower
plateau on transition curve are observed [10, 11].
It is seen that Fmax2 degeneration is well correlated with KCV on the upper plateau
and corresponds to a decrease of Lh zone on the Charpy fracture surface (Fig. 4.4).
Slope angle RCiu accounts for an increase in the brittle fracture component – the
4 Correlation of Instrumented Charpy Load-Displacement Curves. . . 31
more brittle the fracture, the bigger the RCiu value. At the same time, the fiber
fracture zone Lf expanded.
It is clear that the most complete information about material crack resistance can
be obtained by using both Fmax2 and RCiu values as the most sensitive and unique
characteristics for crack propagation. Analysis of these fracture parameters has
clearly shown that fine-grained ferrite-bainite LC steel has a very high crack
resistance.
4.4 Conclusions
In conclusion, characteristic point F and rebound compliance RC on smoothed

instrumented impact load vs. displacement traces reflect the crack initiation and
propagation through the Charpy specimen adequately. This correlates with the
Charpy fracture surface zones of API X80 steel. Co-analysis of the instrumented
impact test curves and fracture surfaces allows determining the crack resistance of
such ultraductile materials like API X80 steel in addition to standard required
characteristics (impact toughness, BDTT, impact yield strength, etc.).
References
1. Arabey, I. Y., Pyshmintsev, I. Y., Farber, V. M., Khotinov, V. A., & Struin, A. O. (2012).
Failure of pipe steel of X80 (K65) strength class. Steel in Translation, 42(3), 212–218.
2. Farber, V. M., Pyshmintsev, I. Y., Khotinov, V. A., et al. (2010). Proc. of XVIII Int. Pipeline
Conf. (pp. 108–117). Chelyabinsk: RosNITI.
3. Manahan, M. P., & Stonesifer, R. B. (2000). The difference between total absorbed energy
measured using an instrumented striker and that obtained using an optical encoder, ESIS/ASTM
STP1380 (pp. 181–197).
4. Tronskar, J. P., Mannan, M. A., & Lai, M. O. (2002). Measurement of fracture initiation
toughness and crack resistance in instrumented Charpy impact testing. Engineering Fracture
Mechanics, 69, 321–328.
5. Kobayashi, T., Inoue, N., Morita, S., & Toda, H. (2000). On the accuracy of measurement and
calibration of load signal in the instrumented Charpy impact test, ESIS/ASTM STP1380
(pp. 198–209).
6. Viehrig, H. W., Boehmert, J., Richter, H., & Valo, M. (2000). Use of instrumented Charpy test
for determination of crack initiation toughness, ESIS/ASTM STP1380 (pp. 354–364).
7. Steel Charpy, V. (2000) Notch pendulum impact test – Instrumented test method, ISO 14556.
8. Standard test method for instrumented impact testing of metallic materials, ASTM E2298
(2013).
9. Botvina, L. R. (2008). Fracture: Kinetics, mechanisms and total regularities. Moscow: Nauka
publishing house.
10. Mannucci, G., & Demofonti, G. (2011). Control of ductile fracture propagation in X80 gas
pipeline. Journal of Pipeline Engineering, 10(3), 133–145.
11. Wilkowski, G., Rudland, D., & Wolterman, R. (2005). Predicting the brittle-to-ductile fracture
initiation transition temperature for surface-cracked pipe from Charpy data. In Proc. of ASME
Pressure Vessels and Piping Conf. 6 (pp. 545–550). Denver, USA.
Chapter 5
Damping Behavior
of Aluminum Replicated Foam
W. Riehemann, A. Finkelstein, U. Arlic, and D. Husnullin
5.1 Introduction
The technology of porous open-cell aluminum production [1] involves pouring

molten aluminum into the interstices of a water-soluble filler, which is sodium
chloride of various particle fractions. Initially this technology was proposed for
structural materials in aircraft industries. However, the material did not find its
proper application in this field. It is mostly used as filtering and noise reduction
material due to its high isotropic structure and porosity.
There are various methods of obtaining isotropic structures, including prelimi-
nary sintering of the filler and subsequent infiltration of liquid aluminum with high
pressure [2], infiltration under vacuum with atmospheric pressure and structure
control based on the analysis of physical chemistry [3], and hydraulic [4] processes
taking place during the infiltration.
The technology of infiltration under high pressure is quite well known. It has been
subjected to comprehensive studies including mechanical features [2]. In fact, this
technology has proven to be extremely expensive, and it does not allow enlarging
from the laboratory level to industrial production.
For this study the vacuum infiltration technology was employed in cooperation
with Composite Materials Ltd. (Kirovgrad, Russia). It allows manufacturing prod-
ucts of any size and shape (e.g., see Fig. 5.1). However, the mechanical parameters
of this material have not been sufficiently investigated or understood.
The aluminum open-cell material obtained by replication casting can replace
close-cell aluminum foams in their traditional area of application – dampers and
W. Riehemann · U. Arlic
Technical University Clausthal, Clausthal-Zellerfeld, Germany
A. Finkelstein (*) · D. Husnullin
Ural Federal University, Yekaterinburg, Russia

https://doi.org/10.1007/978-3-319-75340-9_5
34 W. Riehemann et al.
Fig. 5.1 Aluminum porous

filters of commercial use
produced by replication
vacuum infiltration
technique
impact-absorbing elements. Obviously, there is a particular necessity for complex

research on the mechanical and damping properties of replicated open-cell alumi-
num foams to design quality production.
5.2 Review
Conversion of elastic vibration energy into internal friction heat is the main mech-
anism of damping. There are some values to characterize material damping:
• Damping capacity, which is a ratio of converted vibration energy to full energy of
load-unload cycle [5].
• Loss tangent tan ϕ, where ϕ is the phase lag between stress and strain. The
technique was described in [6], for example.
• Logarithmic decrement of decaying vibration, see Eq. (5.1):

An
δ ¼ ln : ð5:1Þ
Anþ1
where δ is logarithmic decrement of decaying vibration, and An and An+1 are adjacent
amplitudes of decaying vibration.
For different porous metals wide experimental investigations were carried out by
Golovin, Riehemann et al. in Clausthal Technical University. They based their
measurements of damping on the logarithmic decrement technique [7], which has
also been applied for the present research.
5 Damping Behavior of Aluminum Replicated Foam 35
5.3 Sample Preparation Technology
Samples for dumping tests were prepared by the replication casting technology. This
is similar to a chill casting process, but in addition to that, a salt preparation branch is
implemented in the technological cycle. The technological scheme of production is
shown below (Fig. 5.2).
Commercial aluminum alloy AlSi7 (AK7 GOST 1583–93 grade in Russia) was
used for producing samples. Apart from AK7, self-production scrap from feeder
heads was used (25–30 wt. % of charge). The melting procedure was conducted in
resistance-heated pot-type furnace. The melt was overheated up to 720–750 C.
Sodium chloride particles were sieved by fractions using DIN standard sieves
(0.1–0.2 mm, 0.2–0.315 mm, 0.315–0.63 mm, 1.0–1.6 mm) and then heated in
ceramic cells in a chamber furnace up to 600–650 C. After that a portion of
preheated NaCl was placed into a metal mold and compacted by vibration. The
temperature of the metal mold was in the range 350–450 C to provide mold
fillability. At the next stage, molten aluminum was poured over the filler into the
metal form. And then the infiltration of NaCl layer was carried out under pressure
drop between the vacuum receiver (300 hPa) and the atmosphere (1024 hPa).
Finally, finished solidified castings were removed from the mold. After that they
were machined to obtain samples for mechanical tests according to Standard Test
Methods for Tension Testing of Metallic Materials (ASTM E8/E8M) and for
damping tests, Fig. 5.3. Samples for damping measurements are thin plates of
3 mm thickness with cylindrical tip.
Fig. 5.2 The scheme of

replication casting
technology
Fig. 5.3 Samples for

damping measurements
To get the metal porous structure, NaCl was removed from the composite sample
by dissolving salt particles in water with a forced convective stream over the samples
surface. The porosity of finished samples was determined indirectly by weight.
It is worth mentioning that the porous structure of replicated aluminum samples
obtained by vacuum impregnation technique may be characterized as homogenous
and open cell.
For more information on replication casting technology, see Refs. [3, 4, 8].
5.4 Measurement Technique
As a rule, the measurement of damping (δ) of porous materials like foams is not
trivial. Subjecting porous materials to stable vibrations might cause difficulties.
Extended quantity of samples is needed to perform representative measurements
for the whole material. Moreover careful machining and clamping without plastic
deformation is necessary. Due to the extended surface of the porous material, surface
layers of oil or other liquids have to be avoided. In addition, damping is often
confused with acoustical silencer processes: reflection, refraction, and dispersion of
sound. In this study solely material damping of porous metal AlSi7 was measured
and discussed.
Material or solid state damping (δ) was measured in the air of normal pressure as
the logarithmic decrement of free bending beam vibrations. The single cantilever
bending beams fixed at one end were excited into the first bending resonance mode
by means of a permanent magnet fixed at the free end and an exciting coil.
Logarithmic decrement of decaying vibrations was obtained from time dependency
of voltage induced in coil by a permanent magnet. Further details about the exper-
imental setup are described elsewhere [5, 7].
In addition to the abovementioned capability, the experimental setup is able to
measure the elastic modulus of materials [9].
The results of the damping measurements are presented in Fig. 5.4, where the
damping is plotted versus maximum strain amplitude of the vibrating bending
beams for samples with various pore sizes. The numbers of successive measure-
ments after excitation to vibration are also presented.
The damping curves for the samples with pore sizes up to 1.6 mm show typical
metallic behavior with practically amplitude-independent damping value of 0.002 up
to strain amplitudes of about 104. For higher values of strain amplitude strong
monotonously increasing damping is observed. This behavior can be accounted for
progressive dislocation break away from weak pinning points with increasing strain
amplitude, as it has already been explained by the theory of Granato and Lücke
[10]. It is amazing that for maximum pore sizes in the range of 0.63–1.6 mm no
systematic dependency of damping on porosity was noticed. In earlier investigations
concerning the damping of aluminum foams stronger dependencies on foam size
were found [5, 11]. For our samples the statistical fluctuation of strain amplitude-
dependent damping established between different samples of the same mean pore
size (1.5 mm) is even higher than the differences between samples of different pore
sizes (0.315–1.6 mm max).
Contrary to this stable and invariant damping behavior, the whole strain
amplitude-dependent damping curve changes dramatically for samples with bigger
pores (>3.0 mm), as can be noted for measurement #1 and the directly following
measurement #2, shown in Fig. 5.4, at the same sample with >3.0 mm pore size.
Fig. 5.4 Damping versus maximum strain amplitude of porous bending beams for various max-
imum pore sizes, samples, and numbers of successive measurements after excitation to vibration
Table 5.1 Young’s modulus of AlSi7 porous material with different pore sizes
Pore size range Porosity, % Young’s modulus, MPa
Nonporous AlSi7 alloy 0 71,000
0.35–0.63 mm 52 4410
1.00–1.60 mm sample #1 52 3230
1.00–1.60 mm sample #2 53 2960
1.60–3.00 mm measurement #1 54 1910
1.60–3.00 mm measurement #2 54 1900
The damping of these samples proved to be much higher, especially for strain
amplitudes in the medium strain amplitude range. Moreover, it does not necessarily
go up monotonously, as the strain amplitude increases, and it changes during the
measurement itself. This damping behavior is also found in metal foams [5, 11] or
other materials with cracks [12], and it demonstrates time- and temperature-
independent hysteretic behavior instead of time- and temperature-dependent inelas-
tic behavior determined for dislocation damping. The hysteretic damping curves can
also be explained by a simple rheological model [13].
While both the damping and the damping behavior change erratically for mate-
rials with pore sizes between 1.6 mm and 3 mm, the Young’s modulus decreases
continuously with increasing pore size in the whole investigated pore size range.
This is evident from Table 5.1, where the elastic moduli of the materials with various
maximum pore sizes are listed and compared with the bulk material as well.
The damage of the material with the coarse pores (1.6–3.0 mm) by the vibrations
of the damping measurements can be detected by the small drop of the modulus due
the vibration (1910–1900 MPa), but it is obvious that the change in damping due to
fatigue is much higher and therefore much more sensitive to the detection of cracks.
To compare damping of replicated porous aluminum, we took into account some
information on damping behavior of the main competitive material, that is, foamed
aluminum Alp-85 [9] and current results for coarse pore (1.6–3 mm) replicated
aluminum. For full understanding, pure aluminum data were added (see Table 5.2).
Obviously, Alp-85 has a higher damping due to higher porosity but low level of
mechanical properties. That means the higher loadings on damper, the more volume
of material demanded. In this respect, replicated aluminum appears to be more
convenient material to use for damping and impact absorbing.
5.6 Conclusions
In the present work experimental examination of replicated porous aluminum

damping was realized.
According to the results, one can draw the following conclusion: compared to the
replicated porous aluminum, foamed aluminum (Alp-85) exhibits higher damping
properties. But it is worth mentioning that replicated aluminum possesses higher
Table 5.2 Comparison of mechanical properties for porous and compact aluminum
Replicated porous
Material Pure aluminum Alp-85 aluminum
Type of structure – Close cell Open cell
Pore size, mm – 4.0–5.0 1.6–3.0
Damping at strain amplitude 105 0.002 0.040 0.005
104 0.002 0.050 0.01–0.03
Density, kg/m 2700 400 1460
Porosity, % 0 85 54
Specific Young’s modulus, (GPa*m3)/kg 0.0259 0.0055 0.0013
Young’s modulus, GPa 70 2.2 1.9
Ultimate tensile strength, MPa 70 2.5 7.7
mechanical properties, such as specific Young’s modulus and tensile strength.

Combined with good damping properties, it proved to be more attractive material
for designing in the fields of vibroprotection and mechanical energy absorption.
According to the results, the most appropriate pore size of replicated aluminum is
1.6–3.0 mm that corresponds to metal foam damping behavior.
Acknowledgment The authors would like to acknowledge Composite Materials Ltd. (Kirovgrad,
Russia) for the kind assistance in sample production and machining.
References
1. Kuchek, H. A. (1964). Patent US 3138856 Method of producing clad porous metal articles.
2. Despois, J.-F. (2005). Replicated aluminium foam, processing and properties, Ecole
Politechnique Federale de Lausanne, p. 265.
3. Furman, E. L., Finkelstein, A. B., & Cherny, M. L. (2013). Permeability of aluminium foams
produced by replication casting. Metals, 3(1), 49–57.
4. Furman, E. L., Finkelstein, А. B., & Cherny, M. L. (2014). The anisotropy of replicated
aluminum foams. Advances in Materials Science and Engineering, 1–6.
5. Golovin, I. S., Sinning, H. R., Göken, J., & Riehemann, W. (2003). Amplitude dependent
damping of some metallic foams. Solid State Phenomena, 89, 267–272.
6. Zhang, Y., Ma, N., & Wang, H. (2007). Effect of particulate/Al interface on the damping
behavior of in situ TiB2. Materials Letters, 61, 3273–3275.
7. Göken, J., & Riehemann, W. (2002). Thermoelastic damping of the low density metals AZ91
and DISPAL. Materials Science and Engineering A, 324(1–2), 134–140.
8. Kazantsev, S. P., & Husnullin, D. V. Technological processes of obtaining of replicated
aluminium foam. Contemporary Engineering Sciences, 8(16), 723–727.
9. Golovin, I. S., & Sinning, H.-R. (2003). Damping in some cellular metallic materials. Journal of
Alloys and Compounds, 355(1–2), 2–9.
10. Granato, A., & Lücke, K. (1956). Theory of mechanical damping due to dislocations. Journal of
Applied Physics, 27(6), 583.
11. Golovin, I. S., Sinning, H.-R., Göken, J., & Riehemann, W. (2001). Mechanical damping of
some Al foams under cyclic deformation. Proc. of MetFoam, Int. Conf. on Cellular Metals and
Metal Foaming Technology, 323–328.
12. Golovin, I. S., Sinning, H.-R., Göken, J., & Riehemann, W. (2004). Fatigue related damping in
some cellular metallic materials. Materials Science and Engineering A, 370(1–2), 537–541.
13. Göken, J., & Riehemann, W. (2004). Damping behaviour of AZ91 magnesium alloy with
cracks. Materials Science and Engineering A, 370(1–2), 417–421.
Part II
Non-ferrous Metals Metallurgy due to the
Refining of Secondary Raw Materials
Chapter 6
Recovery of Lead and Zinc from Fine Dust
of the Copper Smelting Industry Using
a Chelating Agent
S. Mamyachenkov, O. Anisimova, and E. Kolmachikhina
6.1 Introduction
Structure investigation of fine dust sample is carried out by means of X-ray

diffractometer XRD 7000C (Shimadzu). According to X-ray phase analysis
(Fig. 6.1), dust sample contained further main components: lead sulfate, zinc
oxide, scorodite, and arsenic oxide [1] (Table 6.1).
Aspects of distinct process steps of dust treatment are the subject of wide
speculation in previous works [2–7]. The authors of these papers advanced particular
arguments in favor of one or other solvents and offered ways of improving outdated
processing technology.
The present work is devoted to investigation of metallurgical fine dust treatment.
A speciality of this new innovative hydrometallurgical technology is using
oxyethylidenediphosphonic acid, which is known as OEDP (Fig. 6.2a).
Oxyethylidenediphosphonic acid C2H8O7P2 is white powder grayish or beige gra-
dational, flameproof, and blastproof. This reagent is dissoluble in water, acids,
alkalies, methanol, and ethanol. OEDP forms stable complexonates with metals
ions, which have a chelate structure (Fig. 6.2b) [8].
6.2 Experiment Details
Small-scale tests of fine dust leaching were carried out in thermostated setup
provided with immersion stirrer, pH meter, and temperature compensator system
for pH automatic maintenance (Fig. 6.3). Calculated amount of dried, milled, and
S. Mamyachenkov (*) · O. Anisimova · E. Kolmachikhina

Institute of New Materials and Technologies, Ural Federal University, Yekaterinburg, Russia

https://doi.org/10.1007/978-3-319-75340-9_6
44 S. Mamyachenkov et al.
2
250 2 2
3
Intensity (pps)
1 2 6
200
4
150
1 4 1 3
1 5 5 2
100
50
0
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
2θ
Fig. 6.1 Diffractogram of fine dust: 1 – ZnO, 2 – PbSO4, 3 – ZnFe2O4, 4 – Cu2O, 5 – As2O3, 6 –
FeAsO42H2O
Table 6.1 Fine dust Pb Zn Cu Fe As

composition, %
8.68 13.4 12.9 13.9 3.42
Fig. 6.2 Structural formula a b

of OEDP and complexonate O CH3 O O CH3 O
of metal
HO P C P OH O P C P O
OH OH OH
OH OH OH
Me
screened out (fraction 0.1) dust was leached by water solution of OEDP
(1.5 mol/l). A value of pH ¼ 11 was chosen due to conditions of OEDP selective
complexation with lead. The pH value was held constant during tests by dosing
necessary alkali volume.
After the liquid was tested and solid phases were separated, the received cake was
dried at 383 K and weighed. The cake was triturated and averaged. Achieved
material was pelleted and analyzed by X-ray diffractometer XRD 7000C (Shimadzu)
for lead, zinc, copper, and iron concentration. Filter liquor was analyzed by the
atomic absorption method (spectrometer novAA 300).
On the basis of the cake and filter liquor analysis, we calculated metal extraction.
The resultant extraction value was taken up as the average extraction value within
the accuracy of 5%.
By means of an experiment design, the array of dust leaching parameters was
formed. The following parameters were varied: liquid-to-solid ratio (X1) from 3 to
7 and process temperature (X2) from 298 to 353 K. The extraction of lead into
solution as main component and extraction of zinc, copper, and iron were controlled.
6 Recovery of Lead and Zinc from Fine Dust of the Copper Smelting. . . 45
Fig. 6.3 Setup for dust leaching. 1 – Thermostat, 2 – thermostat stirrer, 3 – thermostat heater, 4 –
contact thermometer, 5 – control module and driver thermostat stirrer, 6 – control module and driver
stirrer, 7 – volume burette, 8 – upright, 9 – pH meter, 10 – combination electrode, 11 – temperature
compensator, 12 – stirrer, 13 – pulp, 14 – reacting glass
With the aim of examination of complex existence, there were received residuals
after leaching of pure components of dust. The IR spectra of separated compounds
and pure OEDP were recorded on FTIR (Fourier transform infrared) spectrometer
ALPHA-T.
6.3 Results and Discussions
6.3.1 Leaching Tests
With the aim of leaching optimization, response surfaces were created in

STATISTICA 7.0. The response surfaces describe dependences of lead (Fig. 6.4a),
Fig. 6.4 Influences of temperature and pulp density on extraction: (a) lead, (b) zinc, (c) copper,
(d) iron
zinc (Fig. 6.4b), copper (Fig. 6.4c), and iron (Fig. 6.4d) extractions on temperature
(X1) and pulp density (X2).
The relations of metal extraction into solution to temperature have extremal
character. Maximum magnitude of extraction was observed in the area of elevated
temperatures. It is possible that leaching process is limited by chemical interaction
step. It should be pointed out that lead extraction reached 96%, whereas a maximum
zinc extraction under the same conditions is 20%, and impurities extraction is equal
to 0.1–3.0%. This phenomenon allows one to assume lead complexation selectivity
at the alkaline conditions.
Maximum lead, zinc, and iron extractions were received at the conditions of
middle diluted pulps (l:s ¼ 5:1), while copper extraction is increased along with pulp
density reduction up to 7:1.
Probably, the value of copper extraction depends not only on pulp density but
also on pH area of complexation with OEDP and MeHL complex indissolubility in
broad pH area [9].
6.3.2 Study of OEDP Complexes
The existence of phosphorus in OEDP structure initiates characteristic absorption

bands on IR spectra. At IR spectra of OEDP, further bands were identified (Fig. 6.5):
1. Intensive absorption bands with medium intensity were observed. This could be
explained by P-H stretching vibrations in area 2500–2350 cm1.
2. Vibrations connected with P¼O group appear at 1350–1175 cm1. This band is
displaced on 50–80 cm1 due to hydrogen bond formation between –OH and
P¼O groups.
O
3. OEDP contains P group in which hydrogen bond is very strong; vibration
OH
band of OH comes out at 3200–2500 cm1 (broad and mild)
4. C-P-O arrangement is accountable for absorbance band at 1100 cm1.
5. P-O-CH3 arrangement causes absorbance at 1000–950 cm1.
6. Bonds P¼CH3 induce absorbance at 700 50 cm1.
7. P-OH group is characterized by absorbance band at 1030 cm1.
0.95 0.96 0.97 0.98 0.99 1.00
3500 3000 2500 2000 1500 1000 500

Wavenumber, cm-1
Fig. 6.5 IR spectra of OEDP

0.995
0.985
0.975
0.965
3500 3000 2500 2000 1500 1000 500

-1
Wavenumber, cm
Fig. 6.6 IR spectra of lead phosphonate
IR spectra of the leaching residues of dust pure components contain absorbance

O
band indicating OEDP. However, in spectra of metals, phosphate bond of P
OH
disappeared. This phenomenon can be explained by the influence of intermolecular
interactions between atoms and further splitting of bands. In addition, there is
displacement of absorbance bands due to intermolecular interactions. Due to strong
hydrogen bonds, the displacement is less than 25 cm1. It is arguable that band
position in the range of 1025–1040 cm1can be used for determining bond character
in complex Me-O (Fig. 6.6).
6.4 Conclusions
In this paper, features of metallurgical fine dust leaching was studied. Optimal
parameters of lead and zinc leaching were established by using chelating reagent;
these parameters are initial OEDP concentration 1.5 mol/l, pH ¼ 11–12, pulp density
5:1, and 303–323 K. Under these conditions, metal extractions in solution are Pb
96–98%, Zn 15–20%, Fe 1–3%, and Cu 0.05–0.1%. By means of IR spectrometry,
OEDP complexing with metals at leaching was determined. The reported study was
funded by State Assignment No. 10.7347.2017/8.9.
References
1. Gorelkin, S. S., Rastorguev, L. N., & Skakov, Y. A. (1970). Rentgenograficheskij i

ehlektronnoopticheskij analiz (pp. 245–250). Moskva: Metallurgiya.
2. Smirnov, M. P., Sorokina, V. S., & Gerasimov, R. A. (1996). Organizaciya ehkologicheski
chistogo gidroehlektrohimicheskogo proizvodstva svinca iz vtorichnogo syr’ya v rossii. Tsvetnye
Metally, 9, 13–17.
3. Antrekowitsch, J., & Antrekowitsch, H. (2011). Hydrometallurgically recovering zinc from
electric arc furnace dust. JOM, 53(12), 26–28.
4. Karelov, S. V., Mamyachenkov, S. V., & Nabojchenko, S. S. (1996). Kompleksnaya pererabotka
cink- i svinecsoderzhashchih pylej predpriyatij cvetnoj metallurgii (pp. 21–23). Moskva:
CNIIIcvetmet ehkonomiki i informm.
5. Antipov, N. I., Maslov, V. I., & Litvinov, V. P. (1983). Kombinirovannaya skhema pererabotki
tonkih konverternyh pylej medeplavil’nogo proizvodstva. Tsvetnye Metally, 12, 12–13.
6. Glazkov, E. N., & Antonov, A. S. (1963). Gidrometallurgicheskaya pererabotka svincovyh
produktov metodom aminnogo vyshchelachivaniya. Tsvetnye Metally, 12, 28–32.
7. Bakhtiar, F., Atashi, H., Zivdar, M., & Seyed Bagheri, S. A. (2008). Continuous copper recovery
from a smelter’s dust in stirred tank reactors. International Journal of Mineral Processing, 86,
50–57.
8. Dyatlova, N. M., Temkina, V. Y., & Popov, K. I. (1998). Kompleksony i kompleksonaty metallov
(pp. 115–117). Moskva: Himiya.
9. Kabachnik, M. I., Lastovskij, R. P., & Medved’, T. Y. (1967). O kompleksoobrazuyushchih
svojstvah oksiehtilidendifosfonovoj kisloty v vodnyh rastvorah. Doklady AN SSSR, 3(177),
582–585.
Chapter 7
High-Pressure Leaching Arsenic
Containing Polymetallic Copper Mattes
K. A. Karimov, S. S. Naboychenko, V. I. Neustroev, and V. A. Menshchikov
7.1 Introduction
Lead, zinc, and arsenic are unavoidable impurities in copper ores. Due to the
concentrates quality deteriorating and being involved into secondary raw material
processing, these impurities are increasingly circulated in copper smelting produc-
tion and accumulated in the dusts.
According to Makhov et al. [1], most of the arsenic (up to 95–96%) goes to the
fumes and fine dusts during smelting of polymetallic raw materials to produce poor
mattes. Fine dusts of OJSC Sredneuralsk Copper Smelter (SUMZ) contain, %: Cu
10.68, Zn 10.67, Pb 14.31, Fe 15.81, S 8.09, and As 7.51. Return of these dusts to
copper pyrometallurgical processing will result in contamination of blister copper
with arsenic and lead [2].
It is reasonable to take out the fine dusts and similar negotiable intermediate
products from recycling and subject them to smelting reduction to produce
polymetallic matte.
Such a technology was implemented at PSTSM “Uralelectromed”
(Top-Neyvinsky plant) where dust reduction smelting was running in the shaft
furnace (SF) and ore-smelting furnace (OSF) [2]. Obtained mattes contained,%:
Cu 30–40, Zn 2–5, Pb 14–23, Fe 7–20, S 15, and As 4–5.
Return of these mattes to pyrometallurgical processing will again result in the
accumulation of arsenic and lead.
Therefore, obtained mattes must be exposed by separate technology.
K. A. Karimov (*) · S. S. Naboychenko · V. I. Neustroev · V. A. Menshchikov

The Ural Federal University named after the first President of Russia B. N. Yeltsin,
Yekaterinburg, Russia

https://doi.org/10.1007/978-3-319-75340-9_7
52 K. A. Karimov et al.
Table 7.1 Composition Materials Cu Pb Zn Fe S As

of mattes, %
OSF 40.1 23.0 2.9 7.1 14.6 5.0
SF 30.2 11.0 1.7 23.3 13.6 5.0
This chapter presents the results for the selective extraction of copper with
oxidative sulfuric acid pressure leaching and pressure leaching with preliminary
treatment of mattes with copper sulfate followed by oxidative leaching.
7.2 Material
The composition of used mattes is shown in Table 7.1.

According to XRD included in mattes are phase sulfides (PbS, Cu2S, FeS, (Zn,
Fe) S) and arsenides (FeAs2, Cu3As, FeAs, Cu0.85As0.15) and the inclusion of
metallic copper.
Mattes of OSF and SF were ground up in a dry grinding ball mill to a particle size
of 0.074 mm.
7.3.1 Oxidative Sulfuric Acid Pressure Leaching
Tests were carried out in titanium autoclave having a volume of one dm3 [3] under
the following conditions: pulp density L: S ¼ 6: 1; oxygen pressure 0.4 MPa;
temperature 140–180 C; sulfuric acid concentration 10–130 g/dm3; values Qa/Qs,
where Qa is the actual amount of sulfate ions, considering quantitative oxidation of
sulfur of matte to SO42 and Qs is the stoichiometrically required amount of sulfate
ions to extract copper matte, between 0.82 and 3.17, and duration of leaching
30–240 min.
Experimental conditions and results are shown in Table 7.2.
Acid consumption significantly affects the results of leaching. The best results of
the copper extraction (94.26%) were achieved at 180 C and an initial acid concen-
tration of 64 g/dm3 (Qa/Qs ¼ 1.35). Extraction of copper from SF matte with a
higher iron content was up to 56% at the same value of Qa/Qs ¼ 1.17. Under these
conditions the sulfide sulfur matte went into solution up to 71%, and the extraction of
iron reached 30%.
The highest arsenic extraction for the leaching of mattes at 160 C was as follows:
• For SF matte reached 57% ([H2SO4]0 ¼ 132 g/dm3, Qa/Qs ¼ 3.2).
• For OSF matte reached 53.8% ([H2SO4]0 ¼ 55 g/dm3, Qa/Qs ¼ 1.3).
At the same time, copper extraction decreased to 18–36% and sulfur to 15–20%.
Iron passing into solution under these conditions greatly increased and reached
80–90%. It is possible that the exchange reaction of copper deposition makes
7 High-Pressure Leaching Arsenic Containing Polymetallic Copper Mattes 53
Table 7.2 Experimental conditions and results of oxidative sulfuric acid pressure leaching of
mattes
H2SO4
Materials Test g/dm3 Qa/Qs t, C Duration, min Copper extraction, %
OSF 1 10 0.82 160 90 35.14
2 37 1.1 160 120 83.19
3 55 1.26 160 120 18.13
4 85 1.55 160 120 16.87
5 62 1.33 180 120 43.50
6 43 1.14 180 120 78.47
7 64 1.35 180 240 94.26
SF 8 10 1.02 140 120 9.90
9 10 1.02 160 120 54.83
10 132 3.17 160 60 36.32
11 22 1.17 180 120 30.40
12 21 1.17 180 240 55.78
progress at T 160 such as CuSO4 + MeS ¼ CuS + MeSO4, where Me ¼ Fe,

Zn, Pb.
The extraction of arsenic and iron to the solution is decreased with temperature
increasing. At 180 C the maximum precipitation of arsenic and iron was 78% and
70%, respectively. This could be connected with the formation of ferric arsenate (III)
and copper (II). Such a formation in acid solutions is typical for high temperatures
[4, 5].
Copper was extracted up to 94% at recommended conditions (T ¼ 180 C,
[H2SO4]0 ¼ 64 g/dm3, Qa/Qs ¼ 1.35, Po2 ¼ 0.4 MPa and a duration of 240 h),
and arsenic iron and lead remained in the cake as well as gold (up to 99%) and silver
(93%). The cake has composition, %: 6.6 As, 39.2 Pb, 8.3 Fe, and 3.9 Cu. The
solution contains, g/dm3: 4.0 Fe, 1.0 As, and 73.0 Cu.
The concentration of iron in the solution is decreased at times due to hydrolysis
and decreasing concentration of the acid in the solution. Copper extraction was
94% after 240 min of leaching, when zinc was leached into solution up to 90–95%.
Sulfide sulfur begins to be rapidly oxidized to sulfate after 70 min of leaching, and
extraction of copper occurs due to the oxidation of this sulfur. The acid concentration
of 8.9 g/dm3 remains constant after 70 min of leaching until the end of experiment.
According to X-ray analysis, most of the lead is in the form of PbSO4,
PbFe2[AsO4]2(OH)2 was also found. Copper is in the form of arsenate,
Cu3(AsO4)2, CuSO4, and anhydrous CuSO4*0.67H2O. Iron is in the form of
FeOOH and Fe4O3[AsO4]2. Sulfides were not found in the precipitate of leaching
that confirms full decomposition of mattes.
It was proposed to send the cake to a lead plant. The cake was subjected to
sulfuric acid pressure leaching (T ¼ 180 C, [H2SO4]0 ¼ 22 g/dm3) in order to
enrich the cake with lead and remove the arsenic. However, even after 4 h of
leaching, arsenic extraction to solution was 28%. Copper and iron remained in the
cake completely. Total removal of arsenic in two stages of leaching was 44%. Cake
contained arsenic at 4.9%; this fact makes it difficult to arrange further cake
processing at lead plants.
Thus, oxidative sulfuric acid pressure leaching of matte shows the following
results:
• Maximum extraction of arsenic during oxidative pressure leaching was 14.7%.
• Extraction of copper was 94.2%.
• Final solution contains up to 4 g/dm3 of Fe and up to 1 g/dm3 of arsenic.
• Copper extraction is decreased from 94.2 to 55.8% with increasing iron content in
the matte from 7 to 23%, respectively.
7.3.2 Pressure Leaching with Preliminary Treatment

of Mattes with Copper Sulfate Followed by Oxidative
Leaching
The cake contains up to 7% of arsenic after leaching, and it became more difficult to
process it by traditional methods [6]; therefore pressure leaching with preliminary
treatment of mattes with copper sulfate was studied.
Pressure leaching with preliminary treatment of mattes with copper sulfate was
based on the exchange reaction mechanism (CuSO4 + MeS ¼ CuS + MeSO4, where
Me is Fe, Zn, and Pb), at temperatures above 150 C [7].
The experiments were carried out under the following conditions: pulp density L:
S ¼ 6:1; temperature of 140–180 C, sulfuric acid concentration of 5–30 g/dm3,
copper concentration of 10–130 g/dm3 (molar ratio of Cu/(Zn + Fe + As +
Pb) ¼ 0.5–1.1), and leaching time of 60–120 min.
The aim of the experiment was to extract iron, zinc, and arsenic and for lead and
copper to remain in the cake. The obtained results are shown in Table 7.3.
Treatment of mattes with copper sulfate at 180 C allows one to extract arsenic
to a solution for matte OSF up to 89% for SF up to 93%. At the same time, zinc and
Table 7.3 Results of treatment of mattes with copper sulfate

Extraction, %
Molar ratio of Copper
Materials Test Cu/(Zn + Fe + As+Pb) t, C Time, min As deposition Fe
OSF 1 1.09 180 60 89.9 68.1 91.8
SF 2 1.08 180 90 91.8 88.2 92.0
OSF 3 1.09 180 90 79.5 71.0 92.4
SF 4 1.08 180 90 93.5 76.9 91.9
OSF 5 0.76 180 60 76.1 92.5 86.0
OSF 6 0.47 180 60 42.7 99.7 79.0
OSF 7 0.76 160 60 42.3 47.4 83.5
OSF 8 0.76 140 60 33.5 25.1 78.1
iron were extracted to solution up to 90 and 92%, respectively. Lead remained

completely in the cake. The cake’s sulfur concentration was similar to that of the
original matte.
Acidity increasing had low influence on removing arsenic and other metals from
the mattes. The optimal copper concentration in the solution was 14 g/dm3
(Cu/(Zn + Fe + As + Pb) ¼ 0.76); herewith 76% of arsenic, 86% of iron, and 86%
of zinc were extracted to solution. The copper deposition was 92.5%. Final copper
concentration in the solution was 1.1 g/dm3. When the concentration of copper in the
initial solution was 9 g/dm3 (Cu/(Zn + Fe + As + Pb) ¼ 0.47), the copper deposition
increased to 99.7%, but the arsenic extraction decreased by half, and iron concen-
tration remained the same. Gold and silver remained in the cake at 99%.
Decrease of the temperature has negative effect on leaching. At 160 C arsenic
and zinc transition into the solution decreased to 42.3% and 51.4%, respectively.
The cake contained, %: 1 As, 0.6 Fe, 0.5 Zn, 48.5 Cu, and 23 Pb after treatment.
According to X-ray analysis, the lead is present in the cake as PbSO4 and PbS;
copper is present in the form of Cu2S and metal. Arsenic is present as Cu3(AsO4)2.
There were basic copper sulfates Cu3(SO4)2(OH)2.
Total extraction to solution at the treatment of the SF matte with copper sulfate in
two stages was, %: 98.2 As. 98.1 Fe, and 98% Zn. Cake contained, %: 0.1 As, 0.4
Fe, 0.1 Zn, 61 Cu, and 12 Pb.
Thus, treatment of mattes with copper sulfate allows the following:
• 92% of iron, 90% of arsenic, and 90% of zinc can be extracted into a solution at
180 C.
• Cakes after treatment contain 50–60% of copper and 23% of lead. Copper is
present in the form of Cu2S and metal, so that oxidative pressure leaching of cake
after treatment of mattes with copper sulfate is attractive for research.
• Acidity of the solution has practically no effect on the treatment of mattes with
copper sulfate and is not changed during the process.
• Treatment of mattes with copper sulfate allows one to process mattes with
different iron content.
Oxidative pressure leaching of the cake after treatment of mattes with copper
sulfate was carried out under the following conditions: pulp density L:S ¼ 6–24:1;
temperature of 160–180 C, oxygen pressure of 0.3 MPa, sulfuric acid concentration
of 21.3–127.33 g/dm3, and leaching time of 90–120 min.
Obtained results are shown in Table 7.4.
As the results show, the acidity has a strong effect on the leaching. The best
results on the copper extraction (98–99%) were achieved at a molar ratio of H2SO4/
Cu 1. Copper extraction decreased to 87% in experiments with a ratio of H2SO4/
Cu ¼ 0.69 that is probably due to deficiency of acid.
Extraction of copper from the cake after treatment of SF matte with copper sulfate
was 99% from the initial content of copper in matte, whereas oxidative pressure
leaching of SF matte without preliminary treatment with copper sulfate allowed one
to extract only 55.8% of copper.
Maximum extraction of 60% arsenic for cakes of OSF matte was achieved at a
molar ratio of H2SO4/Cu ¼ 1 and 160 C. In all other experiments, the arsenic was
Table 7.4 Results of the oxidative pressure leaching experiments for the cakes after treatment of
mattes with copper sulfate (copper extraction from the initial content of copper in mattes)
Copper
Copper content [H2SO4]0, Molar ratio extraction,
Mattes Tests in cake, % L:S g/dm3 of H2SO4/Cu t, C %
OSF 1 49.50 24.69 21.33 0.69 180 87.09
SF 2 60.90 30.00 30.00 0.96 180 99.00
OSF 3 48.50 30.00 26.67 1.07 160 97.50
OSF 4 46.20 12.00 63.67 1.07 160 98.10
OSF 5 47.00 6.00 127.33 1.05 160 98.20
OSF 6 56.30 6.67 115.00 0.88 160 98.60
Treatment of mattes
with copper sulphate
Solution (As,Fe)
Cake (Cu, Pb)
Deposition of
As-Fe cake Oxidative pressure leaching
of cake
Solution (As,Fe)
Regeneration
Lead cake Solution (Cu) (excess of
sulphate ion),
acid
Electrowinning neutralization
Lead production with lime
Cathode copper Electrolytic
solution
Fig. 7.1 Tentative flowchart to process mattes
extracted into solution to 50%. The results obtained differ from those obtained by
oxidative pressure leaching of SF matte without preliminary treatment with copper
sulfate, probably due to a deficiency of iron in the cake which forms a ferric arsenate
with arsenic.
Lead remained in the cake after leaching. The cake contains 48–55% of lead at
copper extraction of 98–99% and is suitable for lead plants. The concentration of
iron, zinc, and arsenic in the solution was less than 1 g/dm3, whereas copper
concentration (at L:S ¼ 6:1) amounted to 83–86 g/dm3.
The obtained results for two-stage pressure leaching including preliminary treat-
ment of mattes with copper sulfate followed by oxidative pressure leaching of cake
allow one to compose a tentative flowchart to process mattes, which is shown in
Fig. 7.1.
7.4 Conclusions
1. Oxidative pressure leaching of mattes without preliminary treatment with copper

sulfate allows one to extract 94.2% of copper, whereas arsenic, lead, and iron
remained in the cake.
2. Pressure leaching treatment of mattes with copper sulfate solution allows one to
extract up to 93% of arsenic and iron, wherein the cake contains up to 1% of
arsenic and 48% of copper. The obtained cake can be sent to oxidative pressure
leaching. This method allows one to process mattes with a high iron content
(23%).
3. A two-stage matte processing circuit is recommended for further investigation.
References
1. Makhov I. E., Mikhaylov S. V., & Shishkina L. D. et al. (1991). Povedenie myshyaka i surmy pri
pirometallurgicheskom proizvodstve medi (behavior of arsenic and antimony during the pyro-
metallurgical manufacturing of copper). Moscow: Central Scientific and Research Institute of
Economics and Information of Non-ferrous Metallurgy. Iss. 2. 56 p.
2. Skopov, G. V., & Matveev, A. V. (2011). Combined processing of polymetallic semifinished
products of metallurgical production. Metallurgist, 7–8, 596–600.
3. Neustroev, V. I., Karimov, K. A., & Naboychenko, S. S. (2013). Autoclave leaching of mattes
from smelting of intermediate metallurgical products. Tsvetnye Metally Nonferrous Metals, 8,
75–78.
4. Gomez, M. A., Becze, L., & Celikin, M. (2011). The effect of copper on the precipitation of
scorodite (FeAsO4*2H2O) under hydrothermal conditions: Evidence for a hydrated copper
containing ferric arsenate sulfate–short lived intermediate. Journal of Colloid and Interface
Science, 360, 508–518.
5. Monhemius, A. J., & Swash, P. M. (1999). Removal and stabilizing as from copper refining
circuits by hydrothermal processing. JOM, 51, 30–33.
6. Pozdnyakov, V. Y. A., & Chetvertkov, M. S. (1975). Povedenie mishyaka pri proizvodstve
cvetnih metallov. Tsvetnye Metally Nonferrous Metals, 11, 17–19.
7. Semenov, M. Y. U., Sirkis, A. L., & Khudyakov, I. F. (1984). Study of the hydrothermal reaction
of copper, nickel and iron sulfides with a copper sulfate solution. Tsvetnye Metally Nonferrous
Metals, 6, 15–18.
Chapter 8
Investigation of TSL Furnace
Hydrodynamics Using Cold Modeling
Method
B. V. Kolmachikhin, V. A. Menshchikov, V. P. Zhukov, and N. G. Ageev
8.1 Introduction
A lot of attention is being paid nowadays to metallurgical processes optimization in

terms of energy and fuel consumption. One of the most efficient pyrometallurgical
processes is top submerged lance (TSL) smelting, known for high oxygen utilization
efficiency and easy maintenance. The first metallurgical plant to use this process in
Russia was Karabashmed, combining it with rotary settling furnace with heating
burner. Our goal was to get a better understanding of process hydrodynamics and
create a basis for further investigation aiming to make recommendations for
Karabashmed on how to improve their operation parameters.
The Tongling Jinchang smelter experience described by Matusewicz et al. [1]
showed that a plant with a single TSL furnace can produce up to 200,000 tons of
blister copper per year (up from an initial 70,000 tpy) without significant flow sheet
changes. They achieved such a result using a high level of oxygen blowing enrich-
ment – up to 90%. Studies of Floyd [2, 3] showed that lance geometry also has a
significant effect on process efficiency.
8.2 Physical Experiments
Cold modeling allows one to observe flows in media and determine the main
dynamic zones in a vessel avoiding problems related to high temperatures and
hard access to sealed internal space of a real metallurgical vessel. Our main goal
here was to observe the torch formation zone at the lance tip and measure various
parameters depending on blowing intensity and lance geometry.
B. V. Kolmachikhin (*) · V. A. Menshchikov · V. P. Zhukov · N. G. Ageev


https://doi.org/10.1007/978-3-319-75340-9_8
60 B. V. Kolmachikhin et al.
8.2.1 Modeling Setup
A cold model was made using Plexiglas at a scale of 1:12 to real vessel. Compressed
air was used for blowing (up to 300 l/min). The lance was made using plastic tubes of
various diameters (most experiments were made with a 5 mm lance). The model was
mounted on a wooden stand to minimize vibrations. The stand was equipped with
LED lights to ensure caption quality.
The lance of a real furnace has an inner swirl to make possible tangential blowing
input, so the model got a steel swirl glued into the lance tube too.
Pressure at the lance tip was measured via manometer attached to the lance. Two
rotameters were used to measure the amount of air blown with four vents for blowing
intensity regulation.
Images were captured using two 100 fps cameras with a resolution of
1920 1080 mounted at a fixed distance from the model. Video capture was used
along with a photo series to ensure maximum quality of images received.
Figure 8.1 shows the scheme of cold model setup main elements.
8.2.2 Modeling Conditions and Results Obtained
The modeling liquid used was water and water-glycerol emulsion. The physical
properties of gas phase were not so important in the approach chosen according to
[4]. The main factors in terms of blowing were volume and velocity. Taking this into
consideration, the criteria of modeling liquid selection come to
ηl 4 ∙ g
M¼ ð8:1Þ
σ 3 ∙ ρl
where g is standard acceleration of free fall, m/s2; ηl is the dynamic viscosity, Pa•s; σ
is surface tension, N/m; and ρl is liquid density, kg/m3.
According to [5, 6], real slag has the following properties at 1300 C: ηl ¼ 0.15 Pa•s,
σ ¼ 0.4 N/m, and ρl ¼ 3700 kg/m3. Entering this data into Eq. (8.1), we obtain
M ¼ 2.1105 which corresponds to water-glycerol emulsion. Using water as the
modeling liquid corresponds to slag systems with lower viscosity and density.
The amount of air blown varied from 0.001 to 0.005 m3/s. For each value, four
test runs were made to ensure minimal error in results received. Some experiments
included usage of an organic indicator to determine the solid particles flow trajec-
tories and get a more consistent image of bath dynamics.
To make sure that optical distraction of media and/or vessel walls is taken into
account properly, a number of scale marks were placed on the lance tip and on the metal
plate that was submerged into liquid along with the lance in one run of each series.
8 Investigation of TSL Furnace Hydrodynamics Using Cold Modeling Method 61
Fig. 8.1 Scheme of modeling setup. 1 – Vessel, 2 – mounting points, 3 – movable plate, 4 – lance,
5 – rotary elements, 6 – liquid level in vessel, 7 – redactor, 8 – vents, 9 – manometer, 10 – safety
pressure vent, 11 – rotameter
At each blowing intensity and each geometrical parameters set (lance diameter,
lance submergence, number of lance tubes, swirl form), four series each consisting
of ten photos were taken.
Figure 8.2 shows an example of the image series taken during one of the test runs.
It should be mentioned that blowing intensity of 0.002–0.0025 m3/s is the closest
experimental condition to real operation modes of the TSL furnace in Karabash.
Blowing modes of higher intensity shall be considered as extreme and are not
suitable to a real process because of lining wear increase and lance lifetime decrease
in such modes.
Figure 8.3 shows the profile of the torch obtained at 0.002 m3/s blowing. It will
serve as initial data to verify results of CFD modeling which is still in an early stage
of development.
Fig. 8.2 Images taken during a test run at 0.002 m3/s blowing intensity
Fig. 8.3 Torch opening

profile
8.3 Data Analysis
Each image was processed using photo editing software to increase quality and to
add the coordinate grid on it. Figure 8.4 shows an example of the image after this
stage’s processing.
The real size of each grid segment was calculated for each series individually
according to the mentioned physical marks on the lance and on the submerged steel
plate. To make possible quantity comparison between series, calculations of blowing
torch volume were simplified to those of a flattened cone.
Figure 8.5 shows the dependency of blowing torch volume on the amount of
blowing with 5 mm lance submergence and 5 mm lance diameter in single-phase
(water) media.
8 Investigation of TSL Furnace Hydrodynamics Using Cold Modeling Method 63
Fig. 8.4 Image with

coordinate grid on
700
600
Torch volume, sm3
500
400
300
200
100
0
0.001 0.0015 0.002 0.0025 0.003
Blowing intensity, m3/s
Fig. 8.5 Torch volume dependence on blowing intensity
A plateau in Fig. 8.5 ranging from 0.0022 to 0.0028 m3/s blowing intensity was
repeatedly appearing both in water and water-glycerol media tests. It shows that for a
further increase of torch penetration, a depth excess of air blowing is required.
Also we measured pressure at the lance tip under different conditions, but no
significant change was observed: pressure raised along with blowing intensity with
no difference of increase curve for submergence level or media density.
The Reynolds criterion was calculated for different blown air velocities using
Eq. (8.2):
υ∙D∙ρ
Re ¼ ð8:2Þ
η
where υ is blown air velocity, m/s; D is lance diameter, mm; ρ is air density, kg/m3;
and η is media dynamic viscosity, Pa•s.
The lance diameter was 0.005 m; media density was 1.84•105 Pa•s.
Calculation results are presented in Table 8.1.
Table 8.1 Reynolds criterion for different blown air velocities

Blowing intensity, m3/s Blown air velocity, m/s Air density, kg/m3 Re
0.0010 52.9 1.22 17605.11
0.0014 73.9 1.24 24684.49
0.0018 94.2 1.26 32372.03
0.0023 115.2 1.29 40508.78
0.0027 135.5 1.34 49343.07
0.0031 155.7 1.39 59085.66
0.0034 174.1 1.48 70042.8
0.0038 192.5 1.57 82328.28
0.0042 211.6 1.68 96874.19
0.0045 230.7 1.85 116228.6
The results obtained allowed us to compare data with real process conditions and
determine if chosen blowing intensities were correct. A comparison showed that
blowing intensity of 0.002–0.0025 m3/s corresponds to real operation modes.
8.4 Conclusion
The data obtained allowed us to determine the basic dynamic characteristics of TSL
furnace liquid bath: torch penetration depth and size increase with blowing intensity,
blowing conditions, and main flows in reaction zone. It is shown that to increase
torch penetration depth from real operation mode excessive blowing is required,
which is not an option for real furnace because of lining damage and lance lifetime
decrease.
Future work will include CFD modeling based on this data and further hydrody-
namic research including colored indicators used and detailed comparison of differ-
ent swirl modes to find optimal lance geometry parameters.
References
1. Matusewicz, R. W., & Lin S. L. (2010). Large scale copper smelting using Ausmelt TSL
technology at the Tongling Jinchang Smelter, Proc. “Copper 2010”: Vol. 3. Hamburg, June
6–10, 2010 (pp. 961–970).
2. Floyd, J. M. (2004). Converting an idea into a worldwide business commercializing smelting
technology. Metallurgical and Material Transactions B, 36(B), 557–575.
3. Floyd, J. M. (1992). The emerging role of New Bath Smelting, Mervyn Willis Symp. and
Smelting and Refining Course. Melbourne: University of Melbourne (pp. 13:1–13:51).
4. Markov, B. L. (1975). Methody produvki martenovskoy vanni (p. 279). Moscow: Metallurgia.
5. Rossinsky, E. E. (1974). Metallurgicheskie shlaki (p. 156). Moscow: Metallurgia.
6. Shmonin, U. B. (1981). Pyrometallurgicheskoe obednenie shlakov tsvetnoy metallurgii (p. 131).
Moscow: Metallurgia.
Chapter 9
Physical Simulation of Melt Lancing
in a TROF Converter
V. A. Menshchikov, B. V. Kolmachikhin, and N. G. Ageev
9.1 Introduction
The tilting rotating oxy-fuel (TROF) converter is a rotary bevel drum-type furnace.
Furnaces of this type are becoming more and more popular. These furnaces have a
number of advantages:
• They are suitable for a wide range of tasks.
• They may process both molten and solid materials.
• The furnaces are compact and do not require a lot of space.
• They are widely automated.
• The gas removal system prevents the release of gases in a working area.
The most important advantage of these furnaces is the ability of a smelting
chamber to rotate during smelting.
While recycling copper-containing materials, slags with high viscosity might be
obtained, which entails high copper losses with slag. Most of all, because of high
slag viscosity, they are very difficult to process, for example, in a refractory furnace.
The composition of copper-containing materials for recycling is unstable. Especially
the content of zinc and tin has the greatest impact on slag viscosity. In the work of
Naboychenko [1], a ratio of tin content in the slag to its viscosity is given. The TROF
converter is perfect for processing such slags and materials. The ability to mix the
produced slag allows one to receive waste slag with low copper containment. The
construction of the TROF converter allows the application of unsubmerged blowing.
In this case, the furnace might be used as a converter unit. For this purpose, the steel
lance embeds through converters nose.
V. A. Menshchikov (*) · B. V. Kolmachikhin · N. G. Ageev

The Ural Federal University, Yekaterinburg, Russia

https://doi.org/10.1007/978-3-319-75340-9_9
66 V. A. Menshchikov et al.
Due to the unsubmerged blowing and the rotating smelting chamber, the material
flow trajectory is very difficult to predict. The better understanding of TROF
converter hydrodynamics is necessary for:
• More efficient use of blowing air
• Lining lifetime increase
• Achievement of best conditions for copper recovery from slag
9.2 Cold Modeling
Cold simulation has been carried out for a better understanding of the TROF
converter operation and to find possible ways for hydrodynamic improvement. For
this purpose, a model of the TROF converter smelting chamber was made of
plexiglass in scale 1:10 to a real unit. As with a real furnace, the model has the
ability to rotate about the longitudinal axis to simulate rotation of smelting chamber
and about the transverse axis to change the model angle and tape of the liquid.
Special frame and bearing allowed the observation of the movement of liquid in any
part of the model. The scheme of the experimental setup is shown in Fig. 9.1.
Fig. 9.1 The scheme of the experimental setup. 1 – The smelting chamber (the model’s body), 2 –
bearing support, 3 – guide rail for the lance, 4 – lance, 5 – driving actuator, 6 – level of liquid in the
smelting chamber; 7 – compressed air inlet and pressure regulator, 8 – valves, 9 – manometer, 10 –
safety valve
9 Physical Simulation of Melt Lancing in a TROF Converter 67
The model is equipped with a steel lance with an external diameter of 10 mm and
internal of 5 mm. In order to minimize the hydraulic resistance of the lance, its
channel was polished. Blowing was performed by compressed air at a temperature of
20 C. A special tank was used to maintain air temperature. The airflow rate was
measured with rate-of-flow meter PM-16 with a working range up to 16 m3/h.
According to airflow rate used in real furnace, it was calculated that the airflow
rate for modeling ought to be about 8.4 m3/h.
During modeling, the following parameters were varied:
• The airflow rate
• The model’s body angle
• Smelting chamber rotational speed
• The position of lance and its angle
In order to determine the speed and trajectory of liquid movement, a dispersed
organic indicator was used. The indicator consisted of a great number of particles
with different sizes (from 1 mm to 8 mm) and different flotation abilities. It allowed
the observation of the trajectory and speed of liquid flows in the bulk of
model’s bath.
In the capacity of liquid, water and mixes of water with glycerin and different oils
were used. The best results were achieved in experiments with pure water.
In order to achieve conditions of similarity, the Reynolds number was calculated.
The physical properties of the gas phase were not so important in the approach
chosen according to Yavoisky et al. [2]. The main factors are the blowing volume
and its velocity. Taking this into consideration, the criterion of modeling a liquid
selection come to
ηl 4 ∙ g
М¼ : ð9:1Þ
σ 3 ρl
where g is standard acceleration of free fall, m/s2; ηl is dynamic viscosity, Pa•s; σ is

surface tension, N/m; and ρl is liquid density, kg/m3.
According to Morsi et al. [3], real slag has the following properties at 1300 C:
ηl ¼ 0.15 Pa•s, σ ¼ 0.4 N/m, and ρl ¼ 3700 kg/m3. Putting this data into Eq. (9.1),
we obtain M ¼ 2.1105 which corresponds to water-glycerol emulsion. Using water
as the modeling liquid corresponds to slag systems with lower viscosity and density.
For data recording, two 100 ps. photo cameras were used. The use of two cameras
was necessary because of the difficult shape of the smelting chamber and the need to
observe the blowing torch in two dimensions. Both cameras were synchronized in
order to get a one-stage full picture of liquid movement.
After getting data, the images were processed, and the coordinate scale was
added. The scale was determined in terms of the lance tip size. An example of the
image is given in Fig. 9.2.
According to coordinate scale, the size of blowing torch was determined. There
were separately determined axial and cross airflow penetration depths. By means of
these measurements, the volume of displaced liquid was calculated.
Fig. 9.2 An example of an

image with coordinate scale
Fig. 9.3 The liquid flow trajectory in the smelting chamber
9.3.1 Analysis of Flow Trajectory
Analysis of all obtained data allowed us to reveal the next picture of flows inside the
smelting chamber. They are presented in Fig. 9.3.
All flows arise under the impact of blowing torch, and their form, trajectory, and
speed depend much on the blowing airflow rate. It was revealed that the rotation of
the smelting chamber does not affect much the bath hydrodynamics if solid materials
are not used.
As can be seen from Fig. 9.3, when the airflow rate is 8.0 m3/h., four main flows
form. Flows numbered 1 and 2 spread closer to the liquid surface and move in the
direction of a spherical bottom. There they change direction and move backward
along the chamber’s body to the zone before the cavern.
The third flow unlike the first one develops below the liquid level. It moves along
the side of the chamber and rises in front of the cavern, but it does not crop out.
The flow numbered 4 is also initiated by blowing torch, but it moves down along
the spherical bottom and moves there along the lower element of a cylinder toward
the zone before the cavern. There it divides into two flows, one of them continues its
movement and imparts the material which is far away from the blowing torch, and
the other one moves up to the cavern. In a place where three flows divide into two,
the dead zone appears.
As already mentioned, the airflow rate greatly influences the flow’s trajectory. At
the flow rate of about 8.4 m3/h directions of same flows change; thus a third flow
joins with the second and forms one, which goes alongside elements of the cylinder.
According to the results of video filming, the average speed of liquid flows was 101
m/s. Taking into consideration the higher viscosity of real slags, it may match the
speed of real melt flow in the TROF converter by about 0.01–0.05 m/s.
9.3.2 Analysis of Cavern
One of the main parameters measured during experiments was the size of the
blowing torch (cavern); in order to determine it, the axial and cross airflow penetra-
tion depths were measured. Results are presented in Fig. 9.4.
By means of these measurements, the volume of displaced liquid was calculated.
The volumes of displaced liquid depending on airflow rate are provided in Fig. 9.5.
For different flow rate speeds, the values Re were estimated using Eq. (9.2).
Results are presented in Table 9.1.
Re ¼ υDρ=μ, ð9:2Þ
where υ is flow rate speed, m/c; D is nozzle diameter, m; ρ is air density, kg/m3; and
η is dynamic viscosity, Pa•c
The nozzle diameter was 0.005 m; the dynamic viscosity was 1.84105 Pa•c.
20
18
Penetration depths, d/L
16
14
12
10
8
6
axial
4
2 cross
0
50 70 90 110 130 150 170 190
Air flow rate, dm3/min
Fig. 9.4 The relationship of blowing torch penetration to airflow rate

300
The volumes of displaced liquid

250
200
cm3 150
100
50
Volume of liquid
0
50 100 150 200
Air flow rate dm3 /min
Fig. 9.5 The relationship between the volume of displaced liquid and airflow rate
Table 9.1 The values of Re Volume flow Airflow Air pressure

for different flow rate speeds rate m3/h rate m/c kg/m3 Re
3.74 52.94 1.22 17605.29
5.17 73.18 1.24 24684.99
6.66 94.20 1.26 32373.10
8.14 115.23 1.29 40510.74
9.57 135.47 1.34 49346.60
11.00 155.71 1.40 59091.41
12.30 174.11 1.48 70052.06
13.60 192.51 1.57 82342.01
14.95 211.62 1.68 96893.84
16.30 230.73 1.85 116257.64
9.3.3 Energy Balance
For every airflow rate, the kinetic energy Ek and potential energy Ep were calcu-
lated. According to the volume of displaced liquid, the energy required for its lift
(El) was estimated. Thereby only one percent of introduced energy is consumed for
lifting and splashing of melt. The results are presented in Table 9.2.
It means that practically all energy of blowing air passes to the liquid.
9.4 Conclusions
Cold simulation was carried out with an airflow speed from 52 to 230 m/s. That
matches the levels of kinetic energy from 1.8 to 223 W/s. Cold modeling permitted
the estimation of speed of liquid flows. It was about 101 m/s. Taking into consid-
eration the higher viscosity of real slags, it may match the speed of real melt in a
Table 9.2 Values of Ek, Ep, Airflow rate Ep Ek Е El

and total energy E of airflow
m3/h H H Н H
3.7 0.002 1.78 1.78 0.006
5.2 0.004 4.77 4.78 0.013
6.7 0.009 10.37 10.38 0.029
8.1 0.017 19.42 19.44 0.063
9.6 0.030 32.70 32.73 0.106
11.0 0.049 51.73 51.78 0.171
12.3 0.079 76.68 76.76
13.6 0.117 110.20 110.31
15.0 0.167 156.69 156.86
16.3 0.246 223.50 223.74
TROF converter by about 0.01–0.05 m/s, and locally the flow speed may exceed the
average flow speed by 5–10 times. The obtained results might be used to improve the
operation of the TROF converter unit.
References
1. Naboychenko C. C. (2005). Processy I apparaty cvetnoy metallurgii – Ekaterinburg: GOU VPO

UGTU-UPI, p. 700.
2. Yavoisky V. I., Dorofeev G. A., & Povh I. L. (1974). Teoriy produvky stalepavil’noy vanni. –
Moscow, Metallurgia, p. 496.
3. Morsi, Y. S., Atapattu, D. D., Yang, W., & Gray, N. B. (1997). Characterization of gas injection
into liquid baths, American Society of Mechanical Engineers (p. 51). Fluids Engineering
Division (Publication) FED, New York.
Chapter 10
Thermodynamic Features Research
of Polymetallic Sulfide Raw Material
Leaching
D. Rogozhnikov, S. Mamyachenkov, and O. Anisimova
10.1 Introduction
Processing of the low-grade sulfide raw materials unshared by traditional breeding

methods leads to problems at the stages of beneficiation and metallurgical
processing. This leads to increased circuit complexity extraction of nonferrous
metals and loss of the valuable components [1].
At the polymetallic sulfide raw materials flotation, there are small amounts of
refractory collective industrial product output in certain nodes of the circuit. The
products have complex non-shared connections. An operation was carried out to
improve the quality of the monometallic concentrates [2, 3].
The introduction of new hydrometallurgical technologies which are more prom-
ising from an environmental and economic point of view compared to conventional
processes is a promising method to solve the identified problem [4].
Nitric acid was used as a reagent for sulfide multicomponent middlings leaching.
This acid has a high chemical reaction heat and allows recycling of the exhaust gases
with nitrous regeneration of nitric acid and high-speed metal sulfide oxidation [5–7].
The aim of this work was to study thermodynamic features of sulfide middlings
nitric acid leaching reactions, to perform calculations of the Gibbs energy change for
the likely reactions of sulfide minerals with nitric acid, and to determine the most
favorable conditions for the leaching process using the Pourbaix diagram.
D. Rogozhnikov (*) · S. Mamyachenkov · O. Anisimova


https://doi.org/10.1007/978-3-319-75340-9_10
74 D. Rogozhnikov et al.
10.2 Experimental
The investigated raw material was an intractable division of the selective flotation
multicomponent sulfurous materials of “Maykain B” deposit, Kazakhstan. The
chemical composition of middling is presented in Table 10.1.
Figure 10.1 shows the phase composition of the investigated raw material
obtained via X-ray diffraction analysis.
The X-ray diffraction analysis showed that sphalerite, pyrite, chalcopyrite, and
galena are the most common minerals represented in the raw material.
Electron microscopic studies were performed to determine the fine structure of
the material, phase composition, chemical composition of the individual phases, and
their crystallographic orientation of raw materials using a transmission electron
microscope JEM 2100 prefix for microanalysis Oxford Inca.
Figures 10.2 and 10.3 show the results of the solid sulfide grains middlings
composition study.
Table 10.1 The chemical composition of raw material “Maykain B,” % mass
Cu Zn Fe S Pb Ca Na Mg As Al
6.37 9.21 33.57 46.3 1.18 1.72 1.66 0.24 0.21 0.1
Au, g/t Ag, g/t Sn Ni P Cd Mn Sb Si Ba
11.5 81.3 0.005 0.009 0.005 0.03 0.01 0.0063 <0.05 0.06
Sr Se Te Ti V Cr K Co Tl
0.013 0.005 <0.005 0.001 <0.001 0.006 0.09 0.016 <0.001
30000
Intensity, pulse/min
1
1
2
2
25000
1 1
20000 2 2
3
15000
2 2
10000 3 2
4 3
3 2 4 1 1
4
5000
0
20 30 40 50 60 70 80 90 100
2 teta, degree
Fig. 10.1 X-ray phase composition of the investigated raw material “Maykain B” : 1 – ZnS;
2 – FeS2; 3 – CuFeS2; and 4 – PbS
10 Thermodynamic Features Research of Polymetallic Sulfide Raw Material Leaching 75
Fig. 10.2 The results of the solid sulfide grains middlings composition study
Fig. 10.3 The results of the study of the solid sulfide grains middlings composition
The results of individual microparticles composition study show the following

composition: 34.63% S, 2.56% Fe, and 62.81% Zn (Fig. 10.2). It can be concluded
that the studied feed contains pyrite and sphalerite.
The presence of 28.01% S, 12.48% Fe, and 56.31% Cu indicates that there is a
chalcopyrite present at a given point (Fig. 10.3).
Comparison of data with the results of X-ray analysis confirmed the presence of
ZnS, CuFeS2, and FeS2.
Interaction of ZnS, CuFeS2, FeS2, and PbS with nitric acid can be represented by
the following reactions [8]:
6CuFeS2 þ 22HNO3 ¼ 6CuðNO3 Þ2 þ 3Fe2 O3 þ 12S0 þ 10NO þ 11H2 O ð10:1Þ
6CuFeS2 þ 22HNO3 ¼ 6CuSO4 þ 3Fe2 O3 þ 6S0 þ 22NO þ 11H2 O ð10:2Þ
CuFeS2 þ 10HNO3 ¼ CuðNO3 Þ2 þ FeSO4 þ S0 þ NO þ 7NO2 þ 5H2 O ð10:3Þ

2CuFeS2 þ 20HNO3 ¼ 2CuðNO3 Þ2 þ Fe2 ðSO4 Þ3 þ S0 þ 6NO þ 10NO2 þ 10H2 O

ð10:4Þ
2CuFeS2 þ 8HNO3 ¼ 2CuHSO4 þ Fe2 O3 þ 2S0 þ 6NO þ 2NO2 þ 3H2 O
ð10:5Þ
CuFeS2 þ 8HNO3 ¼ CuSO4 þ FeSO4 þ 4NO þ 4NO2 þ 4H2 O ð10:6Þ
2FeS2 þ 8HNO3 ¼ Fe2 ðSO4 Þ3 þ S0 þ 8NO þ 4H2 O ð10:7Þ
4FeS2 þ 4HNO3 ¼ 2Fe2 O3 þ 8S0 þ 4NO þ 2H2 O ð10:8Þ

2FeS2 þ 8HNO3 ¼ 2FeðNO3 Þ3 þ 4S0 þ 2NO þ 4H2 O ð10:9Þ
ZnS þ 8HNO3 ¼ ZnSO4 þ 8NO2 þ 4H2 O ð10:10Þ
3PbS þ 8HNO3 ¼ 3PbSO4 þ 8NO þ 4H2 O: ð10:11Þ
In the reactions above it is conventionally accepted that as a result of sulfide

interaction with HNO3, only NO is formed. However, apart from the nitrogen oxide
(II), a variety of compounds can be formed: N2O4, N2O3, N2O, N2, and NH3.
Nitrogen may have to change its oxidation state throughout the possible range,
and the degree of nitric acid reduction depends on its concentration and the activity
of the reducing agent [9].
Gibbs energy change (ΔG, kJ) and the value of the equilibrium constant
(Kd) were used to determine the direction of reactions (10.1)–(10.11) and to study
the interaction of sulfide raw material with nitric acid and reaction completeness.
The value of Gibbs energy change was used to judge the feasibility of the process.
Table 10.2 shows the results of the Gibbs energy change (ΔG, kJ) calculations for
reactions (10.1)–(10.11) for 373 K and 353 K temperatures. The temperature range
was determined by technological considerations.
Table 10.2 The results of the Gibbs energy change calculation

Temperature, K Reaction number, ΔG, kJ
1 2 3 4 5
373 1717.37 4139.89 738.77 1942.85 2886.42
353 1712.37 4076.61 716.77 1898.84 2625.61
6 7 8 9 10 11
1116.75 1624.31 695.74 1292.13 636.699 1829.38
1071.04 1598.14 679.49 1013.24 587.827 1805.36
Table 10.3 Calculated values of the equilibrium constants

Temperature, K Reaction number, Lg Kр
1 2 3 4 5
373 235.66 308 101.27 266.28 211.34
353 235.66 308 105.88 280.88 217.62
6 7 8 9 10 11
152.11 222.21 95.35 113.74 87.99 260.72
161.57 236.54 101.31 119.63 90.27 867.05
Fig. 10.4 Existence diagrams of copper (a) and zinc (b) compounds
Calculated values of the equilibrium constants (Kd) for reactions (10.1)–(10.11)

are presented in Table 10.3.
The calculations of the Gibbs energy change and equilibrium constants of
possible reactions between nitric acid and metal sulfides show that there is large
enough thermodynamic probability of their occurrence with the formation of ele-
mental sulfur, water-soluble compounds of copper, zinc, and iron, and oxides of
nitrogen.
However, in practice it is necessary to determine the conditions of an equilibrium
existence for these compounds with complete suppression of unwanted side
reactions.
The thermodynamic behavior of the multicomponent sulfide raw materials in a
nitric medium was studied in order to determine the most probable conditions of the
desired product formation during sulfide raw materials leaching in nitric acid, as well
as the mutual influence of the produced pulp components on the process perfor-
mance. A computer program “HSC Chemistry 6” was used for modeling Purbe E-pH
diagrams presented in Figs. 10.4 and 10.5.
Analysis of the diagram (Fig. 10.4a) showed that at the negative potential of the
system, the formation of gaseous NH3 and H2S occurs. Along with increase in
system acidity, formation of secondary copper sulfides CuS and Cu2S to
E ¼ 0.5 V begins. Sulfur is oxidized to sulfate form, and copper goes into cationic
form (Cu (II)). The formation of CuSO4 is accompanied by release of NO (g). When
the potential is more than 1.2 V, the formation of Cu(NO3)2 occurs.
Fig. 10.5 Existence diagrams of iron compounds (a) and joint diagram of copper, zinc, and iron in
the nitric medium (b)
The diagram of Fig. 10.4b shows that in the cathodic potential range, formation of
gaseous NH3 and H2S is possible. Sphalerite begins to decompose with the forma-
tion of Zn2+ and S0 at E >0.3 and pH 1.5. With further increase in the acidity,
formation of sulfate ions is observed. This may be accompanied by release of NO
(g). At E >1.2 V, the formation of Zn(NO3)2 is occurred.
Figure 10.5a shows the existence diagrams of iron in nitric medium. Dissolution
of iron raw material components may lead to slower opening speed of minerals
containing copper and zinc. This is due to the fact that films (oxides of iron,
elemental sulfur, etc.) are formed on the surface of the mineral zinc and copper,
preventing oxidation of the middlings components.
At sufficiently low oxidation potential values (up to 0.45 V), in the whole range,
the formation of S0 and Fe2O3 occurs.
To convert iron in the trivalent form, a high potential value of E >1.1 V should
be used.
The joint diagram of copper, zinc, and iron existence during the nitric acid
oxidation of sulfides (Fig. 10.5b) allows prediction of the behavior of all the studied
complex polymetallic middlings main components and also allows one to choose
modes of the sulfide oxidation process with the aim to maximize the transfer of
components from raw materials in a convenient form for further processing.
Diagram analysis showed that the full transfer of sulfide copper-zinc components
of raw materials to the sulfate form required initial high oxidation potentials of
E >0.9 V. It is important that the copper and zinc are completely converted into
cationic form.
The interaction of metal sulfides with nitric acid leads to its degradation and the
formation of nitrous gases. The resulting nitrogen oxides are oxidized to higher
oxides in the absorption column to form a mixture of nitric and nitrous acids. The
resulting mixture was used in the next leaching stages [10].
10.4 Conclusions
1. The results of X-ray and electron microscopic studies of multicomponent sulfide

raw materials phase and mineralogical composition show that the major minerals
in middlings are sphalerite, pyrite, chalcopyrite, and galena.
2. The calculations of the Gibbs energy change and equilibrium constants of
possible reactions between nitric acid and metal sulfides display large enough
thermodynamic probability of their occurrence with the formation of elemental
sulfur, water-soluble compounds of copper, zinc, and iron, and oxides of
nitrogen.
3. Thermodynamic features analysis carried out with the Pourbaix diagrams showed
that the maximum transfer of sulfide middlings components to sulfate form
required initial high oxidation potentials of E >0.9 V. Copper and zinc completely
pass in cationic form; the metal sulfide reactions with nitric acid leads to its
disintegration and the formation of nitrous gases.
References
1. Kozyrev, V. (1991). Some trends in the development of raw material base of ferrous metallurgy
capitalist and developing countries. Tsvetnye Metally, 12, 16–19.
2. Bolatbayev, K. (2001). State, problems and reserves enrichment technology polymetallic raw
materials. Industry of Kazakhstan, 10, 91–93.
3. Bolatbayev, K. N. (2002). Complex use of mineral resources – State, reserves, priorities (p. 33).
Almaty: KazGos INTI.
4. Rogozhnikov, D., Karelov, S., Mamyachenkov, S., & Anisimova, O. (2013). Technology for
the hydrometallurgical processing of a complex multicomponent sulfide-based raw material.
Metallurgist, 57(3–4), 247–250.
5. Rogozhnikov, D., Mamyachenkov, S., Karelov, S., & Anisimova, O. (2013). Nitric acid
leaching of polymetallic middlings of concentration. Russian Journal of Non-Ferrous Metals,
54(6), 440–442.
6. Semun, N., Mamyachenkov, S., & Rogozhnikov, D. (2013). Combined processing of Erdenet
ore-dressing plant pyrite concentrates. Metallurgist, 57(1–2), 77–79.
7. Rogozhnikov, D., Mamyachenkov, S., & Anisimova, O. (2015). Kinetics of nitric acid leaching
of multicomponent sulfide middlings products. Russian Journal of Non-Ferrous Metals, 8,
26–29.
8. Bogacheva, L. M., & Ismatov, K. R. (1989). Hydrometallurgical processing of copper-
containing materials. Tashkent: Publications.
9. Sokolenko, L. M. (2009). Collection and recycling of nitrous gases. Cherkassy: Publications.
10. Locman A. A., Karavaev M. M., & Ivanov Y. A. (1999). A method of nitric acid producing, Pat.
RF № 2127224.
Chapter 11
Investigation of Lignosulfonate Adsorption
on Zinc Materials in Acidic Media
E. Kolmachikhina and S. Naboychenko
11.1 Introduction
The development of pressure leaching processes allowed one to implement

processing technology for sphalerite concentrate to increase the level of ecological
safety and effectiveness at Canadian, German, and Kazakhstan plants. Surfactants
served to improve this technology. Surfactants prevent mineral wetting by molten
elemental sulfur. Quebracho extract, oil, ortophenylene diamine, and lignin deriva-
tives were the most effective among investigated reagents. Lignosulfonates (Ls) are
by-products of sulfite pulp cooking. They are used extensively at pressure leaching
due to their availability, nontoxicity, and low cost. It is common knowledge that Ls
surface activity is defined by amphiphilic construction of the Ls molecules, which
consist of hydrophobic skeleton and hydrophilic ionogenic functional groups [1, 2].
However, at the pressure leaching of the sphalerite concentrates, a high dosage of
lignosulfonates (14–15 kg/t instead 4 kg/t) leads to problems at stages of solution
purification from Cu, Ni, Co, and Cl and at zinc electrolysis [3]. The problems
mentioned are that at the cementation purification stage, zinc dust consumption is
increased twofold, and at zinc electrolysis, current efficiency is reduced by up to
65–70%.
The result analysis of lignosulfonate application at the nickel-pyrrhotine concen-
trate leaching [4] identified that the reagent dosage had a great influence on nickel
extraction and sulfur-sulfide pellet yield. Low lignosulfonate dosage leads to sulfur-
sulfide pellet formation and leaching slowdown. High lignosulfonate dosage results
in particle overgrinding (10 μm). Flotation of such particles is impossible without
the use of additional reagents.
E. Kolmachikhina (*) · S. Naboychenko

e-mail: e.b.khazieva@urfu.ru

https://doi.org/10.1007/978-3-319-75340-9_11
82 E. Kolmachikhina and S. Naboychenko
A number of investigations proved the possibility of lignosulfonate adsorption on

mineral and sulfur surfaces [4–7]. It is shown in Ref. [4] that reagent activity
increases along with its adsorption capability increase on particles. Zinc extraction
and conversion degree from S2 to S0 grow up linearly with lignosulfonate concen-
tration increase. These parameters do not change after reaching Ls concentration of
0.10–0.25 g/l.
Thus, the degree of adsorption is a determinative parameter of surfactant effec-
tiveness at sulfide concentrate leaching. However, previous investigations of the
lignosulfonate adsorption on mineral surface did not take into account the influence
of solution acidity and temperature. The complexity of adsorptive processes and
insufficient knowledge of interfacial phenomena make understanding of the ligno-
sulfonate adsorption mechanism on zinc concentrate surface in acidic solutions at
elevated temperatures difficult. Also, it leads to difficulties in leaching operation
control.
11.2 Materials and Methods
11.2.1 Materials
Zinc concentrate was obtained from Chelyabinsk zinc plant and Uchalinsky mining
and processing complex. The concentrate composition is shown in Table 11.1.
Natural sphalerite was provided by Berezovsky deposit. The specific area was
determined by means of the Kozeny-Carman method. Specific areas of sphalerite
concentrate and natural sphalerite were 0.031 and 0.030 m2/g, respectively.
Studied sodium lignosulfonates (Solikamsky, Kamsky) were preliminary ana-
lyzed by means of FTIR (Fourier-transform infrared) spectroscopy (FTIR spectrom-
eter, Alpha, Bruker Optics, Germany).
11.2.2 Adsorption Experiment
All adsorption experiments were conducted with 1% solid suspension; solid and
liquid phases were separated by centrifugation at 3,000 RPM. The adsorption
experiments were performed with the following varying parameters: Ls concentra-
tion 25–300 mg/l, temperature 298–393 K, and sulfuric acid concentration 5–100 g/l.
The range of sulfuric acid concentration was chosen based on factual concentration at
pressure leaching of sphalerite concentrate. Initial and final concentrations were
determined by means of UV-Vis spectrophotometry (Specord 250, Analytik Jena).
Table 11.1 Composition of Zn Cd Fe Cu Pb S SS SSO4

sphalerite concentrate, %
48.74 0.19 7.41 1.29 0.37 30.15 29.16 0.99
11 Investigation of Lignosulfonate Adsorption on Zinc Materials in Acidic Media 83
Lignosulfonate adsorption on the surface was calculated from Eq. (11.1):

ðС0 C e Þ V m
qe ¼ , ð11:1Þ
S
where qe, adsorption capacity mg/m2; С0 and Сe, initial and equilibrium lignosulfo-
nate concentration, mg/l; m, weight of adsorbent, g; and S specific area of adsorbent,
m2/g.
11.3 Results and Discussions
11.3.1 Lignosulfonate Characteristics
FTIR spectroscopy analysis (Fig. 11.1) allows one to semiquantitatively appraise the
lignosulfonate composition. Broad absorption band at 3300 cm1 is typical for
Fig. 11.1 FTIR spectra of

lignosulfonates: 1 –
Solikamsky Ls, 2 –
Kamsky Ls
0.95 0.96 0.97 0.98 0.99 1.00
2
3500 3000 2500 2000 1500 1000 500
Wavenumber, cm-1
hydroxyl groups (–OH) in carboxylic (–COOH) and phenolic acids. Absorption at

1720–1710 cm1 and 1420 cm1 is related to C¼O vibration in –COOH and –
OHphen. Structural elements of the sulfonate groups were found at 1140–1160 cm1,
1030 cm1, and 643 cm1. Based on the absorbance capacity comparison, it may be
estimated that the content of –COOH, –OHphen, and –SO3H is higher for Kamsky
lignosulfonate.
11.3.2 Lignosulfonate Adsorption Characteristics
The adsorption isotherms allow one to determine the attaching mechanism of

lignosulfonate on mineral surface, as well as to estimate the optimal reagent con-
sumption. This is important for technology overall, because excess lignosulfonate
amount leads to decrease of solution purification stage effectiveness after leaching.
The capacity of adsorbed lignosulfonate was calculated as the difference between
initial and final Ls concentration (Eq. 11.1). The isotherms of lignosulfonate adsorp-
tion on sphalerite concentrate shown in Fig. 11.2 demonstrate adsorption capacity
dependence on sulfuric acid concentration. Plateau on adsorption isotherms shows
that the concentrate is completely covered by lignosulfonate monolayer. As shown
in Fig. 11.2, monolayer formation takes place at lower lignosulfonate concentration
at the presence of sulfuric acid in comparison with water solution. With increase of
sulfuric acid concentration, the monolayer is formed at lower lignosulfonate con-
centration. For example, in water solution and sulfuric acid solution (50 g/l), plateaus
appeared at 100 mg/m2 (Ls concentration is 204 mg/l) and 86 mg/m2
(Ls concentration is 155 mg/l), respectively. As is known, critical micelle concen-
tration (CMC) has an effect on adsorption capacity, and CMC can decrease at
120 0 g/l H2SO4 Experiment
100 20 g/l H2SO4 Experiment

Adsorption, mg/m2
50 g/l H2SO4 Experiment

80
100 g/l H2SO4 Experiment
60
0 g/l H2SO4 Langmuir
40 20 g/l H2SO4 Langmuir

0 50 100 150 200 250
Equillibrium Lignosulfonate Concentration, mg/l
Fig. 11.2 Isotherms of Solikamsky lignosulfonate adsorption on sphalerite concentrate at 298 K

presence of low molecular weight electrolyte. For example, in Ref. [7], CMC of
lignosulfonate was estimated equal to 0.3 g/l. During leaching, increase of surfactant
concentration above CMC is inefficient.
Adsorption isotherm models are often used for describing the adsorption mech-
anism. Both Langmuir (Eq. 11.2) and Freundlich (Eq. 11.3) isotherms were applied
to analyze the experimental data. Langmuir isotherm assumes that adsorption occurs
on homogeneous solid surface, whereas Freundlich isotherm is associated with
nonideal adsorption of heterogeneous surface by multilayer sorption [8]. The valid-
ity of adsorption isotherm models was estimated by regression coefficient, R2 (4).
kL ∙ Ce
qe ¼ q1 ð11:2Þ
1 þ kL Ce
qe ¼ K F ∙ C e 1=n ð11:3Þ
Pn 2
i¼1 qei q c
ei
R ¼ 1 Pn
2
2 ð11:4Þ
i¼1 qei q
where:
q1 – maximum adsorbed amount, mg/m2
kL – Langmuir constant, l/mg
KF – Fruendlich constant, mg/m2
n – dimensionless constant
qei , qc
ei – virtual and calculated adsorption capacity, mg/m
2
and
1 Xn
q ¼ q :
i¼1 ei
n
The values of regression coefficient indicate that the Langmuir model is well
fitted with adsorption isotherm of lignosulfonate on sphalerite concentrate
(Table 11.2). Kamsky lignosulfonate has the greatest adsorption capability. It con-
tains more –COOH, –OH, and –SO3H groups than Solikamsky Ls. As is known,
these groups are capable of hydrogen bonding, so they act as a bridge between the
solid and liquid phases [9]. Study of additional FTIR spectra of sphalerite concen-
trate after adsorption shows the presence of these groups. On the samples with
Kamsky Ls, intensive absorbance was found in characteristic area of –OH and –
COOH, along with weak absorbance for –SO3H.
Sulfuric acid addition (up to 20 g/l) results in noticeable decline of lignosulfonate
adsorption. Adsorption capability reduced by 58% and 34% for Solikamsky and
Kamsky lignosulfonates, respectively. Further growth of sulfuric acid concentration
(from 20 g/l to 100 g/l) increases Ls adsorption.
Temperature increase up to 393 K leads to adsorption isotherm change: the
plateau disappears; the isotherm is consistent with empirical equation of Freundlich
(Fig. 11.3).
Table 11.2 Adsorption isotherm parameters of the lignosulfonates at 298 K

Parameters of Freundlich
Parameters of Langmuir isotherm isotherm
H2SO4 concentration, g/l kL, l/mg q1, mg/m2 R2 KF, mg/m2 n R2
Solikamsky Ls
0 0.024 119.05 0.994 9.75 2.20 0.949
20 0.025 81.30 0.979 8.65 2.54 0.943
50 0.044 82.64 0.987 12.85 2.92 0.835
100 0.052 88.50 0.950 9.90 2.40 0.761
100a 0.009 135.14 0.000 9.65 2.36 0.965
Kamsky Ls
0 0.008 178.57 0.998 6.95 1.94 0.994
20 0.012 99.01 0.982 6.33 2.21 0.932
50 0.022 83.33 0.996 40.79 8.22 0.948
100 0.031 142.86 0.997 14.54 5.01 0.991
100a 0.009 144.93 0.000 12.75 2.69 0.990
a
Tests were conducted at T ¼ 393 K
120
100
Kamsky Experiment
Adsorption, mg/m2
80
60 Solikamsky Experiment
40 Kamsky Freundlich
20
Solikamsky Freundlich
0
0 100 200 300
Fig. 11.3 Isotherm of adsorption of lignosulfonate on zinc concentrate at 393 K, C H 2 SO4 ¼ 100 g/l
The adsorption value on natural sphalerite is directly proportional to the equilib-

rium Ls concentration (Fig. 11.4). This fact allowed one to describe the isotherm by
Henry equation (Table 11.3). Henry model defines adsorption isotherm at low
concentrations of adsorbate. As shown in Fig. 11.4, Ls adsorption capacity on
natural sphalerite is lower than on sphalerite concentrate. Perhaps lignosulfonate
adsorption on sphalerite is limited by Ls diffusion to active site. The influence of
sulfuric acid on adsorption value on sphalerite is the same as on zinc concentrate.
45
40
Adsorption, mg/m2 35
30
25 Solikamsky Experiment
20 Kamsky Experiment
15 Solikamsky Henry
10
Kamsky Henry
5
0
0 100 200 300
Fig. 11.4 Isotherms of lignosulfonate adsorption on sphalerite at 393 K, C H 2 SO4 ¼ 100 g/l
Table 11.3 Parameters of H2SO4 concentration, g/l Henry equation R2

lignosulfonate adsorption on
Solikamsky Ls
sphalerite at 298 K
0 Г ¼ 0.115С 0.997
20 Г ¼ 0.091С 0.975
50 Г ¼ 0.099С 0.993
100 Г ¼ 0.103С 0.997
100a Г ¼ 0.135С 0.987
Kamsky Ls
0 Г ¼ 0.141С 0.994
20 Г ¼ 0.098С 0.979
50 Г ¼ 0.114С 0.987
100 Г ¼ 0.132С 0.997
100a Г ¼ 0.142С 0.984
a
Tests were conducted at T ¼ 393 K
11.4 Conclusions
The investigation of lignosulfonate adsorption at pressure leaching of sphalerite

concentrate is an applicable method for optimal dosage determination and dosage
regimen optimization. However, study of adsorption at pressure leaching is a
complex problem due to lignosulfonate degradation under the action of oxidizing
agents (Fe3+, O2) and changing of solution composition under leaching conditions
(H2SO4, Zn2+, Fe2+, Fe3+).
In this paper, the authors attempted to determine the influence of acidity and
lignosulfonates composition on their adsorption on surfaces of sphalerite concentrate
and natural sphalerite. It was found out that acidity has a substantial impact on the
value of lignosulfonate adsorption: adsorption grows along with acidity (from 20 to
100 g/l of H2SO4). Knowledge of adsorption behavior at different acidities can be

used at two-stage pressure leaching technology with consecutive low-acidity and
high-acidity stages. At first leaching stage, a low lignosulfonate consumption can be
recommended because the low amount of lignosulfonate will be attached on mineral
surface. However, at the second stage of cake leaching, unreacted particles of
concentrate will adsorb Ls actively. Also, it was established that a raise of temper-
ature up to 393 K leads to change of adsorption isotherm: isotherms correspond to
the empirical Freundlich model. At elevated temperatures, coverage of sphalerite
concentrate becomes multilayer.
Adsorption of natural sphalerite proceeds less intensive in comparison with
sphalerite concentrate and is well fitted with the Henry law. In spite of sufficient
lignosulfonate concentration for complete coverage of sphalerite surface, adsorption
capacity is 2–3 times smaller than on sphalerite concentrate. It can be evidence to the
fact that adsorption is limited by lignosulfonate diffusion to active sites of sphalerite
surface.
Comparison of adsorption values showed that at equal consumptions of ligno-
sulfonates the Kamsky Ls has a higher adsorption capability than Solikamsky.
Perhaps it is related to the high content of –COOH and –OH groups. Thus, probable
mechanism of lignosulfonate adsorption can include chemical interactions of ligno-
sulfonate via –OH and –COOH и -SO3H groups with metal ions on mineral surface.
References
1. Trufanova, M. V., Parfenova, L. N., & Yarygina, O. N. (2010). Poverhnostno-aktivnye svojstva

lignosul’fonatov. Zhurnal prikladnoj himii, 6(82), 1041–1043.
2. Telysheva, G. M., & Afanas’ev, N. I. (1990). Poverhnostno-aktivnye svojstva vodnyh rastvorov
lignosul’fonatov. Himiya drevesiny, 1, 3–19.
3. Sadykov, S. B. (2006). Avtoklavnaya pererabotka nizkosortnyh cinkovyh koncentratov
(pp. 321–324). Yekaterinburg: UrO RAN.
4. Shneerson, Y. M., Onackaya, A. A., & Krasnov, A. L. (1982). Primenenie poverhnostno-
aktivnyh veshchestv pri avtoklavnom vyshchelachivanii pirrotinovyh koncentratov. Tsvetnye
metally, 7, 26–30.
5. Tong, L., & Dreisinger, D. (2009). The adsorption of sulfur dispersing agents on sulfur and nickel
sulfide concentrate surfaces. Minerals Engineering, 22, 445–450.
6. Naftal’, M. N., Nabojchenko, S. S., & Lugovickaya, T. N. (2014). PAV v avtoklavnoj
gidrometallurgii tsvetnyh metallov (pp. 263–267). Yekaterinburg: UIPC.
7. Owusu, G., & Dreisinger, D. B. (1996). Interfacial properties determinations in liquid sulfur,
aqueous zinc sulfate and zinc sulfide systems. Hydrometallurgy, 43, 207–218.
8. Bera, A., Kumar, T., Ojha, K., & Mandal, A. (2013). Adsorption of surfactants on sand surface in
enhanced oil recovery: Isotherms, kinetics and thermodynamic studies. Applied Surface Science,
284, 87–99.
9. Owusu, G (1993). The role of surfactants in the leaching of zinc sulphide minerals at temper-
atures at temperatures above the melting point of sulphur. PhD thesis, University of British
Columbia, Vancouver.
Chapter 12
Complex Processing of Refractory Pyrite
Copper, Copper-Zinc and Polymetallic Ores
on the Basis of Flotation and Combined
Technologies
V. Bocharov, V. Ignatkina, A. Kayumov, M. Viduetsky, and V. Maltsev
12.1 Introduction
The development of mineral resource base is determined by the needs of economy as

well as mining and processing complexes [1–4, 5].
The most important among non-ferrous heavy metals are copper, lead, gold and
platinum group metals (PGM). The common types of deposits of non-ferrous metals
include pyrite sulphide ores and ingrained copper-zinc ores, pyrite polymetallic lead-
zinc ores, etc.
The majority of reserves of the deposits of rich and easy-processable ores are
decreasing annually, which means that refractory ores are being processed more
often.
Distinctive features of ores include low content of valuable components, complex
and inconstant mineral and phase composition, nonuniform ingrained minerals from
coarse-grained to fine fraction monomineral and nanoscale ore grains in close
intergrowth of each other with iron sulphide minerals and gangue and availability
of various structural and textural ore occurrences – crystalline, hidden crystalline
metacolloid, collomorphic, emulsion (solid solution form), brecciated, ingrained,
streaky, solid, massive and other forms.
The domination of iron sulphides above the non-ferrous metal sulphides in
various ores is the most difficult problem for the selective flotation. In many types
of ore, pyrite content is up to 90%; in some ores, pyrrhotite content prevails above
pyrite by twice as much, and it is 50–60%. The content of copper has fluctuated at a
V. Bocharov (*) · V. Ignatkina · A. Kayumov

National University of Science and Technology, MISiS, Moscow, Russia
M. Viduetsky · V. Maltsev

https://doi.org/10.1007/978-3-319-75340-9_12
90 V. Bocharov et al.
wide range from 0.7% to 3% when the content of zinc is changed from 0.7% to 3.5%
or more.
Successful selective flotation of ores also depends on the correlation between the
activated and nonactivated types of sphalerite, on the content of impurities in martite,
wolframite (hübnerite) and cleiophane.
The presence of tennantite, secondary copper sulphides and oxidized minerals in
the ores, has a significant impact on the mineral separation.
Pyrite copper-zinc ores are most involved in the processing; they contain 20–30%
of the total copper reserves and production in Russia.
Ores are complex, since gold, silver and PGM and rare earth metals have
commercial value as well as the basic materials such as copper and zinc minerals.
The technology of ore processing in metallurgy provides simultaneous recovery
of basic noble and rare metals. Copper-zinc-pyrite-pyrrhotite gold ores, most wide-
spread in the Ural region, contain a wide range of ores and gangue. Producing high-
quality copper and zinc concentrates presents a challenge, as copper sulphides are
correlated with iron sulphides and with sphalerite and the high flotation response of
the minerals variety.
The loss of metals with pyrite concentrate and pyrite products reaches 20% Cu,
40% Zn, 90% Au and 50–70% Ag; the loss of zinc with copper concentrate is up to
30–40%.
The analysis of the causes for metal loss has shown that considerable losses occur
due to the thin complex mineral splice joints of ferrous metal sulphides with pyrite
and pyrrhotite (with the size of 100 + 10 microns or less), as well as due to the
substantial loose subtly dispersed grains ( 20 + 5 and less microns), which indicates
the imperfection in schemes and regimes of grinding and flotation.
The opening [6, 11] of the pyrite splice joints, splice joints of copper, zinc and
native gold, is not equal.
The problem of pyrite, other sulphides and their modifications and kinds of
separation is an essential factor and reserve in raising the selective flotation indica-
tors [8]. Super thin grinding pyrite ore of non-ferrous metals in Isomill and Vertimill
does not provide high results of selective flotation of copper and zinc sulphides due
to the formation of secondary sludge and a sharp rise in the flotation activity of pyrite
and sphalerite grains caused by the oxidation of sulphides and release of copper
cations.
Flotation activity of pyrite and other sulphide minerals is comparable while using
butyl xanthogenate as a collector; in relation to iron sulphides, xanthogenates with
highest oxidation state are not selective collectors. The flotation separation of
collective copper and zinc concentrates is a complex technological task. The usage
of hydrometallurgical processes may be an alternative solution, but despite being
highly efficient, these processes are much more expensive than the most expensive
enrichment processes and are not safe for the environment.
12 Complex Processing of Refractory Pyrite Copper, Copper-Zinc. . . 91
12.2 Mineral Processing Description
Various technological schemes [9, 10] of copper ore and copper-zinc ore processing,
technological schemes of direct selective flotation and variants of collectively
selective schemes have been developed and introduced for refractory pyrite-pyrrho-
tite-copper-zinc ores of Tarnersky, New Shemursky, Podolsky, Uzelginsky,
Safyanovskoye, etc. and other deposits of the Ural region.
Varieties of sphalerite, zinc magnitude module (the ratio of the original content of
zinc and original content of copper) and the presence of ferrous sphalerite require
special conditioning of rough zinc concentrate.
The success of sphalerite depression depends on the concentration of sulphide
ions in the desorption operations of the collector, in the selection of the collective
concentrate and in pH values. Best sphalerite depression is achieved when using
combinations of bisulphite, sulphide and sulphite of sodium thiosulphate in different
ratios often accompanied by zinc sulphate [6, 11, 12]. The practice of enrichment has
shown that naturally active and easily floating sphalerite with particle size from 0.2
to 0.005 mm including emulsive extrusions of copper minerals contains 3–5 times
more isomorphic copper and iron than nonactivated varieties. At the first stage of
selection of the collective copper-zinc concentrate in the “soft” depression mode, the
flotation of nonactivated sphalerite gets suppressed during the flotation of copper
minerals and flotation of the part of naturally activated sphalerite. After that the
process of sphalerite activation, the copper-zinc flotation out of the chamber product
of copper flotation with following cleaning of the rough zinc concentrate is
performed.
The second stage of “hard” depression mode selection is the copper-pyrite
flotation with pre-desorption of the collector and higher depressor consumption.
Optimum pH values during the selection in the copper flotation are being
regulated by the value of lime, zinc sulphate and sodium sulphide consumption
and comprise about 7.5–9.5.
The improvement of quality of the zinc concentrate obtained in a chamber
product can be attained under the condition of the zinc content in rougher concen-
trate being no less than 10–12% and pyrite content being no more than 25%.
The selective flotation of pyrite-pyrrhotite-copper-zinc ores of Tarnierskoe
deposit is problematic due to the high content of pyrrhotite (up to 70%) compared
to pyrite content. If the content of pyrrhotite equals 20% or less, the simple
technological method of aeration in lime medium is performed before the
collective-selective flotation with following flotation of the butyl xanthate. This
allows obtaining satisfactory flotation performance. The aeration mode and weak
(compared to pyrite and pyrrhotite and inactive sphalerite) sulphhydryl collectors of
М-TF type along with butyl xanthate allow improving the selectivity of flotation.
At the beginning of the ore flotation, the copper “head” liberates. With the return
of cleaning tailings in the ore flotation, the sphalerite is flotated out of the chamber
product. This reduces the circulation of the pyrite-pyrrhotite intermediate products
circulation significantly. An important problem is the presence of tennantite in some
ores. The floatability of tennantite in lime medium is lower than floatability of other
copper sulphides, which reduces the overall copper abstraction. The high content of
tennantite helps to concentrate an arsenic up to 1% in copper concentrate, which
complicates the technology of its pyrometallurgical processing; it requires the
disposal of arsenic from waste gases. A significant part of tennantite can be isolated
in a separated copper-arsenic concentrate by picking up selective collectors, depres-
sors and regulators [13].
Technological schemes with fractional flotation release of monometallic concen-
trates in different cycles of grinding and flotation in accordance with the technolog-
ical properties of minerals are designed and implemented to improve the abstraction
of metals (Fig. 12.1).
A method for complex ore processing has been developed to produce rich
flotation concentrates and poor polymineral products for hydrometallurgy
(Fig. 12.2).
Chlorine processes, intensive tank-leaching or bio-leaching processes can be
applied to poor products. As for rich products, autoclave methods and acid leaching
with preliminary firing are preferable.
Gold ores in the Ural region are mainly associated with pyrite; the content of the
free gold is 20% or less.
Gold abstraction into copper concentrate increases along with the output of the
concentrate and abstraction of sulphur (pyrite), which leads to a decrease in copper
content of the concentrate to 15%. Therefore, improving the quality of the copper
concentrate is accompanied by the loss of gold from pyrite-bearing tailings. Addi-
tional gold abstraction can be achieved by interstadial gravity separation by means of
centrifugal concentrators and concentration tables or combined gravity-flotation-
chemical and metallurgical technologies on gold pyrite tailings.
Sulphide polymetallic lead-zinc and copper-lead-zinc ores are also considered
refractory and have distinctive technological features because of complex mineral,
chemical and phase compositions and the proximity of technological properties of
sulphide minerals, easily sludging galena. For ingrained pyritic and oxidized sul-
phide ores and roughing concentrates, combined techniques are proposed, with the
release at the stage of processing rich selective concentrates and intermediate
products followed by hydrometallurgical processing schemes, as well as for
copper-zinc ores [17, 18].
Stepnoe polymetallic ore and other deposits have complicated textural and
structural characteristics: from crystalline up to corrosion and skeletal. It has been
proposed to use the flotation scheme with allocation of the copper-lead at the
beginning, and with allocation of the zinc and pyrite concentrates afterwards. The
resulting concentrates contain copper in copper 25.0% with abstraction 72.0%; lead
in lead 46.0% with abstraction lead 81%; and zinc in zinc 52.8% with abstraction
73.0%.
Ore
1 Grinding,
classification
Flotation
Tailings 1 Cu
concentrate
2 Classification
2 Cu
2 Grinding flotation
Tailings
Cu
3 Classification concentrate
3 Grinding Conditioning
Cu-Zn flotation
Tailings
Cu-Zn Tailings 2 Cu
concentrate concentrate
Conditioning
1 Zn flotation
2 FeS Tailings
concentrate Cn-Zn Conditioning 1 FeS2
Tailings
1 Zn
concentrate
3 Cu flotation
Cu 2 Zn
concentrate flotation
Conditioning Zn 3 FeS2
Conditioning
3 Cu
concentrate 2 Zn
concentrate
Fig. 12.1 Schematic diagram of complex processing of pyrite copper-zinc ores

Ore
Grinding, classification
Fractional flotation
1 Cu Cu-Zn 1-Zn FeS2

concentrate concentrate concentrate concentrate
Selection Conditioning
2 Cu 2 Zn Cu-Zn FeS2
concentrate concentrate product concentrate
Conditioning Conditioning
Cu Cu-zn-FeS2 Zn-Cu-FeS2 Zn
Concentrate product product Concentrate
Acid leaching (or chlorination)
Fig. 12.2 Schematic diagram of selective flotation of pyrite copper-zinc ore with fractional release
concentrates
12.3 Metallurgy Technology for the Treatment

of the Mineral Resource
During the processing of complex ores of non-ferrous metals in the tailings concen-
trating factories, hundreds of millions tons of pyrite tailings have accumulated. In
these tailings, thousands of tons of non-ferrous and precious metals are contained.
The necessity to use technogenic pyrite-bearing tailings and other products allocated
during the processing of complex copper-zinc ores has arisen due to the reduction in
production volumes and ease of processing rich ores and also in relation with
reduction of the production of marketable concentrates for the metallurgical produc-
tion of copper, zinc, gold and silver. Cost-effective development of technogenic
deposits and their complex enrichment is possible if a number of technological and
organizational issues are solved. Those tasks are related with the inventory of
technogenic tails, geological mapping technology between rich and poor areas and
with the usage of rational processing technologies along with modern ways of
abstraction of the main components into commercial products of high quality.
Pyrite technogenic tailings are more complex and refractory compared to other
technogenic mineral objects. Pyrite technogenic products are highly subjected to
technological properties changing than the raw ore materials in warehouses or raw
ore during preparation and flotation. The oxidation of pyrite and other sulphides is
intensified due to the tight interaction between the micro-galvanic pairs, mostly
made of pyrite, and other components of the solid phase (copper sulphide, gold
particles form iron compounds and others). Compared to ore material, the portion of
thin-sized fractions exceeds 20%. The concentration of thiosulphate, sulphite, sul-
phate and polythionate ions is much higher than the concentration of the ionic
composition of the ore material due to the more active oxidation of sulphides.
Ion-molecular composition of the liquid phase influences the formation of com-
pounds on the separated minerals and on the electrochemical condition of the pyrite
pulp. Optimum composition of the pulp stimulates the rise of the contrast properties
of separatable minerals and differences in the oxidation of sulphide minerals in the
changing pH, temperature and oxygen concentration; other oxidants allow us to
determine the effective regimes of mineral separation.
A number of studies [1, 6, 7] show the basic technological possibility of fractional
allocation of minerals of non-ferrous metals and gold into concentrates and products
in accordance with the technological properties. The research on material composi-
tion of technogenic materials makes it possible to determine the optimal conditions
for gravitational separation of native free gold particles and its gold open splices into
the gold-containing product; also choose the regime of fractionation and concentra-
tion of copper, zinc and pyrite minerals in individual products and their subsequent
conditioning using individual technological schemes based on mineral processing
and hydrometallurgy.
The most used method for better decomposition of pyrite with the release of gold
and non-ferrous metal sulphide scanned in it is a process of chlorine metallurgy,
mastered in the factories of Germany, Spain and Japan; the process was created by
the Gintsvetmet Institute and was applied at the Ryazan pilot plant. Acid leaching
and bio-oxidation are among the most effective types of impact [14, 15, 16].
12.4 Conclusions
1. Distinctive features of ores: complex and variable chemical and mineral compo-
sition, complex and variable phase constitution, different structures, size, differ-
ent oxidations and slime formation tendencies.
2. Combined processing with separation of the mineral varieties into different
flowsheet cycles has been developed.
3. The combined technologies providing the acquisition of rich concentrates of
non-ferrous metals and pyrite products for the hydrometallurgical processing
are described.
References
1. Chanturia, V. A. (2007). The prospects of sustainable development of mining processing

industry of Russia. Mining Journal, 2, 2–9.
2. Arsent’ev, V. A., Baranov, V. F., & Weisberg, L. A. (2007). Current state and prospects of
development of processes of crushing and grinding of minerals. Mining Journal, 2, 10–14.
3. Sazonov, G. T. (2010). Status of metallurgical industry of Russia. Processing Ores, 6, 3–8.
4. Ptitsyn, A. M. (2002). In J. K. Dyudin, A. N. Sindarsky, & B. P. Rudnev (Eds.), Estimation of
prospects of development of mining and metallurgical base of some metals in the Russian
Federation (p. 562). Moscow: Ore and Metals.
5. Bocharov, V. A., & Ignatkina, V. A. (2007). Technogenic mineral processing, Ore and Metals:
Moscow, Part: 1–2, p. 470 and 406.
6. Bocharov, V. A., & Ignatkina, V. A. (2014). On the issue of studying the impact of the genetic
characteristics of varieties of pyrite and its structural associations to contrast and technological
properties. Mining Journal, 5, 14–20.
7. Ignatkina, V. A., & Bocharov, V. A. (2010). Schemes sulphide flotation of nonferrous metals
through the use of a combination of selective collectors. Mining Journal, 12, 58–64.
8. Bocharov, V. A., Ignatkina, V. A., & Alekseichuk, D. A. (2012). Influence of the mineral
composition of sulfides and their modifications in the selection of the scheme and the selective
flotation collectors of non-ferrous metals. Non-ferrous Metallurgy, 4, 3–10.
9. Bocharov, V. A., Ignatkina, V. A., & Khachatryan, L. S. (2014). Problems separation mineral
complexes when processing massive refractory ores of nonferrous metals. Non-ferrous Metal-
lurgy, 5, 11–16.
10. Bocharov, V. A., Ignatkina, V. A., & Abryutin, D. V. (2011). Technology for processing gold
ores (p. 326). Moscow: MISiS.
11. Bocharov, V. A., & Ignatkina, V. A. (2014). Flotation properties of sphalerite and copper
sulphides pyrite ores. Mining Journal, 12, 75–79.
12. Ignatkina, V. A., Bocharov, V. A., & Diachkov, F. G. (2014). Contrast enhancement sulphide
flotation properties of non-ferrous metal ores with the use of sulfhydryl collectors of different
molecular structure. Physical and Technical Problems of Development of Mineral, 6, 161–170.
13. Bocharov, V. A., Ignatkina, V. A., & Kayumov, A. A. (2015). The problem flotation gray ores
and direction of its solution. Physical and Technical Problems of Development of Mineral, 3,
130–137.
14. Bocharov, V. A., Myntsevich, M. I., & Zakharov, B. A. (2007). State and prospects of
development of technology of complex processing of non-ferrous metals. Non-ferrous Metal-
lurgy, 2, 65–71.
15. Zach, M. S., Zhukova, E. F., & Karimov, E. V. (1990). Complex processing of polymetallic raw
materials on the basis of chloride sublimation roasting, Gintsvetmet’s writings (pp. 2–6).
16. Galushenko, V. V., Bagrova, T. A., & Tarasov, A. V. (1993). Recycling gold pyrite concen-
trates, Gintsvetmet’s writings (pp. 46–49).
17. Mantsevich, M. I., & Myzenkov, F. A. (1988). The separation of copper and zinc products by
selectively firing and flotation, Gintsvetmet’s writings (pp. 38–42).
18. Mechev, V. V., Bocharov, V. A., & Shcherbakov, V.A. (1988). The main directions of the
processing of non-ferrous heavy metals combined with processes, Gintsvetmet’s writings
(pp. 3–11).
Part III
Composite Compound Materials Science in
Building Engineering
Chapter 13
Impact of Waterproofing Permeable
Capillary Mixtures on Cement Stone
F. Kapustin, E. Pomazkin, A. Spiridonova, and V. Oleinik
13.1 Introduction
In the market of building materials to increase durability and improve the water
resistance of concrete and reinforced concrete structures, “Vandex”, “Xypex” and
“Penetron” waterproofing penetrative capillary mixture (WPCM) brands are
presented. They usually consist of рortland cement, silica sand and a certain disper-
sion of the complex chemical active substances that dissolve in water and migrate
through the pores and capillaries in the concrete body, interacting with the products
of hydration of portland cement to form sparingly soluble compounds, filling the
pore space and sealing cement stone (CS).
The permeability reduction of the concrete treated takes place at the expense of
the chemical interaction of soluble mineral salts contained in waterproof mixture
with the hydration products of рortland cement to form heavily soluble compounds
which are produced in the pores and capillaries of concrete thus decreasing their
radius [1, 2]. The permeability increase of the cement stone is also achieved due to
the interaction character change of the porous mortar with the pores surface,
i.e. transformation of the capillary surface in such a way as to increase the end
angle value of their wetting.
However, X-ray diffraction (XRD) and differential thermal analyses (DTA)
methods fail to give a full picture of the processes taking place in the cement stone
under the influence of WPCM. At the same time, the insignificant phase constitution
of cement stone structure which is practically inconspicuous for the researchers can
considerably influence the concrete structure permeability. It is our opinion that
electron microscopy with X-ray spectrum microanalyser of the elements, chemical
F. Kapustin (*) · E. Pomazkin · A. Spiridonova · V. Oleinik

Department of Building Materials, Ural Federal University, Yekaterinburg, Russia
e-mail: f.l.kapustin@urfu.ru

https://doi.org/10.1007/978-3-319-75340-9_13
100 F. Kapustin et al.
composition of the hydration and hardening products is one of the most effective
modern complex methods to study the cement stone structure features including the
changes occurring in it on a capillary level by the action of WPCM.
13.2 Preparation of Samples
To study the WPCM action on the cement stone microstructure, samples of рortland
cement (PC) СEM I 42.5 EN 197–1 of ZAO Nevyansky Tsementnik production
have been made, and as WPCM – type the mixture Penetron was used. The cube
samples of cement stone with the rib size of 40 mm were prepared from cement paste
with water-cement ratio 0.4.
In 28 days of air-moist hardening, the cement samples in question were sub-
merged in water for 2 days, and then on one of the edges of the sample cubes, half of
them have been treated with WPCM, the layer thickness being 1.2–1.5 mm (com-
position of cement stone No. 2). The second half of the samples under consideration
which had not been treated with WPCM was the control one (composition of cement
stone No. 1). All the samples in use were periodically moistened (twice a day) within
the first 3 days to allow more effective permeability of the WPCM soluble ion
penetration into cement stone. All the samples under discussion were stored in an
exicator before testing. Then the WPCM mortar was removed mechanically from the
surface of some samples, and all the samples removed were fractured. The cement
stone probe was taken from the central part of the samples to investigate their
structure using electron microscope.
The microstructure of the cement stone was evaluated with the help of a Tescan
MIRAS LMU electron microscope (magnification up to 100,000 times) and JSM–
5900 series microscope with energy-dispersive spectrometer with which not only the
thin structure images can be produced, but element analyses of the samples can be
carried out, too.
13.3 Results of the Study
To determine the active part of the composition, WPCM was mixed with distilled
water, blended for 15 min and filtrated, and the content of different ions in the mortar
investigated was determined. It was established that carbonates, hydrocarbonate
sodium ions in general and also sulphates, chlorides and calcium ions in less
concentration were available in the solution investigated. It was also established
from the cement stone surface square treated with WPCM that the concentration of
carbon ions was 50 g/m2 and hydrocarbon ions 25 g/m2. It can be assumed that the
present ions have been formed on dissolving the complex ion addition present in
WPCM. Comparatively small concentrations of Ca2+ and SO42 could be formed as
13 Impact of Waterproofing Permeable Capillary Mixtures on Cement Stone 101
a result of dissolving nonsignificant quantities of gypsum and some clinker minerals

of PC.
The investigations of the cement stone by using electron microscope have shown
that cracks are available on the spalling surface with the opening width of 1–2 μm for
water penetration and also the cavities the width of which amounts to 5–8 μm. The
distance between them is from 35 to 80 μm (Fig. 13.1).
The products of Cа aluminate and alum ferrite hydration of рortland cement are
distributed evenly on the whole surface (Fig. 13.1a, position 9–15; Fig. 13.1b,
position 1–6). They are depicted in pink colour on the figures mentioned above.
But the availability of large crystals of Ca(OH)2 should also be pointed out (up to
20 μm in size) (Fig. 13.1a, position 13–15) in the regions of dark blue colour.
However, in contrast to the composition of cement stone No. 1, the largest part of
which has been formed by calcium hydrosilicates of (1.26–1.36) CaO∙SiO2∙2.5H2O
content (Fig. 13.1a, positions 3–6, 20, 24), the cement stone under discussion treated
by WPCM (composition of CS No. 2) in general consists of Ca hydrosilicates of low
basicity; the latter content can be expressed with the following formula (1.00–1.16)
CaO∙SiO2∙3H2O and refer to the C-S-H group (I) [3].
There is the possibility to consider the peculiarities of the pores and capillaries
about 2–3 μm in size at a magnification of up to 1500–2000 times (Figs. 13.2 and
13.3) and the shape and sizes of separate crystals in particular. The data obtained
with the help of a microanalyser of the chemical composition confirm that
hydrosilicates of C-S-H (I) group with approximate content of 1.16CaO∙SiO2∙
(2.50–3.00)H2O treated with WPCM form the basis of the cement stone under
discussion (Fig. 13.2, positions 1, 2). Small newly formed needles have aroused
considerable interest being available in the composition of cement stone No. 2 to a
large extent, the newly formed needles being located mostly in the walls of capil-
laries and cavities, making it narrower. The cement stone with the composition of
cement stone No. 1 fails to consist of similar formations (Fig. 13.3).
The more considerable magnification (up to 4,000 times) allowed the peculiarities
of the WPCM action upon the structure of the cement stone to be revealed. The crack
edges with a width opening from 1.0 to 2.5 μm (Fig. 13.4a) and a cavity of 3–8 μm
size are covered with needle-like formations 0.5–1.0 μm wide and 0.05–0.10 μm in
diameter. As this takes place, the crack width decreases by two or more times in
some sections contributing the cement stone water permeability [4, 5]. By using an
X-ray microanalyser, the composition of crystalline hydrates has been determined;
this is represented by calcium hydrosilicates of low basicity having the high crys-
tallization water content, namely, (1.03–1.18)СаО∙SiO2∙(3.9–4.3)Н2О (Fig. 13.4,
positions 2, 3). The content of the compound data was determined using an X-ray
microanalyser; this content comprised calcium hydrosilicates of low basicity with
high water molecule content in its composition, that is, (1.03–1.18)CaO∙SiO2∙
(3.9–4.3)H2O (Fig. 13.4, positions 2, 3).
The composition of needle-like calcium hydrosilicates located at the cement stone
crack edges somehow differs from the main mass content of gel-like hydrosilicates
(Fig. 13.4, position 1). The needle-like calcium hydrosilicates through which the
cement stone permeability is provided consist of two water molecules more in their
Fig. 13.1 Cement stone structure (600 times magnification): (а) control composition (composition
of cement stone No. 1); (b) covered with WPCM (composition of cement stone No. 2)
Fig. 13.2 Cement stone of the composition of cement stone No. 2 (Region A, Fig. 13.1b, 2,000
times magnification)
Fig. 13.3 Cement stone of composition of cement stone No. 1 (1,500 times magnification)
content than the main mass of calcium hydrosilicates removed from the crack edges
and cavities.
Also the composition of cement stone No. 2 under study consists of relatively
large needle-like crystals of ettringite, the length of which is approximately 3.5 μm
and the diameter 0.3 μm (Fig. 13.4, position 4). The quantity of the ettringite crystals
is comparatively small, and, in general, they are located in big cavities, which are
practically fully filled with needle-like calcium hydrosilicate and relatively large
ettringite. The distance between crystals is from 0.1 to 0.5 μm (Fig. 13.4a). It should
Fig. 13.4 Cement stone of the composition of cement stone No. 2 (4,000 times magnification)
be pointed out that aggregates of cube-like crystals of calcite type are available
which will also decrease cement stone permeability (Fig. 13.4, positions 5, 6).
13.4 The Mechanism of the Cement Stone Influence
Thus, when mixing WPCM with water and putting it on the prepared concrete
surface, the dissolution of the chemically active components, which are the part of
ionic additions, and рortland cement components takes place. In this case, on the one
hand, the high ion concentration of Ca32, HCO3 and Na+ and, on the other hand,
comparatively small Ca2+, SO42 and Cl are formed on the concrete surface.
Because ion concentration of the concrete surface is considerably higher than that
of the porous mortar, these ions will move into the depth of the concrete structure
along the developed pore net and capillaries towards the concentration decrease or
reduction on account of their high wetness.
The original ion concentration on the concrete surface will shrink due to the ion
migration into the protective composition hydration on the other one. In the course of
time, the soluble ions will bind in hardly soluble compounds such as calcium
hydrosulphoaluminate and hydrocarbon aluminate of calcium and also calcite.
Therefore, in the initial period after WPCM hardening on the concrete surface, it is
necessary to provide the deep moistening of its surface to give the possibility to
many ions to be able to migrate from the concrete surface into its depth.
The ions penetrating into the concrete will react chemically with the products of
PC hydration and hardening. The most soluble of them is portlandite, and therefore,
the probable reaction with its participation will be
CaðOH Þ2 þ СО3 2 ! СаCO3 þ 2OH ð13:1Þ
C3 AH 6 þ 2CaðOH Þ2 þ 2СО3 2 þ 6Н 2 О
! C 3 A СaСO3 12H 2 O þ СаCO3 þ OH ð13:2Þ
СаðОН Þ2 þ НСО3 ! СаСО3 þ Н 2 О þ ОН ð13:3Þ
3СаО Al2 O3 CaSO4 12H 2 O þ 2СаðОН Þ2 þ 2SO4 2 þ 20Н 2 О

ð13:4Þ
! 3СаО Al2 O3 3CaSO4 31H 2 O þ 4ОН
C4 AH 13 þ 2CaðOH Þ2 þ 3SO4 2 þ 20H 2 O

! C 3 A 3СaSO4 31H 2 O þ 6OH ð13:5Þ
As a result of the active components’ protection composition interaction with the

cement hydration products, except the hardly soluble compounds, sodium hydroxide
is produced, which sharply reduces CaO solubility thus contributing in its turn to
recrystallization of high-basicity calcium hydrosilicates CSH (II) into low-basicity
CSH (I) having the oriented composition (1.03–1.18) CaO∙SiO2∙(3.9–4.3)H2О and
needle-like form. The needle length is 0.5–1.0 μm and 0.05–0.10 μm in diameter; the
crack width, therewith, can be decreased by two and more times on some cement
stone sections. The compounds under investigation are generally formed on the
pores, cracks and capillary walls, thus changing the character of the mortar pore
interaction with the pore surface resulting in the increase of the edge wetting angle
value and concrete permeability reduction [6].
Relatively large crystals of ettringite are in general formed in large cavities, the
width of which is 5–10 μm. As this takes place, the ettringite quantity is not high, but
hydrosilicates and calcite of low basicity play the main role in the cement stone
permeability.
Furthermore, the carbonization of sodium hydroxide is a distinct possibility when
the concrete surface interacts with carbonic acid of air to form Na2CO3 hydrates
which will crystallize within the concrete structure pores on burning; when repeated
wetting takes place in the construction, the Na2CO3 hydrates will react with cement
hydration products.
It should be pointed out that the sodium hydroxide can provoke alkali corrosion
processes when the aggregate content in concrete and mortar is unfavourable.
According to the data [7–9], the alkali quantity in cement or alkali added when
mixing with water must not exceed 1.2% of cement mass in terms of sodium oxide.
The alkali ion concentration when dissolving WPCM samples in water is 50–60 g/m
2
of the cement surface treated in terms of sodium oxide which correlate (or accord)
with 0.2–0.3% of the cement mass in the concrete on condition that all the sodium
ions migrate by 30–50 mm in its body depth.
To decrease the alkali ion concentration in the concrete pores after the WPCM
action is over (according to the point of view of the mixture’s producers, this period
lasts 28 days), one must wash out the treated surface with water which results in the
probability of occureence of alkali corrosion process development on the concrete
construction surface.
It is our opinion that the WPCM action will be most effective for concretes
consisting of sufficient quantity of Ca(OH)2 and having a definite porous structure in
which the predominant capillary pores are 1–2 μm in size. For concretes with coarser
pores, the effect from needle-like compound formation on the pore walls having a
length of 0.5–0.1 μm can be less significant.
13.5 Conclusions
The alteration of the cement stone structure after its surface treatment with WPCM
takes place at the expense of CO32, HCO3, Ca2+, SO42 and Cl ions to form the
proper AFt and AFm phases and calcite, too. The particular role of forming a
waterproof concrete structure belongs to the calcium needle-like hydrosilicates of
low basicity of (1.03–1.11)CaO∙SiO2∙(3.9–4.3)H2O content. Needle-like
hydrosilicates are formed on the pores, cracks and capillary walls of the cement
stone in question in considerable quantity, narrowing them and increasing the angle
edge wetting magnitude. But the effectiveness of the waterproof action of WPCM is
determined primarily by the peculiarities of both the pore structure and the mineral
composition of the cement stone in the concrete under review which depends on
concrete and the type of the cement used.
References
1. Brovkina, V. G., Ovcharenko, Y. I., Bykov, V. G., & Izosimov, M. P. (2010). Influence of
permeable hydro insulation on the phase constitution of the porous cement. Vestnik UrGU:
Series: Building and architecture, 10, 19–21.
2. Kapustin, F. L., Spiridonova, A. M., & Pomazkin, F. P. (2013). Changing of the cement stone
structure on the treatment with hydro insulating permeable capillary mixture. Cement and its
application, 6, 52–56.
3. Taylor, C. (1996). Chemistry of cement. Moscow: Mir.
4. Shark, I., & Bernd, V. (2004). Durability of concrete. Oranta: Kiev.
5. Kubal, M. T. (1993). Waterproofing the building envelope. New York: McCraw. Inc.
6. Kapustin, F. L., & Semerikov, I. S. (2013). Chemistry of mineral binders. UrFU: Ekaterinburg.
7. Royar, Y. S., & Yranoxsraya, I. Y. (1986). Prevention of alkali concrete corrosion with active
mineral additions. Concrete and reinforced concrete, 7, 16–17.
8. Salnikov, N. S., & Ivanov, F. M. (1971). Corrosion destruction of concrete, containing large
additions of potash. Concrete and reinforced concrete, 10, 20–21.
9. Vicktorov, A. M. (1986). Prevention of alkali corrosion of moistened concrete. Concrete and
reinforced concrete, 8, 38–39.
Chapter 14
Composite Cement with a Polymer Addition
E. Gerasimova
14.1 Introduction
The complex use of raw materials and industrial waste is of great practical impor-
tance nowadays [1]. It will contribute substantially to the development of ecologi-
cally pure, resource-saving and nonwaste commercial technologies, whereas
utilization of industrial waste provides the solution to the environmental issues
which are aggravating both in Russia and elsewhere annually.
Various kinds of industrial waste can serve as valuable raw materials due to their
composition and properties. They can be used most effectively and extensively in the
production of building materials, specifically, to obtain composite binding
substances.
Composite binding materials are widely used in modern construction for inside
and outside finishing. Up to three different types of mineral additions of both natural
and technogenic origin can be introduced into their composition, e.g. fly ash, blast
furnace slag, pozzolanas, limestone ground, marble powder, etc. [2, 3].
Besides, the production of high-technology finishing materials requires polymer
modifier application, which allows improving and changing the final properties of
the product in terms of its practical usage [4].
Another objective regarding practical implementation is to investigate the
strength characteristics of composite cements consisting of a certain type of polymer
modifier as well as the quantity of mineral fillers.
E. Gerasimova (*)

https://doi.org/10.1007/978-3-319-75340-9_14
108 E. Gerasimova
14.2 Experimental Procedure
In the course of the experiments, the samples from the mixtures were prepared in
accordance with a specific formulation after storage under the given conditions and
time. Then the necessary quantity of the samples in question was tested.
14.2.1 Raw Materials
Two types of polymer modifiers of non-Russian production have been used in the
investigation proper, namely, vinyl-acetic ester redispersible polymer powder
(PAV-22, France) and styrene-acrylate liquid dispersion (Acronal 290D, Germany).
The polymer characteristics are given in Table 14.1.
Fly ash from Berezovskaya district power station (FY), limestone meal (LM) and
marble powder (MP) have been used as mineral additions to ordinary Portland
cement CEM I 42.5 N (PC). The main properties and chemical composition of
mineral components are presented in Tables 14.2 and 14.3.
Table 14.1 Polymers characteristics

Solid content Particles size,
Trademark (%) (micrometre) Bulk density (kg/m3) рН
RPP РАV-22 99 1 1–5 (80) 980 5–6
PD Acronal 50 1 100 – 7.5–9.0
290D
Table 14.2 Raw materials properties

Raw material Bulk density (kg/m3) Specific surface (m2/kg)
Portland cement 1100 300
Marble powder 950 630
Limestone meal 1200 230
Fly ash 940 370
Table 14.3 Raw materials chemical composition

Mass content (%)
1.1.1.1.1.1.1.1Raw material ΔMпрк SiO2 Al2O3 Fe2O3 CaO MgO SO3
Portland cement 0.24 19.78 5.63 4.37 60.38 2.79 6.81
Marble powder 42.53 3.76 1.70 – 48.22 3.79 –
Limestone meal 42.77 3.68 4.94 0.31 45.37 1.99 0.94
Fly ash 1.40 19.40 10.60 7.30 43.30 6.20 11.80
14 Composite Cement with a Polymer Addition 109
14.2.2 Experimental Technique
A small-scale method has been used for this investigation. A standard mixing
procedure was used.
The polymer additions were combined with water and then added to the cement
while mixing. The time after the addition of polymers was kept constant throughout
the study. The water present in the polymer dispersion was included in the total water
content of a mix. From each mix small prisms were cast in steel moulds. The
specimens were demoulded after 24 h and cured under combined conditions.
The tests for the compressive and flexural strengths were carried out after 3, 7,
14, 21 and 28 days’ time. For flexural strength determination, a Michaelis device for
small samples was used.
All the results presented in the paper are the averages over a maximum of six
specimens and a minimum of three.
14.3 Experimental Results and Discussion
Some data concerning the characteristics of cement-mineral, polymer-cement and

polymer cement-mineral composites are presented in this work.
The first stage of the present work was devoted to the selection of the optimum
quantity of polymer modifiers. Compositions consisting of different quantity of
polymers were formed, and, after the combined storage, the samples were tested at
the points of 3, 7, 14, 21 and 28 days. The results of compressive and flexural
strength determination on the 28th day are presented in Table 14.4.
It has been found that the introduction of at least 2.5% of redispersed powder
enhances both compressive and flexural strength of cement stone. Smaller amount of
redispersed powder yielded results in lower strength as compared with the control
composition, which is most likely due to the fact that its quantity is not enough to
provide proper hardening during the second stage of the combined storage (at the
stage of air hardening). Polymer dispersion reduces both compressive and flexural
Table 14.4 Polymer cement stone strength

Rfl (МПа) Rcom (МПа)
Polymer quantity (%) PAV–22 Acronal290D PAV–22 Acronal290D
0 1.9 1.9 33.5 33.5
1.0 1.4 1.6 21.0 35.2
1.5 1.9 1.6 36.5 36.8
2.0 2.4 1.6 45.6 28.3
2.5 2.9 1.4 53.3 36.7
3.0 2.4 1.6 48.4 31.6
3.5 2.8 1.5 41.0 31.5
5.0 2.8 1.5 41.0 31.5
110 E. Gerasimova
FA = 27.3929-0.0098*x-0.0048*x^2
LM = 49.208-1.2061*x+0.0104*x^2
MP = 34.4642-0.1967*x-0.0031*x^2
Rcom,
MPa 40
35
30
25
20
15
10
0
10 15 20 25 30 35 40 45 50
Quantity of addition, %
FA; LM; MP
Fig. 14.1 Compressive strength of Portland cement stone with mineral additions (28 days)
strength to a certain extent, which is confirmed by some data [5–7]. As a result of

further investigations, the quantity of the polymers equaling 2.5% of the cement
mass has been chosen.
At the second stage of the investigation, the influence of mineral additive fillers
on the physical-mechanical properties of cement stone was determined. Mineral
fillers were added into the mixture in the quantity of 10, 20, 30, 40 and 50%
replacing the same cement quantity. The same water/cement ratio which equals
0.45 was maintained to keep the compositions and therewith the mixture mobility
under control. It has been established that the mobility in question depends on both
the variety and the quantity of the filler.
Marble powder and limestone meal plasticize the mixture increasing the mobility
of the former proportionally to the quantity of the filler introduced, i.e. up to 1.6–1.7
times larger than that of pure composition controlled when the filler consumption is
maximum. It is probably due to the granulometry features and the grain surface of
carbonate fillers. Fly ash introduction fails to affect the mixture mobility, but
increasing its quantity results in mobility ranging from 52 to 55 mm.
Furthermore the flexural and compressive strength of the samples stored under
normal conditions was specified at the points of 3, 7, 14, 21 and 28 days. The results
of the compressive and flexural strength measurement of the composite binders on
the 28th day are given in Figs. 14.1 and 14.2.
In general, the tendencies of the strength reduction on the 28th day depending on
the kind of a filler are similar. The introduction of fly ash decreases the strength
much more significantly than carbonate fillers. On introducing all kinds of fillers, the
cement/filler ratio is 1:1, and the compressive strength experiences nearly a twofold
FA = 1.908-0.0116*x-6.4286E-5*x^2
LM = 2.044-0.0086*x-8.7921E-5*x^2
MP = 1.9584-0.0109*x-1.1554E-5*x^2
Rfl, 2.0
MPa
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
10 15 20 25 30 35 40 45 50
Quantity of addition, %
FA; LM; МP
Fig. 14.2 Flexural strength of Portland cement stone with mineral additions (28 days)
Table 14.5 The matrix of experimental design

Composition no. Cement (%) Addition 1 (%) Addition 2 (%)
1 100 0 0
2 0 100 0
3 0 0 100
4 75 25 0
5 75 0 25
6 50 50 0
7 50 0 50
8 0 50 50
9 50 25 25
decrease. It can be concluded that it is possible to introduce the chosen fillers in the
quantity of up to 20% of the cement mass.
The last stage of the present work focused on the properties of the complex three-
component system containing mineral additives and modified polymers. This stage
of our work was carried out by using the simplex lattice experiment planning
method. The composition of three systems “cement-fly ash-marble powder”,
“cement-fly ash-limestone meal” and “cement-marble powder-limestone meal” has
been formed to fit the planning matrix (Table 14.5).
The test results concerning the strength of the hardened binders obtained on the
28th day were processed with the help of “Statistica 10.0” software package
assuming that the total amount of materials was taken as 100% (Figs. 14.3 and 14.4).
112 E. Gerasimova
MARBLE POWDER (%) MARBLE POWDER (%)

0.00 1.00 0.00 1.00
0.25 0.75 0.25 0.75
0.50 0.50 0.50 0.50
> 38
> 2.5 < 38
< 2.5 < 34
< 2.2 < 30
0.75 0.25 < 1.9 0.75 0.25 < 26
< 1.6 < 22
< 1.3 < 18
<1 < 14
< 0.7 < 10
< 0.4 <6
1.00 0.00 < 0.1 1.00 0.00 <2
0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50 0.75 1.00
CEMENT (%) FLY ASH (%) CEMENT (%) FLY ASH (%)
System“cement-fly ash-marble powder”

LIMESTONE MEAL (%) LIMESTONE MEAL (%)
0.00 1.00 0.00 1.00
0.25 0.75 0.25 0.75
0.50 0.50 0.50 0.50
> 38
> 2.6 < 38
< 2.6 < 34
< 2.3 < 30
0.75 0.25 <2 0.75 0.25 < 26
< 1.7 < 22
< 1.4 < 18
< 1.1 < 14
< 0.8 < 10
< 0.5 <6
1.00 0.00 < 0.2 1.00 0.00 <2
0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50 0.75 1.00
System “cement-fly ash-limestone meal”

0.00 1.00 0.00 1.00
0.25 0.75 0.25 0.75
0.50 0.50 0.50 0.50

> 36
< 36
> 2.4 < 32
< 2.4 < 28
0.75 0.25 < 2.1 0.75 0.25 < 24
< 1.8 < 20
< 1.5 < 16
< 1.2 < 12
< 0.9 <8
< 0.6 <4
1.00 0.00 < 0.3 1.00 0.00 <0
0.25 0.50 0.75 1.00 0.00 0.25 0.50 0.75 1.00
0.00 CEMENT (%)
MARBLE MARBLE
CEMENT (%)
POWDER (%) POWDER (%)
System “cement-marble powder-limestone meal”
Fig. 14.3 The projection of curvilinear strength dependence of three-component systems with
PAV-22 polymer on the 28th day. (On the left side, the flexural; on the right side, the compressive.)
MARBLE POWDER (%) MARBLE POWDER (%)

0.00 1.00 0.00 1.00
0.25 0.75 0.25 0.75
0.50 0.50 0.50 0.50
> 31
>2 < 31
0.75 0.25 <2 0.75 0.25 < 27
< 1.7 < 23
< 1.4 < 19
< 1.1 < 15
< 0.8 < 11
< 0.5 <7
1.00 0.00 < 0.2 1.00 0.00 <3
0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50 0.75 1.00
FLY ASH (%) CEMENT (%) FLY ASH (%)
CEMENT (%)
System “cement-fly ash-marble powder”

0.00 1.00 0.00 1.00
0.25 0.75 0.25 0.75
0.50 0.50 0.50 0.50
> 32
>2 < 32
0.75 0.25 <2 0.75 0.25 < 28
< 1.7 < 24
< 1.4 < 20
< 1.1 < 16
< 0.8 < 12
< 0.5 <8
1.00 0.00 < 0.2 1.00 0.00 <4
0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50 0.75 1.00
System “cement-fly ash-limestone meal”

0.00 1.00 0.00 1.00
0.25 0.75 0.25 0.75
0.50 0.50 0.50 0.50
> 29
< 29
> 1.9 < 26
0.75 0.25 < 1.9 0.75 0.25 < 23
< 1.6 < 20
< 1.3 < 17
<1 < 14
< 0.7 < 11
< 0.4 <8
1.00 0.00 < 0.1 1.00 0.00 <5
0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50 0.75 1.00
CEMENT (%) MARBLE CEMENT (%) MARBLE
POWDER (%) POWDER (%)
System “cement-marble powder-limestone meal”
Fig. 14.4 The projection of curvilinear strength dependence of three-component systems with
Acronal290D polymer on the 28th day. (On the left, flexural; on the right, compressive)
114 E. Gerasimova
The introduction of polymer modifiers considerably increases the flexural

strength limit compared to the compositions without polymers in spite of the
difference in storage conditions.
The projections of the dependence of the compressive and flexural strength limit
demonstrate that the region of the optimum composition is in the range of nearly
100% of the cement content. However, polymers, including PAV-22 powder and
Acronal dispersion, increase the strength of the compositions containing, simulta-
neously, fly ash and marble powder.
The strength of the compositions with polymer powder appears to be higher than
that of the compositions with dispersion.
14.4 Conclusions
In the course of the work, the potentialities of using mineral fillers of various origins
to produce materials based on Portland cement CEM I modified with polymer
addition have been investigated.
The experiments on the impact of mineral fillers upon the strength of water
cement stone have shown that it is preferable to introduce carbonate fillers in the
amount of up to 20%. When replacing cement by using only one type of fillers, it is
better to use limestone meal to make the polymer-modified cement binder.
The three-component polymer-modified systems have been studied with the help
of the simplex lattice method of mathematical planning experiment. The study has
revealed that in order to produce composite materials based on the polymer cement
binders selected, it is recommended to use both fly ash and marble powder with
PAV-22 or Acronal290D with regard to the strength loss. The combined additive can
be introduced in the amount of 25% of cement mass. Under these conditions the ratio
of fly ash to marble powder is to be 1:2.
References
1. Bozhenov, P. I. (1986). Complex use of mineral raw materials for production of building
materials (pp. 10–11). Moscow: Stroyizdat.
2. Kopanitsa, N. O., & Anikavova, L. A. (2002). Fine dispersed additives for filled binding
materials on the basis of cement. Constuction Materials, 9, 2–3.
3. Entin, Z. B. (1993). Chemistry and technology of finely ground multi-component cements, Thesis
for DPh: Moscow.
4. Frederik, A., & Nikolya, R. (2000). Using redispersible powders “Rhoximat” in dry mixes
production. Construction Materials, 5, 8–9.
5. Domanskaya, I. K., Kapustin, F. L., Mokhort, E. S., & Oleynik, V. N. (2003). The main
approaches of component selection for fine polymercement products and coatings. In F. A.
Finger, J. Stark, & H.-B. Fischer (Eds.), Proc. of the 15th Int. Conf. IBAUSIL (pp. 523–530).
Weimar: Bauhaus University.
6. Rogante, M., Domanskaya, I. K., Gerasimova, E. S., & Vladimirova, E. V. (2013). Feasibility
study for a neutron-based investigation of polymer cement concretes. Universal Journal of
Applied Science, 1(1), 11–17.
7. Bhikshma, V., Rao, K., & Balaji, B. (2011). An experimental study on behavior of polymer
cement concrete. Asian Journal of Civil Engineering (Building and Housing), 5, 563–573.
Chapter 15
The Manufacture of Concretes Based
on Unburnt Ash Gravel
F. Kapustin, I. Fomina, and V. Oleinik
15.1 Introduction
In modern building, the use of concretes, specifically high-strength varieties and

those with prescribed physical-technical properties, is being constantly widened.
Aggregates are the basic ingredients of concrete. The proper selection of coarse
aggregate, which comprises up to 85% of concrete mass, allows regulating its
properties as well as reducing its cost. The quality of concrete is profoundly
influenced by the strength and grain composition of the aggregate and the contents
of various impurities in the latter [1].
High-quality crushed stone and gravel are in short supply at plants producing
concrete and ferroconcrete goods, especially in regions where there are no high-
strength rock deposits and the transportation of implies considerable costs.
An alternative to the use of natural aggregates is the production of their artificial
equivalents, such as ceramdor, slag broken stone, unburnt ash gravel, etc., which are
characterized by sufficiently high strength and frost resistance. The production of
unburnt aggregates does not require the expenditures of electrical energy and fuel or
complex furnace installations for high-heat treatment.
Unburnt ash gravel (UAG) is an artificial porous aggregate obtained in granules
from preliminarily moistened mixture of fly ash and Portland cement (PC) with
further hardening. The fabrication of unburnt ash gravel involves the following
operations: proportioning, mixing (fly ash with cement), moistening the mixture
and forming granules of the required coarseness, steaming and fractioning. Fly ash
or slag mixtures, produced by burning brown and bituminous coals or anthracite at
heat power stations, can be used for the fabrication of unburnt ash gravel [2].
F. Kapustin (*) · I. Fomina · V. Oleinik

e-mail: f.l.kapustin@urfu.ru

https://doi.org/10.1007/978-3-319-75340-9_15
15.2 Experiments
The present paper aims to investigate the composition and structure of unburnt ash
gravel as well as the possibilities of using it for the production of high-strength light
concrete.
In the study, the following materials have been used: PC of two types Cement I
42.5 H (Cement I), Cement II/SA 32.5 (Cement II), fly ash from bituminous coal
burning (FA), screening of hornblende and a solidification accelerator, namely
sodium sulphate (Na2SO4).
Fly ash (FA) includes up to 93% of SiO2 + Al2O3 + Fe2O3. It is also acidic and
fine. In terms of its principal properties, it meets the GOST 25818 requirements and
belongs to type 3, i.e. it can be used for the production of both cellular and ordinary
concrete.
There has been developed a new composition and method for the production of
unburnt ash gravel of high strength, consisting of fly ash obtained from heat power
industry (65%), Portland cement (20%), screening from rock crushing (15%) and the
accelerator of hardening. The method for the production of unburnt ash gravel
involves proportioning and mixing the components, moistening the mixture,
forming granules of the required coarseness, steaming and fractioning.
The granules are subjected to steam treatment in a steam chamber for 6 h at 85 C
and are then tested according to the standard (GOST 9757-90 Gravel, artificial
porous crushed stone and sand). During the selection of components for burnt ash
gravel mixture, the influence of the cement type on its properties was investigated.
Table 15.1 presents the compositions of burnt ash gravel and the properties of
unburnt granules before steam treatment. The compositions of granules after steam
treatment are shown in Table 15.2.
It was established that the grain composition of all types of burnt ash granules
meets all the GOST 9757-90 requirements.
The aggregate strength in Cement I is 1.5 times higher than that of burnt ash
gravel in Cement II. As far as physical-mechanical properties are concerned, the
unburnt ash gravel obtained meets the GOST 9757-90 requirements and has both the
strength of P350 and the bulk density of 900.
Table 15.1 Physical-mechanical properties of ash cement unburnt granules

The fraction content
Properties mm in size, mass %
Bulk Pointed granule
Water consumption density, strength, Н/ More than
Cement types of the mixture, % kg/m3 granule 5–20 20
CI 24 963 229 93.5 6.5
C II 28 934 227 94.0 6.0
GOST 9757-90 – – – 85–100 Not more
figures than 10
15 The Manufacture of Concretes Based on Unburnt Ash Gravel 119
Table 15.2 Physical- Values

mechanical properties of
Properties CI C II
unburnt ash gravel after steam
treatment Bulk density, kg/m3 873.6 835.6
Compressive strength in the cylinder, MPa 9.93 6.50
Total porosity, % 26.76 32.46
Open 16.16 26.16
Close 25.6 6.3
Hollowness, % 44.5 43.34
Water absorption, mass % 10.26 17.73
Fig. 15.1 Macrostructure of unburnt ash gravel: (a) in Cement I; (b) in Cement II
In order to justify the differing density of unburnt ash gravel, its microstructure
has been investigated (Fig. 15.1).
The study has revealed that burnt ash gravel in Cement I has small pores, their
size being 0.17–0.32 mm, whereas in Cement II, pores are coarser, and their size
ranges from 0.32 to 0.62 mm. It should be noted that there are fewer open pores in
burnt ash gravel in Cement I. The strength of granules depends on the degree of
porosity to a large extent. It is higher in the case of closed porosity as compared with
open porosity. Open porosity of burnt ash gravel in Cement II is 1.62 times higher
than that in Cement I. Open porosity is caused by excessive water during the
granulation. The amount of water used to obtain burnt ash gravel based on Cement
II is 1.17 times greater than that of based on Cement I, which suggests that the
porosity of the former is higher and the strength is lower.
Burnt ash gravel has a combined structure, i.e. it includes both loose-grained and
conglomerate structure.
15.2.1 Differential Thermal Analysis
Differential thermal analysis of unburnt gravel (Fig. 15.2) confirmed that steam
treatment of ash cement stone with hornblendite addition accelerates cement hydra-
tion, which is supported by large mass loss (19.55%). In the temperature range of
Fig. 15.2 Derivate diagram of burnt ash gravel containing 20% PC + 15% hornblendite+65% fly
ash + 2% of Na2SO4
130–150 C, the crystallization of tobermorite gel is observed. In this case, the mass
loss increases up to 14.40%. In the temperature range of 301–380 C, the dehydra-
tion of calcium hydrosulphoaluminate occurs. It should be added that during deep
endothermic effect in the temperature range of 460–475 C, Na2SO4 dissolves Ca
(OH)2 and thereby decreases its contents. Moreover, the endothermic peak in the
temperature range of 640–669 C is observed on the derivative diagram. The peak is
caused by the burnout of semi-coke and coke residues in ash. In the temperature
range of 950–980 C, the crystallization of the glassy phase of ash occurs [3].
15.3 The Manufacture of Concretes Based on Unburnt Ash

Gravel
Mix design of the construction blocks of V25 and V40 strength class was carried out
using burnt ash gravel produced from Cement I (Tables 15.3 and 15.4). Since bulk
density and hollowness of crushed granite stone and burnt ash gravel differ, during
the concrete proportioning, it was taken into account that the lighter burnt ash gravel
demands a greater amount of crushed stone, the volume being equal. It was
established that the strength characteristics of the optimum concrete contents made
15 The Manufacture of Concretes Based on Unburnt Ash Gravel 121
Table 15.3 The composition and the properties of concrete mixtures and concrete
Materials consumption, kg/m3 Concrete mix properties
No C S UAG G W С-3 Mobility, sm Density kg/m3
1 334 932 837 – 191 1.8 5.0 2131
2 511 550 819 – 210 3.1 10.5 2055
3 293 814 – 1202 173 1.8 5.0 2458
Table 15.4 Physico-mechanical concrete mix properties

Physico-mechanical concrete mix properties
Compressive strength, MPа
After steam In 28 days Concrete
No Density, kg/m3 treatment air-wet storage strength type
1 1904 23.0 38.2 В25
2 2038 39.4 53.8 В40
3 2307 29.3 41.1 В25
Fig. 15.3 Deterioration of

concrete on unburnt ash
gravel
of burnt ash gravel correspond to V25 and V40 classes allowing using it instead of
granite crushed stone.
The durability of concrete is determined not so much by the durability of
aggregates but by the firmness of coupling of cement stone with the grain surface
of the aggregates. Grain porosity of aggregates has a positive impact on coupling.
Due to water suction by porous aggregates in concrete mix, cement paste penetrates
open pores, thereby joining the cement stone and the aggregate.
Concrete deteriorates due to the cracks in both the cement stone and the aggregate
(Fig. 15.3) [4].
15.4 Conclusions
The research has established that physical-mechanical properties of unburnt ash

gravel can vary depending on the cement type used. The experiments have demon-
strated that the change of granule strength is determined by cement hardening
processes. In order to produce unburnt ash gravel of high strength, it is essential to
use cement varieties of brands 500 and 550 because they harden faster and possess
high durability on compression.
The introduction of hornblendite into the mix results in an increase of the strength
characteristics of burnt ash gravel. Strength characteristics of burnt ash gravel can be
increased as a result of physical-chemical processes of hydrated clinker minerals
consisting of Na2SO4 and the compression of unburnt ash gravel with hornblendite,
the latter being a chemically inert material and serving as an aggregate.
The aggregates obtained meet the GOST 9757-90 requirements; as to their
physico-mechanical properties, frost resistance equals F50-100.
Unburnt ash gravel has a combined macrostructure, i.e. it combines both a loose
and a conglomerate structure.
Practical application of the concrete mix suggested for the fabrication of unburnt
ash gravel allows producing lightened construction concrete as well as decreasing
the construction costs by 5–10%. The strength characteristics of concrete made of
unburnt ash gravel of the optimum content correspond to those of concrete made of
crushed stone. Although the volume of crushed stone and that of burnt ash gravel is
the same, the consumption of the former is higher than that of the latter because the
hollowness of the two differs.
Therefore, there is an opportunity to obtain concrete of V25 and V40 types with
lower consumption of burnt ash gravel and natural aggregates. Frost resistance of
concrete made of unburnt ash gravel is F150.
The production of unburnt ash gravel is characterized by the economy of fuel and
energy resources. For instance, in this case, the consumption of conditional fuel is
2–3 times lower than during the production of burnt artificial porous aggregates [4].
References
1. Volzhensky, A. (1970). Unburnt artificial aggregates for lightweight concrete. Building Mate-
rials, 80–81.
2. Cherry, B. L., Ufimtsev, V. M., & Kapustin, F. L. (2006). Promising technology for removal,
storage and use of TPP ash-and-slag (pp. 11–110). Ekaterinburg.
3. Gorchkov, V. C., & Timashev, V. V. (1963). Methods physico-chemical analysis of binders
(pp. 80–130). Moscow: Higher School.
4. Chumakov, L. D. (2011). Technology of fillers of concrete (pp. 55–138). Moscow: Publishing
House of the Association of Construction Higher Education Institutions.
Chapter 16
Physical–Chemical Bases of a Glass Batch
Preparation Technique
V. Deryabin, O. Paramonova, and E. Farafontova
16.1 Introduction
The increasingly demanding requirements for quality of modern glass call for a
serious analysis of the influence of various factors on glass batch uniformity. A glass
batch is a homogenous mixture of raw materials prepared beforehand and weighed in
accordance with a specific recipe. The main parameters of the glass batch quality are
its chemical homogeneity and the conformance to its chemical composition. Uni-
form distribution of batch components allows one to obtain glass homogeneity in
composition and structure. Batch homogeneity depends on the size distribution of
raw materials, the constancy of its chemical composition, the dosing accuracy, the
mixing conditions of batch components and the absence of segregation, dusting and
volatilization at the stages of batch transportation.
The preparation of raw materials is often referred to as the preparation of the
composition. This attitude to the preparation of initial components for the glass
melting was not formed accidentally and is due to the nature of the processes
occurring in the glass melting furnace. Due to relatively high viscosity of the glass
melt, glass furnaces are characterized by laminar motion of glass melt. Under these
conditions the only possibility of glass melt composition averaging is the diffusion
of individual ions and molecules. Since the diffusion rate is low, the homogenization
is possible only in small areas of melt during the time in the furnace. The scale of
glass melt inhomogeneity is predetermined.
The preparation of glass involves several operations, such as grinding, screening,
drying materials, dosing, feeding into the mixer of the individual components and
mixing them. At the last stage, glass batch is also wetted as this is prerequisite to
obtaining homogeneous glass and can significantly reduce dust particle carryover as
V. Deryabin · O. Paramonova · E. Farafontova (*)


https://doi.org/10.1007/978-3-319-75340-9_16
124 V. Deryabin et al.
well as prevent component segregation and stratification, which are likely to be

caused by transportation. The main factors preventing segregation are the capillary
forces connecting the solid particles of batch (quartz sand, cullet particles) due to the
interlayers of dissolved potash, soda, nitre, etc.
16.2 Experimental Technique
A special device to investigate the segregation of glass batch components was

designed. It simulates the effects of mechanical stress and vibration on the tendency
to glass batch segregation. The experimental procedure and description of the device
are presented in Ref. [1]. Applying the technique enabled the study of the redistri-
bution of particles in a simple system “quartz sand–soda” and “quartz sand–soda–
water” and the height segregation of different fractions of dry and wet powder
dolomite. Quartz sand, soda and dolomite are the main components of any glass
batch. The system “soda–sand” analyses the distribution of the components based on
density, while the dolomite analysis involves particles of various sizes.
The first stage was devoted to the segregation in the system “quartz sand–soda”.
We used the following initial component ratio, wt.%: 30/70, 20/80 and 10/90,
respectively. The homogeneous mixture was shaken 30, 100 and 300 times. Then
each composition was divided into five layers. The bulk density of each layer of
batch was determined. To investigate the segregation in the “quartz sand–soda–
water”, the homogeneous mixture was moistened with water (4%), shaken 30, 100
and 300 times. Then the composition was divided into five layers. The bulk density
of each layer of batch was determined too. The experiments with wetted batch were
conducted immediately after moistening as well as with 40 min of conditioning
period. Figures 16.1, 16.2, and 16.3 show the height change in the density of
two-component batch for minimum and maximum number of impacts (the top
layer of the mixture is marked 1, the lower layer 5).
The established dependences indicate the material height redistribution after

mechanical impact. For the system “quartz sand–soda” (Fig. 16.1), soda as a light
material almost entirely transgresses into the upper layers of batch, which is partic-
ularly characteristic of compounds with high proportion of soda (70/30). It should be
noted that the composition from the first to the third layer remains the same, and
there is a sharp decrease in soda amount in the lower layers. It can be most clearly
observed in experiments with prolonged mechanical effect.
Moistening with water (4 wt.%) (Fig. 16.2) and little mechanical impact on batch
make it possible to observe the formation of separate batch conglomerates.
16 Physical–Chemical Bases of a Glass Batch Preparation Technique 125
1.7 1.7
1.6 1.6
90/10 90/10
1.5 1.5
80/20 80/20
70/30
3
1.4
Bulk density, g/cm
70/30
3
1.4
Bulk density, g/cm

1.3 1.3
1.2 1.2
1.1 1.1
1.0 1.0
0.9 0.9
0.8 0.8
1 2 3 4 5 1 2 3 4 5
Layer no. Layer no.
(а) 30 times (b) 300 times

Fig. 16.1 The bulk density of a two-component batch “quartz sand–soda” at different layers. (а)
30 times (b) 300 times
1.7 1.7
90/10 90/10
1.6 1.6
80/20 80/20
1.5 70/30 1.5 70/30
3
3
Bulk density, g/cm
1.4 1.4
Bulk density, g/cm
1.3 1.3
1.2 1.2
1.1 1.1
1.0 1.0
0.9 0.9
0.8 0.8
1 2 3 4 5 1 2 3 4 5
Layer no. Layer no.
Fig. 16.2 The bulk density of two-component batch “quartz sand–soda” at different layers with 4%
wetting. (а) 30 times (b) 300 times
1.7
1.7
1.6 90/10
1.6 90/10
80/20 80/20
1.5
70/30 1.5 70/30
3
1.4
Bulk density, g/cm
3
1.4
Bulk density, g/cm

1.3
1.3
1.2
1.2
1.1 1.1
1.0 1.0
0.9 0.9
0.8 0.8
1 2 3 4 5 1 2 3 4 5
Layer no. Layer no.
Fig. 16.3 The bulk density of two-component batch “quartz sand–soda” at different layers with 4%
wetting and 40 min conditioning time. (а) 30 times (b) 300 times
As a result, the bulk density of the first layer to the fourth remains constant. When
mechanical impact is prolonged, conglomerates of sand particles fixed by layers of
water are destroyed, and there is a gradual increase in bulk density from the upper
layer to the bottom.
Conditioning moistened “silica sand–soda” mixture (Fig. 16.3) results in a more
uniform distribution of components given the same mechanical effects. In the upper
layers, bulk density is higher, and it is lower at the bottom. The reason for such
distribution is capillary-crystallization fixing of individual conglomerates, which
occurs during the conditioning period. The characteristics of this fixing have been
studied in Refs. [2–4]. The bigger the mechanical impact, the more proportional is
the change in bulk density of the mixture.
Dry dolomite was crushed and ground to study its fraction separation. As a result,
we obtained the following ratio of fractions of dolomite wt.%: 1–2 mm – 38.89;
0.5–1 mm – 22.22; lower than 0.5 mm – 37.
The initial batch with uniform distribution of fractions was shaken 30, 100 and
300 times. Each composition was divided into three layers, and the content of each
dolomite fraction in portion was evaluated. Firstly the segregation of various frac-
tions of dried powder dolomite was studied, and then the dolomite powder was
moistened with water. The moisture of the powder under consideration was 1%
and 4%.
Well-mixed powder containing particles of different sizes in each case was
shaken 100 times. For further experiments the dolomite powder was moistened
with 1 mol/l soda solution. The powder was shaken 100 times in all cases.
100%
Fracture content, wt.%
100%
90% 90%
36.60
30.47
37.00

43.00
43.58
37.00
38.29
80%
80%
51.71
70%
70%
60%
17.87
60%
22.22
17.75
22.22
19.28
50%
47.20
50%
15.88
40.01
40%
40%
30%
45.53
30%
38.89
37.19
43.96
38.89
20%
32.32
20%
16.41
22.33
10%
10%
0%
0%
initial 1 2 3
initial 1 2 3
Layer no. Layer no.
< 0.5 mm 1-0.5 mm 2-1 mm < 0.5 mm 1-0.5 mm 2-1 mm
Fig. 16.4 Distribution of fractions of a dry dolomite powder in layers of the batch after mechanical
impact. (а) 30 times (b) 100 times
100% 100%
23.10 13.39
21.22
90% 90%
32.93
37.00
37.00
40.77
45.43
80% 80%
65.50
70% 70%
17.09
60%
23.14
60%
22.22
22.22
20.23
50% 50%
40%
39.57
40%
63.51
44.92
30% 30%
38.89
43.94
38.98
27.34
38.89
20% 20%
14.99
10% 10%
0% 7.16
0%
initial 1 2 3 1 2 3
initial
Layer no. Layer no.
< 0.5 mm 1-0.5 mm 2-1 mm < 0.5 mm 1-0.5 mm 2-1 mm
(a) 1% wetting (b) 4% wetting
Fig. 16.5 Distribution of fractions of moistened dolomite in layers of the batch. (a) 1% wetting (b)
4% wetting
The moisture of the batch was 4%. Experiments involving the batch were performed
immediately after wetting and after a 40-min conditioning period. The graphs
(Figs. 16.4, 16.5, 16.6, and 16.7) illustrate the dependences of the distribution of
various fractions of material throughout batch layers (upper layer of the mixture
components is marked 1, the lower layer – 3).
100%
100%
90%
36.85
37.00
38.39
29.32
90%
41.60
37.00
39.41
80%

45.85
80%
70%
70% 4.84
60% 9.65
22.22
60% 8.89
6.07
22.22
50%
50%
46.65
40%
40%
65.84
53.50
49.41
30%
49.51
54.52
30%
38.89
38.89
20%
20%
14.97
10%
10%
4.74 0%
0%
initial 1 2 3 initial 1 2 3
Layer no. Layer no.
<0.5 mm 1-0.5 mm 2-1 mm 2-1 mm 1-0.5 mm < 0.5 mm
(а) without conditioning time (b) 40 minutes of conditioning time
Fig. 16.6 Distribution of fractions of powder dolomite 1% moistened by 1 mol/l soda solution in
layers of batch. (а) without conditioning time (b) 40 min of conditioning time
100%
100%
90% 90%
35.17
35.62
37.00
36.58
37.00
39.79
43.99
41.20
80%
80%
70% 70%
60% 7.77 10.21 60%
22.22
22.22
10.78 8.10
50% 50%
40.94
40.29
40% 40%
56.61
54.62
52.11
30% 30%
48.02
38.89
38.89
20% 20%
23.12
15.72
10% 10%
0% 0%
initial 1 2 3 initial 1 2 3
Layer no. Layer no.
< 0.5 mm 1-0.5 mm 2-1 mm < 0.5 mm 1-0.5 mm 2-1 mm
(а) without conditioning time (b) 40 minutes of conditioning time
Fig. 16.7 Distribution of fractions of powder dolomite 4% moistened by 1 mol/l soda solution in
layers of batch. (а) without conditioning time (b) 40 min of conditioning time
As shown in Fig. 16.4, the proportion of the coarse fraction is reduced when
passing to the bottom layer.
This tendency can be observed in all experiments. However, the middle fraction
demonstrates the opposite behaviour: its content increases when passing to the
bottom layers. These two fractions change their contents consistently. The content
of the fine fraction increases slightly only in response to minor external impact when
passing to the bottom layer. With significant external impact, its share increases
when passing to the middle level and decreases in the bottom layer. It should also be
noted that the most significant change is observed on passing from 30 to 100 shak-
ings; the character of changes further remains the same.
When the powder dolomite is moistened by 1 wt.% water (Fig. 16.5), the amount
of coarse fraction is reduced from the upper layer to the bottom. This is especially
evident when passing to the third layer. The content of the fine fraction increases
uniformly. The amount of middle fraction becomes smaller only in the bottom layer;
the content of middle fraction virtually does not change on the other layers. At 4%
wetting the amount of coarse fraction is reduced uniformly when passing to the
bottom layer. The content of the fine fraction is increasing. It should be noted that on
the first and second levels, there is an averaging of batch composition: fine and
coarse fractions can be found in roughly equal proportions.
In general the dependences show that wetting with water changes the distribution
of fractions throughout batch levels. The amount of coarse fraction is decreased
when passing to the lower level, whereas the amount of small and middle fraction is
increased. Moreover, with a small amount of water, the changes between them are
insignificant, and there is redistribution when water content is of 4%.
It is known that the capillary force is directly proportional to the size of particles
[2]. A large fraction under water effect becomes independent of other fractions; the
capillary interaction of large particles leads to their consolidation and contributes to
the transition to upper level at the batch column height. Small fraction goes down,
and the capillary force is insufficient to hold the particles. For further experiments,
the dolomite powder was moistened by 1 mol/l soda solution. Humidity was 1 and
4%. The experiments were carried out with the prepared batch immediately after
wetting and with a 40-min conditioning time (Figs. 16.6 and 16.7).
Both experiments indicated almost identical dependences: the components fixing
on the first level and its change when passing to the third layer. The amount of
middle fraction on the first two layers does not change, and on the last layer, it
increases sharply. The characteristic feature of this series of experiments is that the
amount of fine fraction does not change significantly when passing from the upper
level to the lower one. This trend can be most clearly observed in the experiments
with 40-min conditioning time. The fine fraction was fixed in the pores between the
middle and the coarse fraction by means of crystalline aggregates obtained after
batch drying.
16.4 Conclusions
The distribution of components in the two-component system “soda–sand” and the

change of dolomite fractions ratio in response to mechanical impact have been
studied. It has been shown that soda being a lighter component passes up to the
surface layers, whereas the sand remains on the bottom layer. As far as the dolomite
experiment is concerned, it has been revealed that the segregation of its components
occurs because of different particle sizes; the segregation is about 150–200%.
Wetting the mixture of “quartz sand–soda” fixes the initial distribution depending
on the conditions created for the formation of primary particle conglomerates fixed
by capillary forces as well as by the establishment of capillary-crystallization
contacts: the fuller the conditioning is, the higher the degree of the fixation. Wetting
powder dolomite with water does not significantly change the redistribution of
particles after shaking. When dolomite powder is moistened with salt solutions,
the crystals resulting from water evaporation reduce the mobility of the powder
particles thereby preventing segregation. Soda solution serves as a fixing component
due to the appearance of crystal (cementing) phase whereby the powder particles are
immobilized.
References
1. Deryabin, V. A., Farafontova, E. P., Paramonova, O. L., & Panov, I. V. (2012). Study of glass
batch components segregation. Glass and Ceramics, 68(9–10), 319–322.
2. Deryabin, V. A., Malygina, O. L., & Farafontova, E. P. (2006). Capillary counteraction to
segregation of particles in glass batch preparation. Glass and Ceramics, 63(1–2), 3–6.
3. Deryabin, V. A., Malygina, O. L., & Farafontova, E. P. (2006). Interaction between glass batch
particles via potassium-bearing interlayers. Glass and Ceramics, 63(1–2), 40–42.
4. Paramonova, O. L., Deryabin, V. A., & Farafontova, E. P. (2014). Investigation of component
segregation in wetted glass batch. Glass and Ceramics, 70(9–10), 315–318.
Chapter 17
Influence of Ion-Electron Interaction
at the Metal-Oxide Melt Boundary
on the Protective Properties of Enamel
Coatings
O. Lazutkina, E. Farafontova, and I. Voroshilova
17.1 Introduction
Silicate-enamel coatings are widely used for the protection of metal pipeline trans-
portation equipment which is considered to be the most reliable and cheap variety at
the moment. In single-layered thin enamel coatings for industrial use, the enamel
layer is less than 0.2 mm. In that case the coating quality depends on the extent to
which a thin film of melt is enriched by iron oxides formed during the burning
process in enamelling. At high concentrations of these oxides during the cooling
process, the protective coating crystallizes and crumbles off the metal surface.
Modern research methods make it possible to study the boundary of interaction
metal-oxide melt, to determine the thickness of the adhesion layer and the distribu-
tion of elements throughout this layer. The study aims to investigate the mechanism
of metal oxidation during enamel coating burning and to identify the factors affect-
ing the formation of protective coating.
17.2 Experiment
The metal oxidation rate under the enamel melt layer in various atmospheres and
diffusive mobility of iron ions with given amount of Fe2O3 (10–20 wt. %) in melt
was measured by the gravimetric method using derivatograph Q-1500-D. The study
of the adhesion layer at the metal-enamel coating boundary was conducted using
SEM with energy dispersive microanalyzer Oxford Inca Energy 350.
O. Lazutkina · E. Farafontova (*) · I. Voroshilova


https://doi.org/10.1007/978-3-319-75340-9_17
132 O. Lazutkina et al.
In previous studies [1], we have determined that enamel enrichment by iron oxides
occurs not gradually due to the oxidation of iron surface but through the diffusion
into the areas of oxidation in spots where the coating has worn thin (sharp corners,
edges, holes, ribs).
The oxidation process under the melt layer enriched by iron oxides is realized due
to air oxygen in air atmosphere or due to oxygen in argon and oxygen atmosphere
[2]. In that case, oxygen at the film melt boundary is involved in the reaction
1 1
Fe2þ þ O2 ¼ Fe3þ þ O2 : ð17:1Þ
4 2
The concentration of Fe3+ ions at the boundary with the atmosphere is determined
by the law of mass action:
pffiffiffiffiffiffiffiffiffi
CFe3þ aO2
K¼γ , ð17:2Þ
C Fe2þ PO1=4
2
where K, equilibrium constant for reaction (17.2), CFe3þ and C Fe2þ are ion concen-
trations at the boundary with atmosphere, γ, coefficient taking into account the
activity of iron ions:
aFe2þ C 3þ
¼ γ Fe : ð17:3Þ
aFe3þ C Fe2þ
Hence the concentration of the oxidizer (Fe3+ ions) at the boundary with atmo-
sphere is
k CFe2þ PO1=4
0
CFe3þ ¼ pffiffiffiffiffiffiffiffiffi 2 ¼ k PO1=4 : ð17:4Þ
γ aO2 2
At the boundary with metal, the concentration of Fe3+ ions is determined by the
equilibrium of iron oxidation reaction (17.5). The equilibrium of this reaction is
significantly shifted to the right [1], and we can, therefore, assume that CFe3þ 0. Let
us suppose that the process (17.3) rate is limited by the diffusion of Fe3+ ions
through the melt film:
Fe þ 2Fe3þ ¼ 3Fe2þ : ð17:5Þ
In that case
DFe3þ D 3þ
V gr ¼ C Fe3þ or taking into account Eq:ð17:4Þ, V gr ¼ Fe k 0 PO1=4 :
δ δ 2
ð17:6Þ
17 Influence of Ion-Electron Interaction at the Metal-Oxide Melt. . . 133
lgPO2
0.8
0.6
0.4
0.2
2.00 2.02 2.04 2.06 2.08 2.10 2.12 2.14 2.16 2.18
lgVgr
Fig. 17.1 Correlation of advancement rate of the oxidation boundary along 08KP steel under a
layer of Na2O∙aB2O3 melt and partial pressure at 1073 K
160
Vgr, mm/h
140
120
100
2 4 6 8 10 12 14 16 18
PO2, vol. %
Fig. 17.2 Advancement rate of oxidation boundary for Na2O∙aB2O3 melt along 08KP steel versus
air partial pressure
This implies that reducing oxygen partial pressure in the gas phase leads to the
decrease in the oxidation rate Vgr. Therefore, one can expect that for sufficiently
small values PO2 , the oxidation zone distribution rate will be determined by the iron
oxidation rate according to reaction (17.1). In this case the magnitude of Vgr should
be proportional to PO1=4 .
2
Figure 17.1 illustrates the dependence of lgV gr ðlgPO2 Þ at PO2 ¼ 2.18.26102 hPa
for melt Na2O∙2B2O3 at 1073 К. It can be seen that dependence is linear at PO2 ¼
6.22 hPa.
The value of n found from slope ratio of this curve equals 0.276, which is
congruent to the theoretic value calculated according to the equation

E
V gr ¼ Aexp : ð17:7Þ
RT
As expected, in this case the oxidation boundary moves progressively rather than
cyclically. At PO2 ¼ 1025102 hPa, the rate Vgr decreases from 153 to 130 mm/h
(see Fig. 17.2). This is because at PO2 102 hPa the diffusion of the oxidation zone
becomes cyclic.
The dependence of the oxidation rate on the temperature in air atmosphere can be
described by an exponential Eq. (17.7). For Na2O∙2B2O3 and B2O3 melt, this rate
equals 185 and 189 kJ/mol, respectively. These values are close to the theoretical
ones [1]. These data once more confirm that viscous flow of melt significantly
influences the speed of the process described above.
As shown above, if melt contains iron ions, there is an appreciable oxidation rate
under the enamel melt layer in oxidation atmosphere. The air oxygen is involved in
the oxidation process, and the total oxidation process can be described as follows:
1
2Fe2þ þ O2 ¼ 2Fe3þ þ O2 , ð17:8Þ
2
Fe þ 2Fe3þ ¼ 3Fe2þ , ð17:9Þ
1
Fe þ O2 ¼ Fe2þ þ O2 ¼ FeO: ð17:10Þ
2
Process (17.9) can occur without air oxygen but in this case as the concentration
of Fe3+ ions in the enamel melt film decreases, so does the metal oxidation rate.
Let us compare Fe, Co, Ni oxidation curves obtained by thermogravimetric
method in Pt crucible. The melt layer under samples was about 5 mm. The mass
ratio of sample and melt was as 1:5. The experiments were carried out in air
atmosphere. One can see a definite effect of ions of different valence on metal
oxidation under enamel melt layer. At high temperatures 11001400 К, only the
NiO is stable [3], so in the melt Ni, it is presented only as Ni2+. It was established that
at 1373 K, the nickel sample under enamel melt layer did not vary its mass
significantly.
When comparing the oxidation curves for Fe and Co samples covered by enamel
melt layer, it can be observed that the Fe oxidation is more intensive than that of Co.
This is due to the fact that the Co3+ ions equilibrium concentration is higher than that
of Fe3+ at PO2 ¼ const.
Let us assume that the ion portion of Мe2+ (Fe2+, Co2+) is N Me2þ in two initial
melts, and in equilibrium state, the concentration of Fe3+, Fe2+, Co3+, Co2+ ions is
P P P P
equal to N Fe 3þ , N Fe 2þ , N Co3þ , and N Co 2þ , respectively. It is evident that
N Me2þ ¼ N Me3þ þ N Me2þ . In air atmosphere, the equilibrium of Me2+ and Me3+ ions
P P
is established according to reactions:
1
2FeO þ O2 ¼ Fe2 O3 , ð17:11Þ
2
1
3CoO þ O2 ¼ Co3 O4 : ð17:12Þ
2
Reaction (17.12) considers the fact that at high temperatures only Co3O4 [3] is
stable. The ionic form of these reactions can be written as follows:
1
2FeO þ O2 ¼ 2Fe3þ þ O2 , ð17:13Þ
2
1
2CoO þ O2 ¼ 2Co3þ þ O2 : ð17:14Þ
2
The equilibrium constants of these reactions are:
a2Fe3þ þ aO2
K 31 ¼ 1=2
, ð17:15Þ
a2Fe2þ þ PO2
a2Co3þ þ aO2
K 32 ¼ 1=2
: ð17:16Þ
a2Co2þ þ PO2
To approximate evaluation of the relationship between Co3+ and Fe3+ concen-

trations, let us assume that aMenþ ¼ N Menþ . Hence taking into account that PO2 ¼
2.1102 hPa, we obtain
1=2 N P 3þ 1:48aO2
K 31 ¼ Fe 2 , ð17:17Þ
N Me2þ N FeP
3þ
1=2 N P 3þ 1:48aO2
K 32 ¼ Co 2 : ð17:18Þ
N Me2þ N CoP
3þ
Consequently
1=2
K 31 N Me2þ
3þ ¼ ð17:19Þ
P
N Fe 1=2 1=2
,
K 31 þ 1:48aO2
1=2
K 32 N Me2þ
3þ ¼ : ð17:20Þ
P
N Co 1=2 1=2
K 32 þ 1:48aO2
At 1373 K lgК31 ¼ 4.4 and lgК32 ¼ 0.75. The value aO2 < 1, which is why the
3þ N Me2þ . Substituting
P
second term in Eq. (17.19) can be neglected; in that case N Fe
the result into Eq. (17.20), we obtain
1=2
3þ K 32
P
N Fe
P
N Co3þ ¼ 1=2 1=2
¼ bN Fe
P
3þ : ð17:21Þ
K 32 þ 1:48aO2
3þ > N
P P
As b < 1 then it can be concluded that N Fe Co3þ .
In the real conditions of oxidation at the air boundary, the equilibrium of reactions
(17.13) and (17.14) is established. The concentration of Me3+ ions at the boundary
with metal is determined as follows:
Fe þ Fe2 O3 ¼ 3FeO, ð17:22Þ

Co þ Co3 O4 ¼ 4CoO: ð17:23Þ
The equilibrium constants of these reactions equal lgК40 ¼ 2.1, lgК41 ¼ 5.9 at
1373 K, respectively. As these values are too high, considering that Me3+ ions
concentration at the boundary with metal is very small, it can be assumed that
3þ 0.
P
N Me
1.0
Dm, mg/sm2
Fe
0.5 Co
Ni
0.0
5 10 15 20 25
t, min
Fig. 17.3 Oxidation of Fe, Co, Ni under Na2O∙aSiO2 melt layer in air at 1273 K
Assuming that the metal oxidation rate is determined by Me3+ ions diffusion to
metal surface, we find
P
CMe 3þ
V k ¼ DMe3þ , ð17:24Þ
δ
3+
P
where C Me 3þ is the concentration of Co and Fe3+ ions near the melt boundary with
3þ > C
P P
gas. As C Fe Co3þ , hence Fe, according to reaction (17.22), should oxidize more
quickly than Co, according to reaction (17.23), and Ni should not oxidize in the least
3þ ¼ 0. Experimental data (Fig. 17.3)
P
with higher valence ions participation as C Ni
support this conclusion. Figure 17.3 represents the oxidation results at 1273 K of Fe,
Co, Ni samples covered by melt film with insert of FeO, CoO, NiO in amount of
4 mol. %, respectively.
The average oxidation rates of iron and nickel found using straight lines slope at
τ > 5 min are 2.4 and 0.36 mg/sm2, respectively. The iron oxidation rate is
significantly higher than that of cobalt, whereas the nickel oxidation rate is about
zero. In air atmosphere, the decisive role in metal oxidation process under enamel
melt layer is played by metal ions of different valence in the melt. The contribution
of air oxygen is restricted to ions oxidation Me2+ to Me3+ on the film-air boundary.
If the oxidation process of metal with oxygen depolarization, which can occur
during the molecular oxygen diffusion through the film, has evolved considerably,
the nickel would oxidize at 1273 K, according to the reaction
Ni þ Ni3þ ¼ 2Ni2þ : ð17:25Þ
Experience has shown that this is not observed. This confirms the conclusion that
the corrosion process with oxygen depolarization in the system oxygen-oxide film
enamel melt-metal is not essential.
Using energy dispersive microanalyzer, we have performed the qualitative and
quantitative X-ray microanalysis of the adhesion layer at metal-enamel boundary.
The metal-enamel penetration zone is a rough surface. The inclusions of irregular
round shape consisting of metal-oxide film fragments break off from the metal
surface to enamel. Moreover, in metal-enamel interface, heterogenic structures are
formed [4, 5]. These structures consist of dendritic crystals Fe2SiO4, NiO-Fe2O3,
CoO-Fe2O3 of lighter colouration (see Fig. 17.4).
Fig. 17.4 The results of X-ray analysis of metal-enamel coating boundary layer
17.4 Conclusion
The experiments have shown that the iron oxidation rate is considerably higher than
that of cobalt, while nickel oxidation rate virtually equals zero. We can, therefore,
conclude that in air metal ions of different valence play the key role in the metal
oxidation process under enamel melt layer.
The role of atmosphere oxygen is restricted to the oxidation of Me2+ to Me3+ on
the boundary between the film and the air. The corrosion process with oxygen
depolarization in the system oxygen-oxide film of enamel melt-metal is of no
particular significance. During Fe and Co oxidation under the enamel melt layer
containing ions Fe3+, Fe2+, Co3+, Co2+ of variable valence, the metal ions in melt
play the central role in the oxidation process.
During the firing process on certain spots of the surface of steel covered with
enamel melt layer in air, there appear foci of intense metal oxidation with pro-
nounced dark colour, where Fe2O3 concentration is significantly higher than 20%.
At these sites the enamel melt is enriched with oxides of variable valence to the
extent that it obtains electronic conductivity, and this makes the oxidation process
spread in molten enamel throughout the metal surface with constant speed.
There are no depositions of oxide film or metal films of adhesion oxides (Co, Ni)
on the Fe surface. These metals are presented in inclusions of NiO-Fe2O3, CoO-
Fe2O3 compositions drifting in enamel near the metal surface.
References
1. Lazutkina, O. R. (2013). Substrate metal oxidation mechanisms for the appearance of defects in
enamel coatings. Glass and Ceramics, 69(11–12), 416–419.
2. Gutiérrez-Castañeda, E., Salinas-Rodríguez, A., Deaquino-Lara, R., & Márquez-Torres,
F. (2015). High temperature oxidation and its effects on microstructural changes of hot-rolled
low carbon non-oriented electrical steels during air annealing. Oxidation of Metals, 83(3–4),
237–252.
3. Esin, O. A., & Gel’d, P. V. (1962). Physical chemistry of pirometallurgical processes [in -
Russian] (p. 671). Moscow: Metallurgiya.
4. Lazutkina, O. R., Kazak, A. K., & Ponomareva, M. V. (2011). Effect of enamel layer thickness
on defectiveness of enamel coatings. Glass and Ceramics, 68(1–2), 33–35.
5. Deryabin, V. A., & Uglinskikh, M. Y. (2014). Change in the structure of fired glass enamels with
different iron oxide content. Glass and Ceramics, 71(7–8), 258–259.
Chapter 18
Study of Enamel Slip Particles Interaction
Using Model Systems
V. Deryabin and I. Tochilova
18.1 Introduction
During batch preparation for enamel frit synthesis, obtaining a homogeneous mix-
ture of raw materials is of considerable importance. Water droplets falling in
between the solid particles of batch result in the formation of capillary water layers
causing particle attraction [1]. Water menisci arising at low moisture content
between solid particles cause capillary attraction and particle convergence
[2, 3]. As capillary forces have considerable significance in the process of enamel
batch preparation, it is necessary to study them.
18.2 Experiments
The present work is devoted to the study of capillary-crystallization interaction of

particles during the processes of enamel slip drying. To study the adhesion forces,
we used a model of capillary contact “the spherical particle – liquid interlayer – flat
substrate.” This model is optimal for the description of capillary contacts occurring
in real disperse systems [4].
The capillary-crystallization strength of the three types of slip and their filtrates
has been experimentally studied. With regard to the enamel slip, such studies have
been conducted for the first time.
During slip drying, free water between solid particles evaporates [5]. As water
evaporates, salt concentration increases. When water is removed, solid particles and
V. Deryabin · I. Tochilova (*)


https://doi.org/10.1007/978-3-319-75340-9_18
140 V. Deryabin and I. Tochilova
I II III IV
Fig. 18.1 Layouts of model particles at various stages of experiment
clay particles get closer together resulting in shrinkage and the formation of air
voids.
Due to the reduction of liquid volume, isolated capillary layers between particles
appear [6]. Concave capillary isthmuses arising at the contacts of solid particles
trigger the convergence of solid surfaces. While drying, solid particles are pulled
together by capillary bridges and are drawn to the product surface, and hereby biscuit
is formed. At the stage of free capillary adhesion of separate particles, the attractive
forces may contribute to the reorganization of the slurry structure. Until the forma-
tion of crystalline aggregates the reorientation and convergence of solid constituents
of low water, slurry is possible. The greater the capillary adhesion force is, the more
likely the local compaction and reorientation of solids is.
The mechanisms of capillary-dispersed system behavior mentioned above are the
subject of the research. During the experiments, the glass particle was in contact with
the liquid phase since a droplet was applied on it. Throughout the experiment,
persistent evaporation of water from the slurry was observed. There are four typical
stages of the experimental test of capillary-crystallization strength. These stages are
schematically presented in Fig. 18.1.
Stage I – the beginning of the experiment. A liquid drop is deposited onto the top
of the glass spherical particle. The model particle is withdrawn from the flat bottom
substrate.
Stage II – a flat substrate is placed under the glass particle using a microscrew. A
liquid drop forms a meniscus between the spherical particle and the substrate. This
position is observable both during the attachment and the detachment of the glass
particle and the substrate.
Stage III – the flat glass substrate comes into contact with the spherical particle.
Step IV – the glass particle is withdrawn from the flat substrate, whereby the
liquid droplets prevail both on the glass particle and on the flat substrate.
As part of the present research, experiments using model glass particles have been
conducted to study the capillary and crystallization strength of solid particle adhe-
sion during the process of capillary layer evaporation. Capillary layer was obtained
through the immersion of a glass ball into distilled water, slip of coating enamel,
ground enamel, kombi-ground enamel, and their water constituent. The experiments
were performed with changing cup volume due to the evaporation of liquid. In the
18 Study of Enamel Slip Particles Interaction Using Model Systems 141
case of mobile liquid, the evaporation progresses more rapidly, which can cause
more rapid crystallization of liquid solution and adhesion of particles.
The droplets of solutions under consideration form concave menisci attracting
particles and bringing them closer up to the immediate contact. When the external
force causing the deformation of torsion balance coil exceeds the maximum capillary
strength, the capillary isthmus ruptures. The force was fixed at the time of formation
of the cup as well as at specified intervals.
The measurements were performed in dynamics since the crystal structure was
constantly forming and further collapsing.
The experiment was repeated several times until the liquid layer dried out or the
attraction forces of model particles disappeared.
Based on the experimental data, the dependence of capillary-crystallization
strength of coupled model particles on contact duration has been plotted on the
graphs.
18.3.1 Study of Contact Layers of Water Component

of the Coating Enamel Slip
The average adhesion force at the initial time is 0.6 mN (Fig. 18.2). The measure-
ment ends at time lags of 6–8 min. Increasing water contents makes it possible to
take a large number of measurements. As a result, the experiment is prolonged.
This is due to the increased volume of the liquid layer. Extending the exposure
time during the successive measurements leads to the rise of the adhesion force. This
is due to the occurrence of crystallization component as the filtrate is a salt solution.
In the withdrawn state, crystals grow from the interface. The solid content in slip
slurry is from 50% to 60% whereas the content of particles smaller than 0.14 mm in
4 0.036 g
Adhesion force, mN
0.037 g
3 0.034 g
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8
Duration, min
Fig. 18.2 Dependence of capillary-crystallization strength on contact duration (cup material –

water component of the coating enamel slip, diameter of spherical particle 2.96 mm)
4 0.050 g
Adhesion force, mN 0.051 g
3 0.045 g
0
0 0.5 1 1.5 2
Duration, min

coating enamel slip, diameter of spherical particle 2.96 mm)
the filtrate is not more than 0.2% in accordance with the requirements of the
laboratory filter paper (GOST 12026–76).
The interaction forces between different particles between molecules or ions in
solution are not identical [7]. Water has higher surface tension σ ¼ 72.8 MJ/m2
which is due to the relatively strong hydrogen bonds. In molecule solutions, the
particles forming weaker bonds are pushed up into the surface layer. Thereby the
surface tension decreases. The reduction of the surface tension in the solutions under
study is caused by such compounds as sodium nitrite and others.
18.3.2 Study of Contact Layers of Coating Enamel Slip
It should be noted that in this case, the number of experiments is far lower than in
previous one. This is due to the high viscosity (103.5–104 Pa∙s) and low water content
(approximately 40%) in the slurry, which resulted in rapid drying out. Figure 18.3
shows that not all measurements could be taken. The drying process occurred too
fast, and, as a result, the adhesion force exceeds the upper limit of the measuring
instrument. The exposure was conducted in the withdrawn state (without solids
contact). Crystals grew from the interface. At high viscosity evaporation is in
progress too. In this case there appear crystallized areas in the layer bordering with
air. Since evaporation occurs from the liquid surface, the high viscosity fluid does
not have time to flow to the surface layer, and solely the cup shell hardens.
Therefore, when viscosity is high, only the outer layer of the cup hardens.
The maximum adhesion force of enamel coating is 2.36 mN. The maximum
number of measurements is 2.
4 0.035 g
3 0.037 g
0
0 0.5 1 1.5 2 2.5 3 3.5 4
Duration, min

water component of the ground enamel slip, diameter of spherical particle 2.96 mm)

of the Ground Enamel Slip
During the experiment with water component of ground enamel slip, it had been
established that virtually all measurements finish within 3 min. The sample weight is
between 0.034 and 0.037 g. It should be mentioned that the viscosity of the aqueous
component is much lower than that of the enamel slip. A greater mass leads to the
increase in the volume of the solid phase, adhesion force and the number of
experiments. The pattern persists. However, the number of points of the ground
enamel filtrate fixed was lower than that of the coating enamel filtrate. Measuring at
time lags of 1 min made it possible to register the maximum adhesion force, which
equals 0.83 mN as the crystallization component appears (Fig. 18.4).
18.3.4 Study of Contact Layers of Ground Enamel Slip
In contrast to the water component, the number of measurements for the slip ground
is much lower since the slip ground enamel is characterized by high viscosity and
low amount of liquid layer. The greater the sample mass is, the longer the experiment
is. The average value of adhesion strength at the initial time ranges from 0.8 to 1.0
mN. Thus, the general pattern in case of the slip ground enamel compared to the
coating enamel slip persists. The adhesion force of the slip is considerably greater
than in previous measurements. The viscosity of the ground enamel slip (102–103
Pa∙s) is lower than that of the coating enamel slip (103.5–104 Pa∙s); water content is
greater, and so is the number of measurements.
In the case of a cup at a low viscosity, the solidification occurs throughout the cup
volume. At low viscosity liquid flows more freely to the air interface, and it can be,
therefore, assumed that the entire capillary layer hardens as a result. If the device had
4 0.039 g 0.041 g 0,040 g 0.042 g 0.037 g

Adhesion force, mN 0.043 g 0.037 g 0,039 g 0.043 g
3
0
0 0.5 1 1.5 2 2.5 3 3.5 4
Duration, min
Fig. 18.5 Dependence of capillary-crystallization strength on contact duration (cup material – the
ground enamel slip, diameter of spherical particle 2.96 mm)
4 0.016 g
Adhesion force, mN
0.015 g
3 0.014 g
0
0 0.5 1 1.5 2
Duration, min

water component of the kombi-ground slip, diameter of spherical particle 2.96 mm)
had a broader measuring range, it would have shown that low viscosity causes higher
strength, as the whole cup is crystallized (Fig. 18.5).

of the Kombi-Ground Slip
It is vital to note that the average initial weight equaled 0.015 g, which is more than
two times higher than the average weight of the water component of the coating
enamel slip at the initial point of the experiment. This is due to the increased
viscosity of the slip. The average adhesion strength at the initial time is 0.75
mN. As the graph demonstrates, few values could be measured due to fast drying
(Fig. 18.6).
4 0.013 g
3 0.015 g
0
0 0.5 1 1.5 2
Duration, min

kombi-ground slip, diameter of spherical particle 2.96 mm)
18.3.6 Study of Contact Layers of the Kombi-Ground Slip
In the study of the adhesion force of the kombi-ground slip, only two graphs could be
drawn since at 1.5 min intervals the slip dries out very fast, and the time is
insufficient to make any measurements. Both lines are directed straight upward
due to the emergence of the crystallization component. When measured at a time
lag of 30 s, the slurry starts to dry out at the point of 0.5 min (Fig. 18.7).
18.3.7 Study of Crystallization Process of Water Component

of Slip
To study the crystallization process of the water component of enamel slip, similar
experiments have been carried out, but not taking into account the adhesion force.
The drops of water component of enamel slip were analyzed under the microscope
after liquid evaporation to determine the patterns of particle distribution (Fig. 18.8).
The macrostructure of crystalline precipitate obtained after drop drying of water
component of kombi-ground slip (Fig. 18.8a) is inhomogeneous. A crystalline roller
has been formed at the drop edge. A secondary ring of small particles is emerging
along the drop edge.
The structure of the water component of coating enamel slip (Fig. 18.8b) is also
inhomogeneous. There are dense rings of particles resulted from approximating and
withdrawing the glass particle. The area of ring formation is wider than in case of
kombi-ground slip, which is probably due to the composition of water component.
As far as the water component of ground enamel slip (Fig. 18.8c) is concerned, it
shows heterogeneous structure and clear zoning. There is a crystalline roller at the
drop edge. There is a dark area: dark crystals fall from outside whereas smaller
crystals are inside.
Fig. 18.8 Macrostructure of crystalline precipitate (35x) obtained after drop drying of water
component of kombi-ground slip (a), coating enamel slip (b), and ground enamel slip (c)
The analysis of droplets of all filtrates has made it clear that there is consistent
formation of precipitate with crystals deposition mainly at the drop edge. As the
wetted perimeter is extended, salt deposition due to evaporation is observed, and this
is the cause for the ring-shaped distribution of precipitate.
18.4 Conclusion
When the capillary liquid volume is increased, the retention of liquid phase at the
particles contact is prolonged. If distilled water is used as capillary liquid, it is
possible to register the maximum amount of experimental points. When the filtrate
is used as capillary liquid, crystallization occurs due to water evaporation, and, as a
result, the retention time of liquid capillary phase is reduced. If enamel slip is used as
capillary liquid, in some cases the contact strength exceeds the upper limit of the
measuring instrument.
For various types of slips the capillary-crystallization effect reveals itself differ-
ently. For example, ground enamel slip shows longer retention time of liquid phase
at the particles contact in contrast to coating enamel slip as the viscosity of ground
enamel (102–103 Pa∙s) is lower than that of coating enamel (103.5–104 Pa∙s), and
hence water content is greater. The maximum number of measurements was taken
for kombi-ground slip.
References
1. Saavedra, J. H., Rozas, R. E., & Toledo, P. G. (2014). A molecular dynamics study of the force
between planar substrates due to capillary bridges. Journal of Colloid and Interface Science, 426,
145–151.
2. Amarasinghe, P. M., Anandarajah, A., & Ghosh, P. (2014). Molecular dynamic study of capillary
forces on clay particles. Applied Clay Science, 88–89, 170–177.
3. Shinto, H. (2012). Computer simulation of wetting, capillary forces, and particle stabilized
emulsions: From molecular-scale to mesoscale modeling. Advanced Powder Technology, 23
(5), 538–547.
4. Deryabin, V. A., Farafontova, E. P., & Malygina, O. L. (2001). Specifics of interaction of glass
batch particles via interlayers of two-component solutions. Glass and Ceramics, 62(1–2), 39–41.
5. Zarate, N. V., Harrison, A. J., & Litster, J. D. (2013). Effect of relative humidity on onset of
capillary forces for rough surfaces. Journal of Colloid and Interface Science, 411, 265–272.
6. Deryabin, V. A. (1997). Capillary forces in disperse systems [in Russian]: Izd-vo UGTU,
Ekaterinburg, 64 p.
7. Breinlinger, T., Hashibon, A., & Kraft, T. (2015). Simulation of the influence of surface tension
on granule morphology during spray drying using a simple capillary force model. Powder
Technology, 283, 1–8.
Chapter 19
Peculiarities of Formation of Phase
Structure and the Hydraulic Activity
of High-Calcium Fly Ash
I. Domanskaya and V. Oleinik
19.1 Introduction
The recovery of heat power engineering waste is an important environmental issue

for many countries at present. Fly ashes generated by the burning of solid fuel are of
high-quality, and low-cost mineral raw materials fail to require additional grinding
when combined with it. Fly ashes can replace natural raw materials in the production
of building materials for civil and highway engineering, landscape construction,
agriculture, and other branches of industry. The choice of the most effective ways of
waste disposal depends primarily on their chemical composition. Fly ashes
containing more than 10% of calcium oxide are referred to as high-lime ashes;
they possess hydraulic activity to a certain degree. In Russia a great quantity of
high-lime fly ash (HLFA) is produced by the commercial combustion of brown coal
Kansk-Achinsk field. Fly ashes containing up to 50% or more of silicon oxide can be
related to low calcium; they possess pozzolana activity. Low-calcium fly ash is
formed by the commercial combustion of bituminous coal.
19.2 Comparative Characteristics of Fly Ash Obtained

by Burning of Brown Coals by Various Means
The formation of phase composition of HLFA depends more on combustion tech-

nology as compared to low-calcium fly ash. This is due to the differences in the
mineral composition of lignite and bituminous coal.
I. Domanskaya (*) · V. Oleinik


https://doi.org/10.1007/978-3-319-75340-9_19
150 I. Domanskaya and V. Oleinik
19.2.1 Features of the Mineral Matter of Kansko-Achinsk

Brown Coals
The mineral part of the original solid fuel is a complex, heterogeneous substance
consisting of formations related to multiple genetic classes. Among its basic types
are biogenic, sorption, concretion, infiltration, and terrigenous ashes. The latter is
composed of minerals consisting of coal seams: quartz, clay substance, feldspars,
micas, volcanic ash, and others. As a rule, this is the predominant class dominating in
all coals possessing moderate- and high-ash content. Low-ash lignites are charac-
terized mainly by biogenic and sorption ash, the main element being calcium. In
sorption ash calcium and, to a lesser extent, aluminum, iron, and magnesium form
salt-like compounds – humates – or complex ones of chelates type. Biogenic ash is
formed from the basic components of chlorophyll (calcium, silicon, magnesium,
potassium) and also traces elements entering the enzymes composition. As the
thermal metamorphism of coal from lignite to anthracite, their ash is depleted of
biogenic and sorption components [1, 2].
Concretionary ash is formed together with sorption ash on peat coal formation
stage. It is not associated with organic matter but represented by such mineral forms
as siderite, ankerite, dolomite, kaolinite, and others. Infiltration ash is formed in the
cracks of coal seams from hot or cold groundwaters and is represented by sulfides,
carbonates, sulfates, calcium, iron, quartz, and other minerals. The particle size of
сoncretion and infiltration ash can be very different, from molecular size to tens of
centimeters, and the share in the overall balance is extremely changeable.
In Russian scientific literature devoted to the issues of burning of Kansk-Achinsk
coal, there is a conventional distinction between “external” and “internal” ash. It is
assumed that “internal” ash is a combination of sorption and biogenic ash, while
“external” ash is represented by terrigenous ash and separate large particles belong-
ing to other genetic classes. Young Kansk-Achinsk coals are characterized by high
content of “internal” ash, up to 50–60%. With a decrease in ash content to less than
3%, the “internal” mineral part is revealed in coals. The content of Cao may increase
to 70% and above [3].
19.2.2 Characteristics of the Fly Ash Tested
Three groups of fly ashes were investigated in the present work. Samples Nos. 1–6
were obtained at the Siberia TPS when burning brown coals in a flame burner in
question according to the molten slag removal (the temperature in the core of the
torch reaches 1600–1700 C). Samples Nos. 7–12 were obtained at the TPS when
burning brown coals in a flame burner in question according to the hard slag removal
(the temperature in the core of the flame is 1300–1400 C). Samples Nos. 13–16
were obtained as a result of experimental burning of brown coals at the commercial
pilot plant with circular fluidized bed (CFB) at a temperature of about 900 C.
19 Peculiarities of Formation of Phase Structure and the Hydraulic. . . 151
Table 19.1 Binding properties of the fly ashes investigated
Specific Normal Terms of setting, Compressive Content

surface, m thickness of h/min. strength, MPa, of CaO
2
Numbers /kg the paste, % Beginning Ending 28 days free, %
1 388 35 0–20 0–27 7.7 11.5
2 363 33 0–29 0–46 8.8 8.5
3 430 25 0–44 1–09 4.8 5.6
4 480 31 2–35 3–20 10.6 1.0
5 640 26 0–35 1–25 8.3 6.0
6 310 25 0–27 0–35 10.0 3.2
7 240 25 0–40 0–57 5.2 2.8
8 250 20 0–30 0–43 3.0 4.0
9 240 21 0–27 0–37 6.0 3.1
10 700 27 0–09 0–12 20.0 3.9
11 650 32 0–22 0–28 17.5 8.3
12 420 30 .0–17 0–30 10.0 6.0
13 350 29 0–30 0–39 6.3 7.5
14 840 86 1–40 2–50 4.0 5.9
15 610 54 0–32 0–40 5.9 5.4
16 500 45 0–25 0–38 11.0 7.7
All the samples of ashes studied contain free lime (free СаО) and possess binding
properties. The hydraulic activity of ashes was assessed by the size limit of the
compressive strength. The results of the determination of the binding properties of
the fly ashes are presented in Table 19.1.
It was determined that the lightest fly ashes with bulk density 470–800 kg/m3
were formed in the furnaces CFB. The particles of such ashes are the aggregates of
tiny grains vitrified and mineralized remnants of organic origin in the form of
“chains” and “branches.” Fly ashes obtained by burning brown coals by flame
burners having bulk density of 990–1200 kg/m3 consist of coarse ball-type particles
of different size and color with the refractive index 1.49–1.79 [4].
As to the chemical composition of fly ashes, it is characterized by instability
(Table 19.2).
The reduction of the temperature of burning brown coals leads to a decrease in the
content of vitrified phase from 67.32% to 16.98% (according to the rational analysis
of chemical). The quantity of CaSO4 and СаСО3 increases (according to X-ray
phase analysis). It should be noted that among crystalline phases regardless of the
method of producing ash, β-quartz can be identified, free СаО, MgO, and also some

clinker minerals identified in the range of angles θ ¼ 15–18 [4].
Table 19.2 Evaluation of chemical composition of fly ashes investigated

Oxides content, %, for ashes obtained at the temperature, C
Oxides 1600–1700 1350–1400 850–880
SiO2 23.68–32.22 17.05–34.16 10.18–21.80
Kvar, % 13.74 22.68 44.05
Al2O3 7.69–10.13 9.36–13.02 7.35–10.88
Kvar, % 12.34 13.01 16.24
Fe2O3 9.35–11.17 6.87–12.70 5.33–12.87
Kvar, % 7.31 23.75 32.47
CaO 33.75–38.82 31.33–43.92 31.87–45.30
Kvar, % 5.81 9.65 12.24
MgO 4.52–6.20 4.58–6.97 5.62–3.71
Kvar, % 12.07 13.78 14.74
SO3 2.61–5.94 2.64–12.62 6.72–15.14
Kvar, % 30.92 46.91 32.35
Kvar – variation coefficient
19.3 Discussion of the Results and Predicting Fly Ash

Contents Depending on the Ways of Brown Coals
Burning
From the analysis of fly ashes, we can conclude that considerable differences of the
composition and fly ash properties obtained from burning brown coals in different
furnaces are first and foremost conditioned by the availability of “external ash”
(quartz, clay, feldspars, limestones, gypsum, and other enclosing rocks) and “inter-
nal ash” of biogenic origin. The flame burning way is characterized by a high degree
of coal grinding (up to 0.2 mm) providing more uniform distribution of mineral part
on fractions and better interaction of components of “external” and “internal” ashes.
For coal grains to be burnt in CFB, their diameter is adjusted – to 10 mm – and is
decreased as the even burning out takes place by multiple circulation through the
burning zone. Redistribution of mineral components depending on their grinding
and enrichment of fly ash CFB by components of “internal ash” is likely to take place
in this case.
In order to determine the most probable low temperature reactions of the products
influencing the hydraulic activity of fly ash afterward, thermodynamic calculations
of Gibbs energy were performed. It was established that the supposed CaO isolation
from the organic substance (400–600 C) and its interaction with sulfate component
of gas phase are more advantageous thermodynamically. Therefore, CFB fly ashes
compared to flame burned ones are enriched by anhydrite. Free CaO is likely to be a
product of CaCO3 decomposition coming from the “external” mineral part, also the
secondary one, the formation of which cannot be excluded taking into account the
calculated data (Table 19.3). As far as flame burned fly ashes are concerned, the main
19 Peculiarities of Formation of Phase Structure and the Hydraulic. . . 153

Table 19.3 Data of Gibbs –ΔGТ, kJ/mol/ C
energy calculation
Compounds 600 800 1000 1200
CaSO4 280.69 243.94 208.11 173.62
СаСОз 82.80 52.47 22.97 5.79
CaОSiО2 90.17 90.63 90.97 –
2 CaОSiО2 130.48 132.29 134.29 136.44
CaOA2O3 27.19 31.40 36.01 41.11
12 CaO7A2O3 191.42 234.17 276.75 319.99
2 CaOFe2O3 61.13 68.47 75.67 82.62
Fig. 19.1 Scheme of the transformations of the mineral part of brown coal
processes of the phase formation include desulfurization, solid phase interaction and
caking, melting, and crystallization from the melt (Fig. 19.1).
The analysis of the CaO-Al2O3–SiO2 state diagram and the fusibility curve
construction of Nos. 1–12 compositions allowed us to establish that the most likely
phase crystallizing on melt cooling consisting of more than 33–35% CaO is belite,
and on that consisting of less CaO content is gelenite. However, the low viscosity
indicators of the compositions under investigation in the latter case contribute to the
conservation of vitrified state at the moment of fly ash particles cooling down, which
is confirmed by the X-ray diagram character and is also indicative mainly of
pozzolana mechanism of their hardening when mixed with water. CaO free present
in flame burned ashes is likely to be the product of the secondary sulfates
decomposition.
Thus, it can be concluded that the phase composition and the hydraulic activity of
high-calcium fly ashes depend on their mineral part and the “external”: “internal”
ratio of ashes, the degree of grinding, temperature, the way of coal burning proper,
oxidation-reduction character of gas medium, the duration of the particles stay in the
furnace chamber, and the place of sampling in the system of fly ash trapping.
References
1. Karlowska, M. S., & Rivkin, A. S. (1973). In A. Ots (Ed.), The influence of the mineral part of the
Siberian coal contamination of the heating surfaces of steam generators. Novosibirsk: The
Institute of physical and chemical principles of mineral processing.
2. Yudovich Ya, E., & Ketris, М. P. (2005). Toxic trace elements in coal. Ekaterinburg: UrB RAS.
3. Gamow, M. I., & Granovsky, N. (2012). In S. V. Levchenko (Ed.), Metals in coals. Rostov-on-
Don: SFU.
4. Domanskaya, I. K., & Oleinik, V. N. (2006). High-calcium fly ash: Forming of composition and
hydraulic activity. Ibausil 16. Internationale Baustofftagung – Weimar, рр. 1-1071–1-1079.
Part IV
High-Pressure Treatment of Metals and
Alloys
Chapter 20
Modernisation of the Method of Rolling
of Hot-Rolled Tubes
A. Bogatov, D. Pavlov, and E. Pavlova
20.1 Introduction
The advantages of pipe-rolling plants (PRP) with an automatic plug rolling mill are
high maneuverability enabling one to change over from one pipe dimension type to
another within a short time; relatively high output (150,000–250,000 ton of pipes per
year) [1–3]; and the ability of making large tonnage batches of a wide range of rolled
products from carbon, alloy and high-alloy steels. The disadvantages of PRP with an
automatic plug rolling mill are low elongation ratio, long time of auxiliary operations
and non-uniform rough tube wall thickness. The installation of a continuous mill
instead of an automatic one would eliminate the above-mentioned shortcomings;
however, the reconstruction of a PRP always involves considerable material costs.
Besides, new equipment may fail to be installed in place of the old within the existent
shop layout. In these terms, it seems expedient to improve the current process of
plugging.
The PRP-140 pipe-rolling plant made by the “Sintz” public joint-stock company,
which comprises a tandem-type automatic plug rolling mill consisting of two length-
wise rolling mills (LRM-1 and LRM-2) has enabled the time of auxiliary operations
to be reduced due to a sequential arrangement of the stands. However, the elongation
ratios remain rather low. With LRM-1, the elongation ratio is λ ¼ 1.161.5, and with
LRM-2 it is λ ¼ 1.071.15. Rough tubes have transversely non-uniform wall
thickness, which is partially eliminated during rolling by a three-roll sizing mill.
The study aims at improving the plug rolling process, when rolling is performed
with high elongation ratios, and wall thickness variation of rough tubes becomes
less. A higher elongation ratio in plug rolling will enable PRP-140 to produce
A. Bogatov · D. Pavlov (*) · E. Pavlova

Institute of Material Science and Metallurgy, Ural Federal University, Yekaterinburg, Russia
e-mail: d.a.pavlov@urfu.ru

https://doi.org/10.1007/978-3-319-75340-9_20
158 A. Bogatov et al.
thin-walled pipes with the ratio D/S >33 and to reduce the elongation ratio in
piercing. A lower elongation ratio in piercing will increase the precision of shells
and decrease rolling skin.
20.2 A Study of Forming in the Rolling of Round and Oval

Billets
It was found during industrial research that a higher elongation ratio on an automatic
tandem mill causes increased spoilage due to various defects, including “guide
marks.” A “guide mark” defect appears as follows (Fig. 20.1): (1) when rolling is
performed on LRM-1, there is intensive metal flowing into the tapers, and this results
in thicker pipe walls in the tapers than in the upper part of the groove. This causes
stripes on the pipe surface (Fig. 20.1a); (2) after turning about the pipe axis through
90 , the pipe is rolled in LRM-2; and the stripes get into the tapers (Fig. 20.1b). After
the groove is filled (Fig. 20.1c), the stripes are deformed on the mandrel, and this
causes jamming (Fig. 20.1d); (3) When rolling is performed in a three-roll blooming
mill and then in a stretch-reducing or sizing mill, jamming on the inner tube surface
turns into longitudinal “guide marks.”
Staper
Wall thickness in a taper is characterised by the nondimensional parameter Supper
(Staper and Supper are rough tube wall thickness, respectively, in the taper and the
upper part). Figure 20.1 presents the cross sections of a deformation zone for
plugging on LRM-1 (a) and LRM-2 (d, b, c).
Fig. 20.1 Scheme “guide mark” defect formation on the inner tube surface. (a) The formation of
stripes on the pipe surface. (b) Deformation of the stripes into the tapers. (c) The groove filling.
(d) The formation of the jamming
20 Modernisation of the Method of Rolling of Hot-Rolled Tubes 159
Fig. 20.2 A 3D model of

LRM-1 with edger rolls
Fig. 20.3 A schematic of bite in the rolling of round (a) and oval (b) shells
In the course of computer simulation in the DEFORM software, it was found that
the stripe size can be decreased by mounting edger rolls before the stand of LRM-1,
which make the shell oval before plugging in LRM-1 (Fig. 20.2). When tasks were
set in DEFORM, the boundary conditions were specified according to the practical
data and recommendations given in Ref. [4].
When a round shell is fed into LRM-1, the bite begins at the tapers (Fig. 20.3a).
Flattening and some reduction result in the filling of the whole groove, the metal
flows intensively into the groove tapers, and the pipe wall becomes thicker in the
groove taper. When an oval shell is fed into a hexahedral groove, it is bitten by the
working rolls of LRM-1 in the upper part of the groove (Fig. 20.3b), not in the taper
zone. This reduces shell flattening and offers a better bite. Besides, edger rolls
restrain metal flow into the groove tapers and reduce the size of the stripes. Thus,
the stripes appearing during oval shell rolling are smaller than those appearing
during round shell rolling, and, consequently, the appearance of a “guide mark”
becomes less probable.
1.9
1.85
1.8
1.75
Staper 1.7
Sup
1.65
1.6
1.55
1.5
1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2
λ
Staper
Fig. 20.4 The parameter Sup as dependent on the elongation ratio λ in rolling on LRM-1 with edger
rolls
The computer simulation has shown that, when the shell ovalisation coefficient
S
ξ ¼ 1.25 [5, 6], the nondimensional parameter Staper
up
decreases by 31%, i.e., the use of
edger rolls reduces the size of stripes.
According to experimental data on shell plugging
on LRM-1 without edger rolls,
Staper S
the ratio Sup must not exceed the critical value Staper
up
¼ 1.80 [7, 8]. When it does, a
cr
S
“guide mark” defect occurs. Figure 20.4 presents a plot of Staper
up
as a function of the
elongation ratio for rolling in LRM-1 with edger rolls.
It is obvious from Fig. 20.4 that, as the elongation ratio λ increases, the wall
S
thickness in the groove taper increases. When λ ¼ 2.00 and Staper
up
¼ 1.77, it does not
exceed the critical value. Thus, when edger rolls are placed before the stand of
LRM-1, the elongation factor can be increased from 1.50 to 2.00.
20.3 Developing the Process of Pipe Plugging on a Stub

Mandrel with Kinematic Tension
In order to study the possibility of a further increase in the elongation factor,

computer simulation of pipe plugging with kinematic tension was made. Tension
was created by means of another pair of edger rolls mounted behind the working
stand of LRM-1. Figure 20.5 presents a hard-body model of a mill with two pairs of
edger rolls.
The study of forming of a rough tube rolled in LRM-1 has shown that kinematic
tension considerably decreases the intensity of wall thickening in the tapers.
S
Table 20.1 demonstrates measured values of Staperup
as dependent on the kinematic
tension coefficient ω.
20 Modernisation of the Method of Rolling of Hot-Rolled Tubes 161
Fig. 20.5 A hard-body model of LRM-1 with two pairs of edger rolls
Staper
Table 20.1 Measured values of Sup as dependent on the kinematic tension coefficient ω
Computational experiment number 1 2 3 4 5

Kinematic tension coefficient ω 1.02 1.04 1.06 1.08 1.1
Staper 1.49 1.47 1.46 1.44 1.42
Sup
It is obvious from Table 20.1 that, as the kinematic tension coefficient grows, the
S S
parameter Staper
up
decreases. The lowest value of Staper
up
¼1.42 is observed when ω ¼ 1.1. It
has been found by computer simulation that this value of kinematic tension on
one to increase the elongation ratio to λ ¼ 2.40, with the critical
LRM-1 enables
S S
value of Staper
up
not being exceeded (when λ ¼ 2.40, Staper
up
¼ 1.73).
cr
20.4 Conclusion
It has been found within the study that shell ovalisation with the aid of edger rolls
before rolling in LRM-1 reduces the non-uniformity of rough tube walls. Besides,
with the maximum possible kinematic tension on LRM-1, that is, ω ¼ 1.1, one
manages to reduce wall thickening in the groove tapers considerably, thus decreas-
ing the probability of “guide mark” defects at high elongation ratios. Computer
simulation of pipe rolling in LRM-1 suggests that the elongation ratio can be raised
from 1.5 to 2.4. A higher elongation ratio in plugging enables one to produce thin-
wall pipes with D/S >33 on PRP-140 and to increase the precision of shell dimen-
sions due to lower elongation ratio in piercing.
This research is supported by the President of the Russian Federation grant

number MK-3011.2017.8.
References
1. Kharitonov, V. V., Bogatov, A. A., & Vakhrushev, V. Y. (2008). Equipment for pipe rolling,
extrusion and drawing. Ekaterinburg: USTU-UPI.
2. Potapov, I. N., Kolikov, A. P., & Druyan, V. M. (1991). Theory of pipe making. Moskva:
Metallurgiya.
3. Danchenko, V. N., & Kolikov, A. P. (2002). Romantsev, B.A., pipe-making technology. Moskva:
Intermetinzhiniring.
4. Karamyshev, A. P., Nekrasov, I. I., & Pugin, A. I. (2010). A manual for the program deform-3D
software package. Ekaterinburg: UrFU Publ.
5. Bogatov, A. A., Pavlov, D. A., Lipnyagov, S. V., & Suvorov, V. N. (2012). Simulating the
formation of a “guide mark” defect on the inner tube surface in lengthwise rolling. Proizvodstvo
prokata, 8, 37–39.
6. Bogatov, A. A., Pavlov, D. A., & Dresvyankina, E. A. (2014). Development of a mathematical
model for a new process of lengthwise pipe rolling: In Metal forming 2014, fundamental
problems (Advanced materials and technologies, pp. 102–106). Ekaterinburg: UrFu Publication.
7. Bogatov, A. A., Pavlova, E. A., & Pavlov, D. A. (2014). Finite-element simulation of the process
of lengthwise pipe rolling on a stub mandrel. In: Proceedings of the 3rd International Conference
COMAT.
8. Bogatov, A. A., Pavlov, D. A., Lipnyagov, S. V., Suvorov, V. N., & Pavlova, E. A. (2014).
Rolling hot deformed pipes on a stub mandrel. Steel in Translation, 44(12), 912–915.
Chapter 21
New Engineering Solutions
in the Production of Laminated Composite
Pipes for the Oil Industry
N. A. Bogatov, A. Bogatov, and D. R. Salikhyanov
21.1 Introduction
Russia is one of the world leaders in oil production and the largest participant in the
world energy market. Since the 2000s, oil production in Russia had been growing
steadily before this growth slowed down some time ago. Note that the conditions for
oil production in Russia have changed since the early 2000s. Thus, the development
of new oil fields shifts to more and more unfavorable regions in terms of geological
and climatic conditions, whereas oil extraction in regions discovered and developed
30–50 years ago is characterized by high water cut and intensive corrosive attack of
downhole equipment. Due to the simultaneous effect of such factors as the presence
of dissolved H2S and СO2 gases in the fluid to be extracted, abrasive wear and tensile
stresses, pump-compressor pipes (PCP) suffer the hardest conditions. This is verified
by the analysis of the reasons for the failure of downhole pumping equipment, which
demonstrates that the contribution from the failure of PCP into malfunction is
predominant, and it amounts to about 60%. The experience of operating corrosive
wells shows that the service life of PCP in them sometimes does not exceed 4 months
[1–7]. The operation of such a well is extremely difficult and involves considerable
costs for the restoration of the efficiency of the pump-compressor column. The
restoration costs for each well amount to about 350,000 RUB, annual emergency
failures of pump-compressor columns, including those in oil industry, are numbered
in thousands, and expenditures for failure elimination amount to hundreds of
millions RUB.
N. A. Bogatov (*)
“TEMP” Limited Scientific Production Association, Moscow, Russia
e-mail: nb0612@yandex.ru
A. Bogatov · D. R. Salikhyanov
Institute of Material Science and Metallurgy, Ural Federal University, Yekaterinburg, Russia

https://doi.org/10.1007/978-3-319-75340-9_21
164 N. A. Bogatov et al.
To replace PCP that have exhausted their service life, the pipe industry of Russia
annually provides oil companies with about 250,000 ton of new pipes. Medium-
carbon manganese steels (30G2, 35G2S, etc.) and chromium-molybdenum steels
(30KhMA) are more often used as pipe material; however, they are not corrosion
resistant enough.
The analysis of the scientific and technical documentation for PCP [8, 9] shows
that the Russian standards do not provide any sufficient requirements in terms of
resistance to corrosive attack, and this, to some extent, restrains the improvement of
the quality of pipe products. The world practice of oil production pays much
attention to the resistance of PCP to attack by aggressive media. Thus, PCP made
of various groups of stainless steels and corrosion-resistant alloys, namely, austenitic
stainless steels, ferritic stainless steels, and martensitic stainless steels, has found a
wide application under conditions of complicated oil extraction. A number of
Russian and foreign studies deal with an efficient choice of steel or alloy grades
and formulation of the matrix of choice for the pipe material depending on specific
conditions of oil production, namely, on temperature and the content of the CO2 and
H2S components in the well [1–5, 10–12].
21.2 Trends in Increasing the Durability of Pump-

Compressor Pipes
The main trends in solving the problem of increasing the life of downhole pumping
equipment [13] used by oil-producing companies are (1) corrosion inhibition by
feeding a chemical reagent to the pump intake and to the hole clearance,
(2) downhole treatment by periodic pumping of a chemical reagent, (3) use of
corrosion protectors against electrochemical corrosion (sacrificial anodes), (4) intro-
duction of PCP made of high-alloy steels in the anticorrosion version, and (5) appli-
cation of special anticorrosion coatings onto the inner surface of PCP. These
measures require extra costs. Another line of increasing the life of PCP is the
application of repair technologies, service companies having been created for this
purpose. The current repair technology consists of cleaning the inner surface of pipes
from deposition and cutting out defective areas; however, the lifetime of repaired
pipes is reduced due to the retention of defects and corrosion pits intensifying the
processes of corrosion in the second stage of pipe operation. The performance,
reliability, and lifetime of pipes can be radically increased through making them
from laminated composite materials. In the world practice, these materials have
found application in many industries. Laminated composite pipes can be produced in
several principally different ways, namely, longitudinal welding of bimetal sheets,
producing pipes by simultaneous expansion, liquid diffusion welding along inter-
faces, explosion welding, centrifugal casting, and hot isostatic extrusion [14–18]. In
oil and gas industry, there is a positive experience of testing experimental-industrial
batches of laminated composite pipes in oil wells in the Netherlands, the USA,
Indonesia, New Zealand, Norway, the UK, the Philippines, Malaysia, Japan, and
21 New Engineering Solutions in the Production of Laminated Composite. . . 165
Russia. Among the known methods of manufacturing pipes from laminated com-
posite materials, lining should be distinguished. Lining consists of simultaneous
expansion of a pipe made of conventional carbon or low-alloy steel (external shell)
and a thin-wall pipe made of corrosion-resistant high-alloy steel (internal shell), the
pipes being joined due to compressive residual stresses on the interlayer boundary.
21.3 Developing a Technology for Producing Lined

Pump-Compressor Pipes
The general flow of the process of lining pump-compressor pipes is discussed in

enough detail in Refs. [17–19]. The process is based on simultaneous expansion of
shells on a mandrel (Fig. 21.1). A distinctive feature of the pipe lining technology is
the presence of a sealant between the shells, which is intended for preventing
corrosion on the interlayer boundary between the metals of the shells, avoiding the
loss of air tightness of the annular gap and increasing the reliability of the adhesion
between the shells. Another advantage of using a sealant is the possibility of using
worn pump-compressor pipes as initial billets. In this case, the sealant fills internal
defects and pits formed in a worn pipe in the first stage of operation and excludes the
risk of the resumption of corrosion processes on the inner surface of the external shell.
The technology being developed includes the following principal operations:
1. Incoming inspection and preparatory operations
2. Calibration of the inner surface of the PCP by expansion on a mandrel
3. Preparation of the PCP ends and the liner for expansion
4. Installation of the PCP and the liner with a sealant applied to its outer surface
5. Simultaneous expansion of the PCP and liner on a mandrel
6. Polymerization of sealant of the lined pipe
Fig. 21.1 A scheme for simultaneous expansion of pipes on a mandrel

Lined pump-compressor pipes produced by this technology have a longer service

life than new seamless pipes due to the following advantages:
• The internal thin-wall liner made of high-alloy steel is responsible for corrosion
resistance, the external shell (pump compressor pipe) being responsible for
structural strength.
• Low content of harmful impurities in the liner metal contacting with the aggres-
sive environment in a well.
• Higher plasticity of the liner metal than that of the seamless pump-compressor
pipe, which makes lined pipes reparable, reliable, and durable.
• The smoothness of the inner surface of the liner Ra of 0.5–0.6 μm.
• The presence of a sealant on the interlayer boundary, which prevents electro-
chemical corrosion between the shells made of dissimilar metals and increases the
reliability of adhesion between them.
• Feasibility of heat treatment under different conditions for the internal and
external shells, depending on the purpose (ensuring good mechanical property
for the external shell and high corrosion resistance for the internal one).
The proposed technology of manufacturing lined corrosion-resistant pipes is
pioneered in the Russian and world practice of pipe production, and this is validated
by the analytical survey of the literature discussing only some theoretical results
concerning the process of manufacturing lined pipes. Therefore it is necessary to
develop requirements for billets and performing individual technological operations
of making lined pipes. To produce high-quality lined pump-compressor pipes, it is
required that (1) reliable adhesion between the liner and the pump-compressor pipes
be ensured and (2) the lined pipes meet the requirements of the Russian and world
standards in terms of size precision, the level of mechanical properties, and corrosion
resistance.
To solve the problems, it is necessary to study the stress-strain state of pipes
during simultaneous deformation on a mandrel, as well as the mechanics and
kinematics of the flow of the layers. Since the process is new and poorly studied,
the problems stated is solved in the Deform-3D finite element simulation software,
which enables design and technological problems to be solved. A general view of the
solution is presented in Fig. 21.2.
Fig. 21.2 A general view of the computer simulation of simultaneous pipe expansion on a mandrel
In view of the features of expanding laminated composite materials on a mandrel,

a mandrel design has been developed, and the dimensions of the mandrel ensuring
the adhesion between the initial round billets have been calculated.
21.4 Testing Lined Pump-Compressor Pipes Under Field

Conditions
Pilot models of a composite pipe were made from six pieces of worn PCP, 1700 to
1900 mm long. Before lining, on three of the six worn PCP with more than 1.9 mm
deep defects, 3 mm diameter through holes were additionally made in the midsection
(four on each). The worn PCP was lined by expansion with 47 1.5 mm electrically
welded pipes made of steel 10. The interlayer clearances and thread connections of
the fabricated pipe were sealed with a sealant. The pieces were joined on the thread
by sockets. The fabricated bimetal pipes were tested on a “Brocker” hydraulic press
in pipe-making department No 4 of the Pervouralskiy Novotrubniy Zavod JSC
(Pervouralsk New Pipe Plant). The hydraulic pressure was changed in six steps
from 14.7 to 56.9 MPa with a 60 s hold. The test results have demonstrated that the
fabricated 9500 mm long bimetal pipe withstands a test under pressure exceeding by
13% the standard value according to the Russian standard GOST R 52203–2004 for
conventionally made PCP of the D strength group. No depressurization of the
interlayer clearances and thread connections with complete preservation of the
carrying capacity along the entire bimetal pipe, including the portions with 3 mm
diameter through holes drilled in body of the PCP, is observed.
Pilot batches of bimetal PCP made by lining from worn 73 5.5 mm pipes with
1.9–3.4 mm deep defects have been tested under field conditions on four facilities
the “Tatneft” JSC. The PCP service conditions on all the facilities are estimated as
severe. Thin-wall electrically welded liner pipes were made of steel 22GYu
according to the Russian standard specifications TU 1373-021-05757850-07. The
lined PCP from the pilot batch have been operated since March 4, 2009 (for more
than 2000 days), and there is no criticism about the quality and efficiency of repaired
pipes. Regular inspection of the quality of PCP by visual examination and
hydrotesting, both involving pipe lifting from the wells, has not revealed any quality
faults. The inspected pipes continue being operated in the normal mode.
21.5 Conclusion
The creation of the process of producing lined PCP and bringing it to commercial
level is aimed at increasing the engineering and economic performance of oil
production in Russia and multiply decreasing power inputs for the maintenance
and operation of oil wells, and this corresponds to the national and global scientific
and technological priorities, the state program “Energy Efficiency and Energy Sector
Development” approved by Russian Federation Government Regulation No
321 dated April 15, 2014, the priority lines of research, technology and engineering,
and the list of critical technologies approved by RF Presidential Edict No 899 dated
July 7, 2011.
The cost-effectiveness of the production and consumption of lined pump-
compressor pipes results from lower maintenance costs of pump-compressor col-
umns due to longer service life of lined PCP than that of new pipes. The restoration
of PCP by lining offers a more than four times increase in durability and a multiple
decrease in the expenditure of material and financial resources for buying new pipes
(instead of lined), repairing, and maintenance of PCP and oil wells.
The study was made within the basic part of the state job in the field of scientific
activity No. 11.9538.2017/8.9; it was supported by Act 211 of the Government of
the Russian Federation (agreement No. 02.A03.21.0006).
References
1. Ioffe, A. V., Vyboishchik, M. A., Trifonova, E. A., & Suvorov, P. V. (2010). Effect of chemical
composition and structure on the resistance of oil pipelines to carbon dioxide corrosion. Metal
Science and Heat Treatment, 52(1–2), 46–51.
2. Ioffe, A. V., Tetyueva, T. V., Vyboyshchik, M. A., Trifonova, E. A., & Lutsenko, E. S. (2010).
Tubing with high corrosion resistance. Metal Science and Heat Treatment, 52(1–2), 13–19.
3. Ioffe, A. V., Tetyueva, T. V., Vyboyshchik, M. A., Knyaz’kin, S. A., & Zyryanov, A. O.
(2010). Corrosion-mechanical fracture of tubing from carbon and alloy steels operating in
environments containing hydrogen sulfide. Metal Science and Heat Treatment, 54(9–10),
492–497.
4. Knyaz’kin, S. A., Ioffe, A. V., Vyboyshchik, M. A., & Zyryanov, A. O. (2010). Special features
of corrosion fracture of tubing operating in environments with elevated content of carbon
dioxide. Metal Science and Heat Treatment, 54(9–10), 498–503.
5. Ioffe, A. V., Tetyueva, T. V., Revyakin, V. A., Borisenkova, E. A., Knyaz’kin, S. A., &
Denisova, T. V. (2010). Corrosion-mechanical fracture of tube steel in operation. Metal Science
and Heat Treatment, 54(9–10), 512–518.
6. Smith, L. (1999). Control of corrosion in oil and gas production tubing. British Corrosion
Journal, 34(4), 247–253.
7. Brondel, D., Edwards, R., Hayman, A., Hill, D., Mehta, S., & Semerad, T. (1994). Corrosion in
the oil industry. Oilfield review, 6(2), 4–18.
8. GOST R 52203–2004. Pump-compressor tubes and couplings for them. Specifications.
9. API Specification 5CT. Specification for casing and tubing. 8th ed, July 1, 2005. ISO
11960:2004, Petroleum and natural gas industries – Steel pipes for use as casing or tubing for
wells.
10. Cerruti, S. (1998). An overview of corrosion resistant alloy steel selection and requirements for
oil and gas industry. Conference: Convegno IGF XIV Trento. 1–9.
11. Craig, B. D., & Smith, L. (2011). Corrosion Resistant Alloys (CRAs) in the oil and gas industry
– selection guidelines update. 3rd ed. US: The Nickel Institute.
12. Craig, B. D. (2011). Selection guidelines for corrosion resistant alloys in the oil and gas
industry. Materials selection for the oil and gas industry, Nickel Institute Technical, 10(73),
1–11.
13. Safonov, V. N., & Kim, S. K. (2012). Performance of the wells of the OOO Lukoil-Komi under
corrosive conditions. Inzh. Praktika, 1, 50–59.
14. Smith, L. M. (1992). Engineering with clad steel. NiDI Series, 10(064), 20.
15. Wang, X., Li, P., & Wang, R. (2005). Study on hydro-forming technology of manufacturing
bimetallic CRA-lined pipe. International Journal of Machine Tools & Manufacture, 45,
373–378.
16. Koning, A. C., Nakasugi, H., & Ping, L. (2004). TFP and TFT back in town (Tight Fit CRA
lined Pipe and Tubing). Stainless steel world, 53–61.
17. Bogatov, N. A., Bogatov, A. A., & Salikhyanov, D. R. (2014). Corrosion-resistant lined pump
and compressor pipe. Steel in Translation, 44(11), 867–869.
18. Bogatov, N. A., Bogatov, A. A., & Salikhyanov, D. R. (2014). Use of the lining method to
restore the service characteristic of pump-compressor tubing that has exhausted its original
service life. Metallurgist, 58(11–12), 1006–1010.
19. Bogatov, N. A. Patent № 2344266 RF, IPC E21V17/01, “Method of making pump-compressor
tubing”, subm. 04.17.2007, publ. 09.20.2007.
Chapter 22
Precision of the Tubes Produced
by Drawing and Cold Rolling
G. Orlov
22.1 Introduction
Classical methods of cold deformation оf tubes are drawing through stationary dies
and cold rolling by rolls and rollers. The combination of these methods provides a
wide assortment of cold-deformed tubes and their high quality. However, classical
methods have a number of deficiencies: in the case of drawing, the probability of
formation marks is great, and cold rolling is characterized by high power consump-
tion, small productivity, complexity of adjustment of camps, and tool manufactur-
ing. Therefore, the problem of working out and research of new or combined
methods of cold deformation is topical.
There are “technological niches” that can be discovered in the course of devel-
oping new and combining the existing methods of drawing and cold rolling. One
such opportunity is the design of dies with specific technological characteristics. For
example, for the drawing of tubes – in which case the main tools are a die and a
mandrel – it is possible to construct a matrix of drawing methods Bij based on the
type of movement of the tools (see Table 22.1).
The use of a die in accordance with scheme B11 corresponds to the traditional
method of drawing metal through stationary mandrel; method B31 corresponds to
drawing on a long moving mandrel. Methods B12 and B32 entail drawing through
rotating dies. Methods of type B41 make use of a reciprocating mandrel. One of these
methods, called periodic drawing, was developed with the author’s participation and
is examined below. Methods B13 and B14, which also employ a rotating mandrel and
have the die move counter to the tube, are not known to have yet been put into
practical use and are probably regarded as technological niches. А countermoving
die can also be employed for the cold rolling of tubes. In this case, the types of
G. Orlov (*)

https://doi.org/10.1007/978-3-319-75340-9_22
172 G. Orlov
Table 22.1 Matrix of Motion of the die

drawing methods
Types of motion of the mandrel 1 2 3 4
1 – Stationary 1–1 1–2 1–3 1–4
2 – Rotation 2–1 2–2 2–3 2–4
3 – Translation 3–1 3–2 3–3 3–4
4 – Reciprocating motion 4–1 4–2 4–3 4–4
Fig. 22.1 The computer

model of roller drawing of
tubes: 1, rollers; 2, tube;
3, mandrel
movement of the working stand and the mandrel and the number of rolls in the stand
are among the most important technical factors.
This chapter describes the use of mathematical modeling to examine several
approaches to improving the operations of drawing and cold rolling.
22.2 Сomputer Modeling
The finite-element method was used to study the correction of initial eccentric
thickness variation in the course of roller drawing of tubes through one and two
consistently established die cases [1] (Fig. 22.1). As cross-section thickness varies
by 70–80%, it is defined by an eccentric component; for theoretical analysis, the
initial thickness variation is presented in the following way:
Sθ ¼ Sm E cos θ, ð22:1Þ
where Sm ¼ (R0 – r0) is the medium thickness of a wall; R0 and r0, respectively, the
external and internal radiuses of cross section of stock; Е, excentricity; and θ ¼ 0 . . . 2π,
angular coordinate of the cross section (zero value corresponds to the minimum
thickness of a wall).
22 Precision of the Tubes Produced by Drawing and Cold Rolling 173
As a result of processing data of computing experiment, the regression depen-

dence for final thickness variation was obtained:
δК ¼ 2:36 þ 3:13μ 501:07K P þ 13260:44K 2P þ 5:44K P δ0

ð22:2Þ
2125:90K P ψ þ 23:84μψ þ 39:16ψ,
where μ is the elongation ratio factor; Kp, factor of roller pass; δ0, initial excentric
thickness variation; and ψ, friction factor by Siebel.
The optimum factor of roller pass providing minimum thickness variation is
found from Eq. (22.2) on the condition ∂δK/∂Кр ¼ 0:
2125:90ψ 5:44δ0 þ 501:07

KP ¼ : ð22:3Þ
26520:88
The analysis has shown that for the correction of the initial thickness variation
δ0 in the course of roller drawing, certain conditions must be met, providing
minimum factor of the friction ψ ¼0.1 and elongation ratio factor μ ¼2. On the
basis of known factor of a friction ψ and δ0, the choice of optimum factor of roller
pass under the dependence, Eq. (22.3), is made. The result is the possibility of
obtaining tubes with a thickness variation from 9% to 12% at its initial to 30%. By
the results of the research, technological recommendations for manufacturing of
light-wall corrosion-resistant steel tubes are prepared.
One of the new methods of production of thin-walled tubes from hardly deformed
alloys is periodic drawing [2], for which deformation of a tube at the expense of back
and forth motion of mandrel is portional. The method of finite elements (Fig. 22.2)
admits a condition for velocity of drawing of pipes without longitudinal thickness
variation:
Fig. 22.2 The computer model of periodic drawing

174 G. Orlov
νℓk
v∗ ¼ ,
μ 1 2πarccos 1 2 ℓℓ0k
1
where ν is the rate of back and forth motion mandrel; ℓk, a way of mandrel at wall
calibration (length of a calibrating corbel of die case); ℓ0, a full way of mandrel; and
μ, elongation ratio factor.
For the correction of thickness variation, Eq. (22.1), in traditional methods of cold
deformation, it is necessary to provide the nonuniform scheme оf drafts in cross
section, which can be presented in the following way:
v∗ ¼ a1 þ a2 sin ðθ=2 þ θ0 Þ, ð22:4Þ
where constants a1, a2, and θ0, accordingly, characterize the minimum and maxi-
mum speed оf draft and an orientation angle of scheme оf drafts concerning the main
axis of thickness variation, connecting the maximum and minimum thickness of
a wall.
Unknown parameters of function, Eq. (22.4), are found from the decision of
variation problems of theory of metal forming with the use of a principle of virtual
speeds. It was shown that the nonuniform scheme оf drafts can be realized by
application of the tool of not round cross section with the subsequent deformation
in round caliber. The parameters of the tool are found from dependence
0:343 0:978 0:866

ζ¼ δ0 δк , ð22:5Þ
N
where ζ is the relation of the area of internal thickenings to the area of section of
initial stock; δ0 and δk, respectively, the initial and final (demanded) relative
thickness variation in unit shares; and N, the number of sides of a profile.
22.3 Experimental Results
The proposed method of periodic drawing has been tested at production of trial parties
of tubes in the sizes 16–20 0.25–1.0 mm from copper alloys and also molybdenic
tubes in the sizes 12–18 0.5–1.5 mm from hot-pressed stock 26 2.5 mm.
Under the dependence, Eq. (22.5), optimum parameters of mandrel profiles for
maintenance of demanded level of thickness variation δk were defined. Intermediate
profiling is realized by applying profile mandrels at the rolling by rolls and rollers [3]
and pressing and drawing of copper and brass tubes. For profiling at a pressing stage,
a trihedral pin was used and at a drawing stage, profile self-established mandrel.
At a cold rolling, advanced calibration for the reduction of longitudinal thickness
variation formed in the end of a reducing site is proposed. Mathematically the
problem of calculation of calibration is reduced to plotting of the forming caliber
D (x) and mandrel d (x) on a reducing site in length l, satisfying boundary conditions
Fig. 22.3 Distribution of true relative drafts for various design procedures: 1, MISiS; 2, PU tube
plant; 3, Ural tube institute; 4, according to Eq. (22.6)
and some criteria. Thus the tube section is considered ideally round, not dependent
on angular coordinate. Boundary conditions provide the necessary sizes for rolling
of the tubes: D (0) ¼ D0, D (0) ¼ d (0) + 2S0 + Δ, D (l) ¼ DТ, and d (l) ¼ DТ-2ST,
where D0, S0, DТ, and SТ are the initial and final sizes of a tube and Δ is a backlash
for input mandrel. Curves of the forming caliber and mandrel are coordinated as D
(x) ¼ d (x) + 2S (x) and D / (l) ¼ d / (l) where the stroke designates the derivative of a
function. The last condition provides a reduction in longitudinal thickness variation
of tubes.
Initial parcel for definition of function S (x) and calculation of a profile of calibers
is the assignment of a mode true relative drafts f (x) ¼ ΔSi/Si. In order to prevent the
formation of longitudinal thickness variation, this function should satisfy the condi-
tion lim f ðxÞ ¼ 0:
x!l
The analysis of known design procedures of calibrations has shown that the last
condition often is not satisfied (Fig. 22.3); therefore, it is proposed to set a mode in
the following way [4]:
x x
f ð xÞ ¼ B 1 eA l , ð22:6Þ
l
where factor A ¼1.2 and В is defined from a boundary condition.
Factor A in Eq. (22.6) varied and was found from the condition of the minimum
loading on a precalibrating site in maintaining the minimum longitudinal thickness
variation of tubes.
On the tandem cold rolling, the tube is deformed simultaneously by two succes-
sive pairs of rolls of the same size. This scheme makes it possible to increase the
draft during the rolling operation by a factor of 1.5–2. The first pair of rolls, which
176 G. Orlov
initiates the deformation of the incoming semifinished product, is usually referred to

as the breakdown pair. The second pair of rolls is called the sizing pair. These mills
are difficult to operate because of the complicated adjustments that must be made to
their equipment and the distinctive features of the process of deformation in two
pairs of rolls simultaneously. These features should be reflected in the design of the
equipment. Most of these problems are related to the fact that the specific features of
the rolling operation on these mills have not been adequately taken into account.
One of the most important features of the type of mill being discussed is that
rotation is transferred from the breakdown pair of rolls to the sizing pair through a
unilateral diagonal transmission with the gear ratio Dg2/Dg1 ¼ 1.03–1.06. As on a
conventional mill, the rolls of the breakdown pair are brought into rotation by drive
pinions with a pitch-circle diameter Dp1. The nominal diameter of the drive pinion
of the second (sizing) roll pair is determined by the gear ratio
Dg2
Dp2 ¼ Dp1 ð22:7Þ
Dg1
where Dg2 and Dg1 are the pitch-circle diameters of the gear wheels on the break-
down and sizing rolls, respectively.
To a large extent, Eq. (22.7) determines the deformation conditions and the axial
forces transmitted by the second pair of rolls. Thus, it is possible to choose an
efficient ratio for rolling with substantial drafts while avoiding having the tube
become unstable due to large axial forces.
The deformation conditions in the breakdown pair of rolls differ from a conven-
tional mill, in which the metal is subjected to an additional load (tension or thrust)
from the sizing roll pair, depending on the direction of the axial forces. Thus, the
axial force in the i-th instantaneous deformation zone (IDZ) is determined with
allowance for the axial force in the corresponding IDZ of the second roll pair. The
additional axial load has a substantial effect on the stress state of the metal, its
cumulative damage content, and the degree to which any variation in the thickness of
the wall of the tube can be corrected.
The method discussed above was used on a computer to design new rolls and
analyze the rolling of steel 45 tubes on the tandem rolling mill at the pipe plant in
accordance with the new schedule 45 3 ! 25 1 mm. The draft was 5.25.
It is investigated that the compressive axial forces increase more rapidly in the
first pair of rolls. The axial forces decrease in the zone where the deformation cones
overlap due to the low rate of compression. The forces exerted by the metal on the
rolls in this zone decrease for the same reason. Because the amount of metal rolled in
the sizing roll pair during the reverse stroke of the stand is greater than in a normal
mill, the forces on the rolls are greater during this stroke than during the forward
stroke.
We subsequently studied the effect of the gear ratio of the diagonal transmission
in Eq. (22.7), which determines the nominal diameter of the pinion of the second roll
pair and the axial forces that the pair transmits. The gear ratio on the stand being
discussed is 1.057, which led to high axial forces and destabilization of the tube.
To lower the axial forces, it was proposed that the gear ratio be reduced to 1.032 by
decreasing the diameter of the gear wheel of the second roll pair. A larger decrease in
the gear ratio would be inadvisable, since it would increase the area of the lead zone
and increase the axial compressive force created during the forward stroke of the
stand. This situation is illustrated by the data below:
Gear ratio 1.057 1.032 1.028
Maximum axial force, kN 79.8 52.1 56.2
Maximum relative stress 0.92 0.70 0.76
The change in the gear ratio lowered the axial forces by 32–37%, which makes it
possible to avoid butt joining of the ends of tubes. The change in gear ratio had
almost no effect on the distribution of the forces on the rolls.
22.4 Summary
We have considered advanced ways of producing cold-deformed tubes: roller

drawing on a long mandrel and periodic drawing. Correcting the thickness variation
in the roller drawing and conditions for tube drawing without longitudinal thickness
variation have been studied with the help of the finite-element method. The formulas
for the selection of the drawing process parameters have been obtained. An
improved calibration to reduce the loading and longitudinal thickness variation of
tubes has been proposed for the rolling mills.
References
1. Orlov, G. A., & Vagapov, E. N. (2012). The use of modeling to develop a method for the roller
drawing of tubes on a long mandrel. Metallurgist, 56(1–2), 109–114.
2. Pupyshev, A. A., Akchurin, R. Z., & Orlov, G. A. (2000). Geometric and kinematic constraints of
the periodic tube drawing. Nonferrous Metallurgy (Russia), 3, 49–55.
3. Orlov, G. A., Igoshin, V. F., & Mizhiritskij, O. I. (1993). Reduction of thickness variation during
rolling on shaped mandrels of rocking and roller-type rolling mills. Steel in Translation, 10,
59–61.
4. Orlov, G. A. (2005). Estimating the quality of cold-deformed pipes. Steel in Translation, 35(3),
49–54.
Chapter 23
Features of Multihole Stamping of Platinum
Glass Melting Apparatus Elements
Yu. Loginov and A. Fomin
23.1 Introduction
The use of platinum and platinum alloys in industry is caused by its unique
properties: resistance to high-temperature corrosion and oxidation in contact with
oxide materials at high temperatures [1, 2] as well as the ability to deep drawing
[3]. One of the important fields of precious metal industry is the application of
platinum alloys in manufacturing of the equipment for the production of glass and
basalt fiber [4, 5]. The glass melting apparatus (bushing) is a container for placement
of melted glass or basalt, made of heat-resistant platinum-rhodium alloy [6]. The
essential component element of platinum bushing is bottom tip-plate with tips.
23.2 Problem Description
There are two basic technologies for bushing bottom tip-plate manufacturing: the
first one is multistage stamping of tips from a solid plate, and the second one is
welding of tips into a plate with prepunched holes. Stamped tip-plate has a number
of advantages, including the possibility of a more close packing of tips on tip-plate.
However, the close packing of tips creates some technological challenges, one of
which is maintaining the symmetrical execution of each tip to ensure the required
dimensional accuracy.
Y. Loginov (*)
e-mail: j.n.loginov@urfu.ru
A. Fomin
EZOCM-ENGINEERING, Verhnjaja Pyshma city, Sverdlovsk Region, Russia

https://doi.org/10.1007/978-3-319-75340-9_23
180 Y. Loginov and A. Fomin
Fig. 23.1 Side view (a) and top view (b) of platinum strip with stamped tips after the first stage of
stamping
In the first stage of stamping, a strip of a required thickness with a number of

projections on its lower side is received. The workpiece is stamped by an upper die
on the lower die with holes whose location corresponds to the location of tips on the
bottom tip-plate. The metal of the workpiece becomes thinner over the flat surface of
the lower die and concentrates in its holes under the pressure of the upper die. After
each stroke of the upper die, the multihole lower die with the workpiece moves
relative to the upper die in a direction opposite to the direction of the metal flow. So,
step by step, the process lasts until the end of the strip. The resulting projections are
located on the lower surface of the workpiece in the form of a required number of
rows arranged consecutively. Each row of the projections consists of two semi-rows,
staggered relative to each other. In Fig. 23.1, the appearance of the glass melting
apparatus bottom after the first stage of stamping is shown.
This step-by-step technology can lead to the formation of defects, for example, a
difference in form between the first and second (in the direction of the metal flow)
semi-row of each row of projections, owing to an asymmetrical filling of the holes of
the stamp. While the first semi-row has a distinct sloping site, the second semi-row
has a more correct conical shape (Fig. 23.1). Also the projections of the second semi-
row have a great height, compared with the first semi-row. This is due to the design of
the stamp. Each row of holes of the lower die is in a small recess with a height up to
0.25 mm, which has a trapezoid shape with rounded corners on the top view.
Because of this, as well as the longitudinal metal flow, the second semi-row is in
more favorable conditions for the metal plastic flow. Metal abuts the shoulder
23 Features of Multihole Stamping of Platinum Glass Melting Apparatus Elements 181
Fig. 23.2 The fragment of a

lower die
(Fig. 23.2) formed by the recess and flows through the path of least resistance
because of the minimum energy law, i.e., in the hole of the stamp second semi-row.
As a result, the second semi-row has a larger volume. It happens that the volume of the
first semi-row is not even enough for the formation of a high-grade tip at the second
stamping stage.
All the above-described defects occur due to the step-by-step processing tech-
nology, resulting in intensive longitudinal metal flow. One approach to improve this
technology could be an increase in the contact area of the upper die to the maximum
value, based on the capabilities of stamping equipment, and the second approach is
stamping step selection, which must be a multiple equal to the distance between two
adjacent rows of projections.
23.3 Finite Element Modeling
Deformation during sheet metal stamping can be simulated by finite element

method, as shown, for example, in Refs. [7–10] with various software products:
PLAST, RAPID, and PAM-STAMP 2G.
To assess the impact of the stamping step on the defectiveness of the workpiece
after the first stamping stage, this process was simulated in the software DEFORM-
3D, designed for solving problems in the field of finite element calculations of metal
forming processes.
Two simulations with different stamping step size were produced. Simulation
with a stamping step of 3 mm is a modeling of standard technology, currently used in
production. For the experimental technology, 12 mm step was used, selected based
on the configuration of the simulated lower die.
The first step of modeling was to create the original geometry of the stamp (upper
and lower die) and the workpiece in a CAD package and then export directly to the
package DEFORM-3D. The simulation type – the deformation, the system of units –
SI, the type of calculation – a method of Lagrange finite increments were selected.
The next step is setting the parameters of the stamp and the workpiece. The stamp in
the simulation was considered as an absolutely rigid body, the workpiece – the
elastic-plastic body – so the division into finite element mesh had to be made only for
the model of the workpiece. Since the workpiece has a simple geometric shape, the
automatic determination of the finite element mesh was used. As a result, the mesh,
consisting of 85,160 tetrahedra uniformly distributed throughout the volume of the
workpiece, was obtained. The next step was to set the properties of the workpiece
material. In glass fiber industry platinum-rhodium alloys are the most commonly
used; their chemical composition is constantly improving [11, 12]. In this work, as
the material alloy PtRh-10DS (dispersion-strengthened) was selected, whose
Young’s modulus is equal to 193,100 MPa and the Poisson’s ratio is 0.34. Plastic
properties were set by an equation, which establishes a relationship between the
deformation resistance and the plastic strain. This equation is
σ S ¼ a þ b ∙ εC , ð23:1Þ
where σ S is the deformation resistance, ε is the plastic strain, a is the yield strength,
b is the hardening coefficient, and c is the hardening exponent. The applicability of
such law for platinum hardening was shown in Refs. [13, 14]. For alloy PtRh-10DS,
these values were adopted as follows: a ¼ 241 MPa, b ¼ 444 MPa, and c ¼ 0.419. At
the boundary of contact of the workpiece with the stamp the implemented friction is
described by the friction law of Siebel with the friction coefficient of 0.12 [15]. The
displacement of the upper die is defined by the direction and a constant speed of
50 mm/s. The calculation lasted until the ultimate distance between the dies is equal
to a specified tip-plate thickness.
23.4 Modeling Results
The results of the first simulation are shown in Fig. 23.3a. In the figure, the blue
triangles denote the finite element mesh of the workpiece; the green triangles depict
the body of the stamp. It is seen that the results correspond to reality: the first semi-
row of projections has a small volume and a sloping site, and the second semi-row
has a large amount of metal and a conical form.
Fig. 23.3 Modeling of the workpiece deformation with a different processing step: (a) 3 mm, (b)
12 mm
Fig. 23.4 The upper die for

the first stamping operation:
1 – flat base; 2 –
rounded edge
The results of the second simulation are shown in Fig. 23.3b. You may notice a
significant change in the pattern of filling the stamp: the first semi-row of projections
began to have a more correct conical shape; its volume has increased about two
times. In addition, the sloping site appeared on the second semi-row, but at this
height of the projections, this site is not a defect, because the workpiece is subjected
to further machining.
Therefore, this approach of increasing the stamping step resulted in a more
symmetrical and more complete filling of the holes of the lower die. However, it
also implies the increase of the stamping force by several times.
Another approach of improving the uniformity of filling of the stamp is the
selection of the geometric parameters of the upper die. The first stamping stage is
carried out by the upper die, which is shown in Fig. 23.4 and has a flat base and a
rounded edge.
The flat base is the deforming element; the rounded edge creates a longitudinal
flow of metal. The influence of a rounding radius value on the filling of the stamp
was investigated using finite element modeling. Three radiuses – 2 mm, 10 mm, and
20 mm – were selected; the simulation results are shown in Fig. 23.5a, b, c,
respectively.
The projections on the workpiece bottom at a rounding radius of 2 mm and
10 mm have a more regular shape than at a radius of 20 mm. The largest volume of
projections is observed at a radius of 2 mm and 20 mm.
Therefore, the radius of 2 mm is the best of the three selected options. The
comparison of the simulation results shows that the smaller the rounding radius of
the upper die, the more correct form and a greater volume of the projections have the
first and the second projections semi-row. This pattern of the stamp filling shows the
positive effect of reducing longitudinal metal flow due to the decrease of the upper
die rounding radius. However, the complete absence of rounding leads to the
appearance of stripes of metal on the top of the workpiece, so this solution is not
rational.
Thus, the computer simulation shows that a change in stamping process param-
eters can lead to a more symmetrical filling of the stamp.
Fig. 23.5 Modeling of the workpiece deformation with different rounding radius: (a) 2 mm, (b)
10 mm, (c) 20 mm
23.5 Conclusion
1. Current technology of bushing tip-plate stamping is not optimal because of the

unevenness filling of stamp holes by deformable metal.
2. Modeling of the deformation process by the finite element method showed that
the increase of the processing step and the use of the upper die with a minimum
rounding radius increase the symmetry of the die filling.
References
1. McGrath, R. B., & Badcock, G. C. (1987). New dispersion strengthened platinum alloy.
Platinum Metals Review, 31(I), 8–11.
2. ElGuindy, M. (2001). Platinum group metals: Alloying, properties, and applications. Encyclo-
pedia of Materials: Science and Technology (2nd ed, pp. 7117–7121).
3. Kameneckij, B. I., Grohovskaja, L. G., Loginov, Ju. N., & Studenok, G. I. (2007). Issledovanie
deformacionnyh harakteristik i struktury splava PlN-4,5 pri izgotovlenii polyh zagotovok
metodom glubokoj vytjazhki. Cvetnye metally. № 8. С. 51–53.
4. Rytvin, Y. (1999). I. Platinum metals and silicates: from the 20th century to the 21st century.
Proceedings of International Symposium on Precious Metals. Kunming, Yunnan Science and
Technology Press (pp. 89–98).
5. Koch, M., & Lupton, D. (2006). Design and manufacture of bushings for glass fibre production.
HVG-Colloquium Production, Properties and Applications of Refractory and Platinum Group
Metals for the Contact with Glass Melts. Düsseldorf (pp. 1–12).
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cel’noshtampovannyh fil’ernyh uzlov stekloplavil’nyh apparatov, Platinovye splavy dlja
stekloplavil’nyh apparatov. M.: VNIISPV. S. 96–101.
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plasticheskogo sloja v mnogorjadnom shhelevom shtampe. Kuznechno-shtampovochnoe
proizvodstvo. Obrabotka materialov davleniem. № 4. S. 14–17.
8. Loginov Ju. N., Kameneckij, B. I., & Studenok, G. I. (2006). Modelirovanie deformirovannogo
sostojanija krugloj plastiny pri vytjazhke. Izvestija vysshih uchebnyh zavedenij. Chernaja
metallurgija. № 3. S. 26–28.
9. Völkl R., Fischer, B. Teschner R., & Lupton, D. F. (2001). Finite element modelling of strains
and stresses in platinum alloy bushings for textile glass fibre production, Glass Science and
Technology, Glastechnische Berichte. Vol. 74 (pp. 142–151).
10. Ershov, A. A., & Loginov, Y. N. (2013). Using the INVERSE solver “INVERSE” in
PAM-STAMP 2G. Metallurgist, 57(5–6), 372–377. https://doi.org/10.1007/s11015-013-
9741-x.
11. Darling, A. S., Selman, G. L., & Bourne, A. A. (1968). Dispersion strengthened platinum.
Improved high temperature creep properties. Platinum Metals Review, 12(l), 7–13.
12. Rdzawski, Z. M., & Stobrawa, J. P. (2004). Microstructure and properties of the new Pt–Rh
based alloys for high-temperature applications. Journal of Materials Processing Technology,
153–154, 681–687. http://dx.doi.org/10.1016/j.jmatprotec.2004.04.130.
13. Loginov, Y. N., Yermakov, A. V., Grohovskaya, L. G., & Studenok, G. I. (2007). Annealing
characteristics and strain resistance of 99.93 wt.% platinum. Platinum Metals Review, 51(4),
178–184. https://doi.org/10.1595/147106707X237708.
14. Loginov, Ju. N., Ermakov, A. V., Grohovskaja, L. G., & Studenok, G. I. (2006). Uslovija
razuprochnenija i soprotivlenie deformacii platiny. Cvetnye metally. №6. S. 85–88.
15. Loginov, Ju. N., & Studenok, G. I. (2010). Izuchenie trenija pri listovoj prokatke platiny i ee
splavov. Proizvodstvo prokata. № 7. S. 14–16.
Chapter 24
Research on Metal Forming in the Pipe
Ends Upsetting Process
M. Erpalov and A. Bogatov
24.1 Introduction
The pipe ends upsetting process is a local increase of the wall thickness of a pipe at a
predetermined distance from the end. Wall thickening is performed outside, inside,
or on both sides using dies and a punch [1, 2]. Greater wall thickness increases the
strength of threaded tubing connection with couplings or welded drill pipe connec-
tion with tool joints. Couplings and tool joints are used to build the pipes in the
columns in the extraction of oil and gas.
Now, the conditions of oil and gas production are becoming more complex. This
fact sets high demands on the quality of pipes produced. The practice of the
production of pipes with upset ends shows that most defects are located on the
inner surface. These imperfections are surface cracks that reduce the effectiveness of
pipe wall thickness [3]. They are detected close to the ends of pipes (Fig. 24.1).
Mueller and Arem [4] show that the cause of such defects is a lower temperature at
the end of the pipe relative to the rest of the heated part of the pipe. However, the
temperature increase directly at the pipe end does not improve the product quality.
Therefore, the purpose of this paper is to research metal forming in pipe ends
upsetting process and to identify the defects associated with the process. The study
involved finite element simulation and a full-scale experiment. The influence of the
diameter and wall thickness of the pipe, friction conditions, the temperature of the
heated pipe ends, and the temperature of the tool on the defect creation has been
studied.
M. Erpalov (*) · A. Bogatov

e-mail: m.v.erpalov@urfu.ru

https://doi.org/10.1007/978-3-319-75340-9_24
188 M. Erpalov and A. Bogatov
Fig. 24.1 The defect on the

inner surface of the pipe
upset end
24.2 Finite Element Simulation
To achieve the goals of this research, finite element simulation in DEFORM-3D was
performed. The simulation was carried out for the tubing with nominal dimensions
73.02 5.51 mm in accordance with API specification 5CT [5] and for drill pipe
73 9.2 mm in accordance with State Standard R 50278-92 [6]. The actual
dimensions 73.23 4.82 mm and 73.81 6.2 mm of the tubing were also used
taking into account the tolerances on the diameter and the wall thickness of the pipe.
The steel grade AISI-1045 was selected in DEFORM-3D’s material library. These
blanks were used for computer simulation with the following upsetting process
variables: Siebel friction factor is ψ ¼ 0.3; the length and the temperature of heated
pipe ends are Lh ¼ 240 mm and T ¼ 1200 С, respectively; and the dies and the
punch temperature are Td ¼ 200 С and Tp ¼ 130 С, respectively. The tool calibra-
tion and abovenamed variables of the process are used taking into account the
practice of production of pipes with upset ends at JSC Pervouralsk new pipe plant.
In addition, the problems with Siebel friction factor ψ ¼ 0.7, the temperature of
heated pipe ends T ¼ 1100 С, the temperature of dies Td ¼ 150 С and Td ¼ 250 С,
and the temperature of punch Tp ¼ 100 С and Tp ¼ 180 С, respectively, had been
solved. Moreover, the temperature in a narrow region near the face plane of the pipe
was taken equal to Tf.p. ¼ 1100 С and Tf.p. ¼ 1290 С. All additional problems were
solved for the tubing 73.02 5.51 mm upsetting. In total, ten problems had been at
the stage of computer simulation.
According to the simulation results, there are several stages of the upsetting process
which are characterized by different velocity fields [7]. The first stage is the expansion
of the pipe by the punch. It begins from the time when the punch first contacts the
blank and continues until the punch contacts the face plane of the pipe. The velocity
values at this stage are close to zero. In this regard, there is no attention paid to this
stage in the literature. However, it is characterized by intensive heat removal from the
heated end of the pipe through the contact surface into a cold tool (Fig. 24.2).
The value of cooling defines the change of metal thermomechanical behavior of
blank in the region close to the pipe end. The maximum temperature change near the
contact surface of the blank is as follows:
24 Research on Metal Forming in the Pipe Ends Upsetting Process 189
1300
T0
1200
Temperature, °С
1100 T1max
1000
900 T1min
800
0 50 100 150 200 250
The distance from the conical section of the dies to the face
plane of the pipe, mm
Temperature field in the initial time Temperature field at the end of pipe expansion
Fig. 24.2 The change of the temperature field of the blank during the first stage of the process
L2 15
50 L3
Radial velocity, mm/s

The radial coordinate
of pipe profile, mm
40 5
1 2 3
30
r1 r2 r3 -5
20
-15
10
0 -25
-80 -60 -40 -20 0 20
Axial coordinate of pipe profile, mm
The pipe profile in longitudinal section Radial velocity field
Fig. 24.3 Field of the radial velocity
T 1max T 1min
K temp ¼ : ð24:1Þ
T 1max
In the process of the pipe profile buckling, there is a gradual increase in the outer
and inner diameter of the end of the blank, whereby the contact of a pipe with a
punch disappears. Then the filling of the die space starts. The die space is formed
with the working surfaces of the die and the punch. The filling of the dies occurs in
the direction from the periphery to the axis of the blank [8–10]. Due to the
nonuniform deformation resistance of the metal in the axial direction specified by
cooling in the initial stage of upsetting, the field of radial velocity is characterized by
two local maxima (Fig. 24.3).
A closed air cavity appears between the surfaces of the punch and the inner
surface of the pipe. It appears in the case when the metal particles that are on the
boundary of domains 1–2 have a larger radial velocity than the particles on the
boundary 2–3 (Fig. 24.3). This cavity does not disappear completely to the end of the
upsetting process. To quantify the tendency to the creation of defects on the inner
surface of the upset pipe, the following parameter is introduced:
0.05 Tf.p.=1100°C
0
0.12 0.17 0.22 0.27
-0.05 KTemp
ψ=0.7
-0.1
Kdef
-0.15
-0.2
-0.25
-0.3
Fig. 24.4 The dependence of the Kdef from Ktemp
r2 r1
K def ¼ : ð24:2Þ
L2
Figure 24.4 shows the dependence of a parameter Kdef on the parameter Ktemp that
characterizes nonuniform deformation resistance along the axis of the blank at the
end of the stage of expansion of the pipe. It is seen from the diagram that the inner
defect is formed when the temperature of metal in face plane of the pipe is
Т ¼ 1100 С. It is 100 C below the temperature of the rest heated part of the pipe.
The decrease of tool temperature leads to a slightly increased probability of defect
formation. The increase of friction factor leads to the increased nonuniformity of
deformation in the pipe end [10], which in turn increases the tendency to the creation
of defects. This can be seen from Fig. 24.4 where the value Кdef is very different from
the trend line.
The increase of the tool temperature, as well as the increase of temperature in the
face plane of the pipe, provides more uniform temperature on the end of the blank. It
should be said that the values of parameter Ktemp are equal when two pipe ends are
heated, one to the temperature 1200 С and the other one to 1100 С. This leads to the
fact that the tendency to the creation of defects is equal in both cases.
An additional parameter is added in the process:
2S
K tool ¼ , ð24:3Þ
Dd d p
S – wall thickness of the pipe, mm

Dd – diameter of the cylindrical part of the dies, mm
dp – diameter of the conical part of the punch, mm
Figure 24.5 shows the dependence of a parameter Kdef on the parameter Ktool that
characterizes wall thickness of the blank relative to the clearance between the dies
and the punch. It is clear that with the increasing amount of clearance between the
dies and the punch, the tendency to the appearance of defects is evident. The results
of simulation show that inner defects appear close to the upset end of the pipe
0.1
73.81x6.2
0.05
0
0.5 0.55 0.6 0.65 0.7 0.75
-0.05 Ktool
Kdef
-0.1
73.23x4.82 73.02x5.51
-0.15
-0.2
-0.25
-0.3 73x9.2
Fig. 24.5 The dependence of the Kdef on Ktool
73.81 6.2 mm. Statistical analysis of experimental data suggests that there is a
linear relation between the parameters Kdef and Ktool regardless of the pipe dimen-
sions and the tool sizes. Thus, correlation has been found between the tool calibra-
tion parameters with the maximum wall thickness at which the defect creation is
observed:

Smax ¼ 0:3486 Dd dp : ð24:4Þ
24.3 Full-Scale Experiment
In order to confirm the results obtained at the stage of computer simulation, a full-
scale experiment was carried out at JSC Pervouralsk new pipe plant on a hydraulic
press made by SMS Meer. Blanks with nominal dimensions 73.02 5.51 mm were
chosen for this experiment. According to the existing tool calibration at JSC
Pervouralsk new pipe plant and Eq. (24.4), the maximum wall thickness is
5.96 mm. Blanks with average wall thickness of 5.28 mm, 5.36 mm, 5.49 mm,
5.79 mm, 5.87 mm, and 6.09 mm were chosen for the full-scale experiment. The
upsetting was made with the following process variables: the length of the heating
pipe ends is Lh ¼ 310 mm, the heating temperature is T ¼ 1290 C, the pressure in
the main hydro cylinder is 10 MPa, and the time delay before moving the punch in
the opposite direction is 1.8 s.
The full-scale experiment has shown that the pipe in which inner defects were
found had wall thickness equal to 6.09 mm. This exceeded the maximum wall
thickness equal to 5.96 mm. Inner defects were not found for the rest pipes with
wall thickness of less than 5.96 mm. Thus, the full-scale experiment has confirmed
the validity of Eq. (24.4) that allows one to establish requirements either to blanks
coming on the upsetting operation or to the tool calibration based on the actual
dimensions of the pipes.
Fig. 24.6 Upset end of drill pipe 73 9.2
Figure 24.5 shows that the parameter Kdef is minimal in the case of upsetting the
drill pipe with dimensions 73 9.2 mm in accordance with State Standard R 50278-
92 in one pass. This is caused by the fact that the step of expansion of pipe is omitted.
So, inner defects near the pipe end are excluded. The experimental work was carried
out at JSC Pervouralsk new pipe plant to test the possibility of upsetting drill pipes
73 9.2 mm in an industrial environment in one step. As a result, 30 tons of the
pipes were successfully treated, and the coefficient of the pipe wall thickening was
about 1.85. Defects on the inner surface of the pipes were not detected (Fig. 24.6).
This confirmed the results of theoretical research.
24.4 Conclusion
This paper presents theoretical and industrial research on the pipe ends upsetting
process in one step. Special attention is paid to the quality of the inner surface of final
products. The results of computer simulation show the influence of technological
parameters of upsetting on defect formation on the inner surface of the pipe. Full-
scale experiment confirms the correlation between maximum wall thickness and the
calibration parameters of the process tool (Eq. 24.4).
This research was performed as part of the project of the state task in the field of
scientific activity №11.1369.2014/K from 07/18/2014 (state registration number:
114122470051).
References
1. Development of OCTG ends upsetting technology at JSC “PNTZ”, Erpalov M. V. et al. OMD
2014. Fundamental problems. Innovative Materials and Technologies: Proceedings of the
International Scientific and Engineering Congress. Moscow: Publishing House “Bely veter”.
2014 (Vol. 2, pp. 64–69).
2. Erpalov, M. V., Kondratieva, G. N., & Bogatov, A. A. (2014). Upgrading pipe ends upsetting
technology in order to increase the efficiency of hydraulic presses SMS Meer, Innovative
technologies in metallurgy and mechanical engineering: Proceedings of the International

Conference. Ekaterinburg: Publishing House Ural. Univ. (pp. 581–592).
3. Erpalov, M. V. (2013). The research of pipe ends upsetting process on hydraulic presses to
enhance their quality: The final research report, Ural Federal University named after the first
President of Russia B.N. Yeltsin; Supervisor A.A. Bogatov; Executor M.V. Erpalov.
Ekaterinburg, 11 p.
4. Mueller, W., & Arem, R. (2009). Work technology. Upsetting press: Presentation, JSC
“PNTZ”. Pervouralsk, 28 p.
5. API 5CT. (2011). Specification for casing and tubing. Ninth edition. Effective date 2012-01-01.
Published by American Petroleum Institute (API).
6. GOST R 50278-92. (2010). Drill pipes with welded locks. Technical conditions. Effective Date
1994-01-01. Moscow: Publishing House Standartinform.
7. The pipes for the oil industry, Tkachenko V. A. et al., Moscow: Metallurgy, 1986, 256 p.
8. Ostrenko, V. Ja. (1965). Technological features of pipes upsetting in closed tool, Metallurgical
and Mining Industry. №1. (pp. 33–35).
9. Ostrenko, V. Ja. (1968). Analytical method for determining the energy-power parameters of the
pipe ends upsetting, Production of pipes: Proceedings VNTITI. Moscow: Metallurgy. №20.
(pp. 223–230).
10. Theory of metal forming (1963). Tarnowski I.Ja. Moscow: State Science and Technology
Publishing House of ferrous and non-ferrous metallurgy (pp. 382–387).
Chapter 25
The Study of Residual Stresses and Surface
Hardening in Tubes After Finishing
Processes
M. Rozenbaum, An. Serebryakov, I. Bazhukov, and G. Shimov
25.1 Introduction
Nuclear power development and the necessity to increase the durability of power
units up to 80–100 years [1] have established higher expectations for reliability and
safe operation of A-plant equipment.
The steam generator (SG) is one of the most important as well as the most
damageable elements of an A-plant. The main factor affecting the durability of a
steam generator (SG) is the condition of heat exchanger pipes. The process of
deterioration of heat exchanger pipes in steam generators has been thoroughly studied
by the “Prometey” construction materials scientific institution and “Hydropress”
construction bureau (Podolsk). One of the most common types of damage related
to heat exchanger tubes in SG is corrosion cracking – the deterioration of metal
caused by tensile and residual stresses along with the impact of corrosive environ-
ment [2–5].
The techniques for manufacturing heat exchanger tubes are represented by the
following operations: boring and grinding hot-rolled pipe billet, cold rolling middle-
sized pipes, heating, rolling final-sized pipes, straightening, electropolishing the
inner surface and burnishing the outer surface, and checking the final quality.
Correcting and burnishing operational modes predetermine residual stresses in
pipes during the delivery process.
This chapter presents the results of the research on residual stresses and surface
peening formed during finishing operations (correcting and burnishing).
M. Rozenbaum (*) · G. Shimov

Institute of New Materials and Technologies, Ural Federal University, Ekaterinburg, Russia
e-mail: m.m.rozenbaum@urfu.ru
A. Serebryakov · I. Bazhukov
Pervouralsk New Pipe Plant, Pervouralsk, Russia

https://doi.org/10.1007/978-3-319-75340-9_25
196 M. Rozenbaum et al.
Fig. 25.1 The sequence of

finishing operations
Fig. 25.2 Ring samples for defining residual stresses: a – ring with increased diameter (tension
residual stresses); b – ring with reduced diameter (compression residual stresses)
25.2 Research Materials and Methods
Residual stresses. Steel pipe samples 08Х18Н10Т size 16 1.5 mm (manufactured

in accordance with ТУ14-3Р-197-2001 standard) were used as research materials.
Sample selection was made after heating, correcting, sandblasting, and grinding. The
sequence of the finishing operations is shown in Fig. 25.1.
The value and the character of residual stresses were determined by the ring
method [6], which involves cutting a ring out of a pipe perpendicular to its axis
(Fig. 25.2).
The next step after cutting is measuring the diameter. Then ring samples are cut in
generatrix and the diameter is measured again. Tension residual stresses lead to
diameter increase (Fig. 25.2a); compression residual stresses lead to diameter
decrease (Fig. 25.2b).
25 The Study of Residual Stresses and Surface Hardening in Tubes After. . . 197
Cutting the ring in generatrix and measuring the changes of its diameter make it
possible to calculate residual stresses (Eq. (25.1)):
σ res ¼ E Δd S
ð25:1Þ
D,
σ res – residual stresses value, mPa
E – Young modulus of elasticity that equals to 205,000 mPa
Δd ¼ (d1 d0) – the difference of diameters measured before and after cutting, mm
S – the pipe wall thickness, mm

D ¼ ðDout SÞ – the average diameter, mm
Dout – the outer diameter before cutting, mm
This method is based on the assumption that the distribution of circumferential
residual stresses throughout the pipe wall section is linear. It gives an opportunity to
estimate the influence of technological operations on residual stresses.
Surface peening. Solidity measurement was done using FISCHERSCOPE
HM2000 XYm series measurement device that is designed for microhardness
estimation. This method conforms to ISO 14577, DIN 50359, DIN EN ISO
14577–1, DIN55676, and VDI/VDE Guidance N 2616 standards that define the
requirements for tools operating by an indentation principle to determine solidity
value and other parameters. Measuring and analyzing procedures are automated in
the system.
The standardized interpretation of the term hardness is defined in ISO 14577
standard approved in 2002. This standard was elaborated by ISO/TC 164 technical
committee (metal mechanic testings) and SC3 subcommittee (solidity testing).
According to this document, solidity is defined as resistance of a material-to-gradual
penetration of harder matter of another kind.
Scratch hardness value HM is calculated through indenter submergence depth
and load value in accordance with the following international standards: ISO 14577
(ISO 14577 Metallic Materials. Instrumented indentation test for hardness and
materials parameters. Part 1: Test method) and DIN 50239 (DIN 50359–1 Testing
metallic materials – Universal Hardness test Part 1: Test method).
The recording of the indentation diagram and preliminary results processing were
done with the use of WIN-HCU device software. The following indenters were used
for the measurements: Vickers four-sided diamond pyramid nanoindenter with
restricted requirements to geometry (VV064 DKD-K-06301 № 430,009,544 certif-
icate dated 11/23/2005) and Berkovich three-sided diamond pyramid indenter
(VB034 DKD-K-06301 # 430009940 dated 3/16/2006). Hardness calibration of
the devices was done according to BK7 material.
ISO 14577 standard regulates using two main hardness indicators: scratch hard-
ness HM and indention hardness Hit. With the continuous increase of indention force
(F), the corresponding depth value (h) of the indenter penetration is determined.
Taking into consideration the geometrical correlation between penetration depth
and the shape of the indenter, the measuring system generates the universal hardness
Table 25.1 Tangential residual stresses calculation results

Operation type d0, (mm) d1 (mm) Δd (mm) σres (mPa)
Heat treatment 16.260 16.239 0.021 32.27
16.261 16.260 0.001 1.56
16.262 16.256 0.006 8.84
16.271 16.249 0.022 34.81
16.271 16.246 0.025 38.97
16.279 16.263 0.016 24.91
16.270 16.251 0.019 29.62
16.266 16.248 0.018 27.56
16.264 16.241 0.023 35.89
16.271 16.235 0.036 56.64
16.278 16.256 0.022 33.74
Correcting 16.256 16.285 0.029 45.82
16.263 16.299 0.036 55.66
16.253 16.280 0.027 42.72
16.263 16.275 0.012 18.21
16.267 16.277 0.010 15.6
16.288 16.331 0.043 66.35
Sandblasting 16.258 16.335 0.077 120.24
16.256 16.381 0.125 195.78
16.265 16.333 0.068 105.56
Grinding 16.131 16.205 0.074 117.59
16.186 16.254 0.068 107.24
16.189 16.257 0.068 107.2
Grinding after correcting 16.183 16.194 0.011 16.83
16.181 16.208 0.027 42.61
16.188 16.259 0.071 112.47
index value according to HM ¼ F/A physics formula in which А ¼ f(h) stands for
imprint surface area. Scratch hardness denotes metal hardness value.
25.3 Research Results
25.3.1 Technological Operations’ Influence on Residual

Stresses Value
Table 25.1 demonstrates the average values of samples diameters before and after
cutting as well as the calculations of tangential residual stresses. Calculation results
with + mark apply to stretching residual stresses, and results with – mark apply to
shrinking residual stresses. The data from Table 25.1 are illustrated in Figs. 25.3 and
25.4.
140
130
120
110
100
90
Residual stresses, σres mPa
80
70
60
50
40
30
20
10
0
-10
-20
-30
-40
1 2 3 4
Technological operations
Fig. 25.3 Changes in residual stresses by technological operations: 1 – heat treatment; 2 –

correcting; 3 – sandblasting; 4 – grinding
Figures 25.3 and 25.4 show the changes of the average values of residual stresses
depending on finishing operations. As can be seen in Figs. 25.3 and 25.4, residual
stresses shrink after heat treatment and equal to 29.53 MPa. Further pipe correction
creates stretching residual stresses equal to 40.72 MPa. Sand jetting the surface of
inner pipes additionally increases stretching residual stresses up to 129.28 MPa;
subsequent grinding reduces the tensile residual stresses down to 78.29 MPa.
Excluding sandblasting (Fig. 25.4) causes residual stresses to retain the same level
of tension as after straightening.
The data from Table 25.1 are illustrated in the boxplot (Fig. 25.5), consisting of
the following elements:
– Central quartiles (shown as rectangles that point out that 50% of data are located
within required interval, 25% are above those limits, and the remaining 25% are
below those limits)
– Distribution range (intervals limited by lines coming out of smaller rectangle
sides show distribution interval for the majority of values or all of them)
– Median/average value (line inside a rectangle)
This diagram enables an analysis considering the wide range of experimental
data. The analysis of the diagram supports the results presented in Figs. 25.3 and
25.4.
55
45
35
25
15
-5
-15
-25
-35
1 2 4

correcting; 3 – grinding
25.3.2 Pipe Correction and Polishing Operation Influence

on Surface Peening
Pipe samples after heating, correcting, and polishing were taken for this test. Each
sample underwent ten measurements. The measurements were made with 200 g
loading and indenter penetration depth of 7 μm. The results of the measurements
were obtained as files containing electronic tables. A file formed by the measuring
system contains 6400 records. These files contain information about the experimen-
tal results: indentation pressure, the depth of indenter penetration into a sample,
pressure time, and scratch hardness values.
Then the test data are adjusted for automatic analysis in open package statistics
programming R designed for statistics data processing and graphic operations [7]. In
order to analyze large amount of data, a special script program was installed in R
programming package. The program provided the dependencies of hardness on the
depth of indenter penetration for the pipe samples under study as well as generated
the averaged dependencies of hardness on the indentation depth based on the
experiments. The results of processing the experimental data are graphically
shown in Fig. 25.6.
Figure 25.6 shows the averaged dependencies of hardness on indentation depth of
ten measurements after heating, correcting, and burnishing.
200
180
160
140
120
100
80
60
40
20
-20
-40
-60
1 2 3 4 5

correcting; 3 – sandblasting; 4 – grinding after sandblasting; 5 – grinding after correcting
25.4 Conclusion
1. Shrinking residual stresses occur in pipes after heat treatment. Correcting oper-
ations form stretching residual stresses. Further sand jetting further increases the
level of stretching residual stresses. Burnishing decreases stretching residual
stresses but not significantly.
2. According to the research results, finishing operations of correcting and burnish-
ing in pipe production cause surface peening. The lowest hardness level is found
after heating the pipe samples. Further correction and burnishing additionally
increase hardness.
3. Applied finishing operations during production create residual stresses and sur-
face peening that decrease pipe resistance to corrosion during exploitation. The
objective of improving the quality of heat exchanger pipes can be reached by
Fig. 25.6 Hardness dependencies on indentation depth after finishing operations: 1 – pipe heat
treatment; 2 – correcting; 3 – correcting and grinding
creating new production techniques that will prevent the formation of stretching
residual stresses and increase pipe surface peening during the delivery process.
4. The ring tangential method can determine the integrated tangential residual
stresses. An interesting development of the work may be the determination of
the residual stresses on the surface of the tubes [8, 9].
Acknowledgements The study was made within the grant of Russian Science Foundation
(№ 17-79-100072), supported by Act 211 of the Government of the Russian Federation (agreement
No. 02.A03.21.0006).
References
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ment. Proceedings of the 8th International Conference on A-plants with VVER safety securing
Podolsk.
2. Karzov, G. P. Dynamics evaluation of VVER-1000 steam generator heat exchanger pipes
damages appearance and development in operating conditions. www.gidropress.podolsk.ru/
files/proceedings/seminar7/documents/f63.pdf
3. Karzov, G. P. Main heat exchanger pipes damages mechanisms in various exploitation stages of
VVER-1000 type steam generators. Proceedings of the 7th International Conference on Hori-
zontal Steam Generators. www.gidropress.podolsk.ru/files/proceedings/seminar7/seminar7/
authors.htm
4. Neklyudov, I. M. (2003). Researching reasons of corrosion defects appearance in VVER-1000
steam generators heat exchanger pipes. Proceedings of the International Conference on South-
Ukraine A-plant steam generators heat exchanger pipes corrosion damages: Sevastopol
National University of Atomic Energy and Industry collected articles (pp. 5–63).
5. Fedoseev, A. E., Bulanova, T. M., & Goncharenko, U.D. (1998). Researching Balakovo
A-plant’s second part steam generator heat exchanger pipes damages origin, New technologies
for energetics, industry, and construction: collected articles (pp. 38–42). Dimitrovgrad: Atomic
reactors scientific research Institute.
6. Birger, I. A. (1963). Residual stresses, M.: State scientific and technical publishing office
engineering literature.
7. R Development Core Team. (2011). R: A language and environment for statistical computing. R
Foundation for Statistical Computing, Vienna, Austria. ISBN 3–900051–07-0. www.R-project.org
8. Shimov, G. V. (2018). Rapid Method for Determining the Distribution of Residual Stresses in
Pipes. Materials Performance and Characterization 7(4):20170050
9. Shimov, G., Rozenbaum, M., Serebryakov, A., & Serebryakov, A. (2016). The method for
measuring residual stress in stainless steel pipes. Journal of Chemical Technology and Metal-
lurgy, 51(4), 458–464.
Author Index
A Gervasyev, M., 3–9

Ageev, N.G., 59–64 Gruzdeva, I.A., 11–16
Anisimova, O., 43–48, 73–79
Arlic, U., 33–39
H
Husnullin, D., 33–39
B
Bazhukov, I., 195–202
Bocharov, V., 89–95 I
Bogatov, A., 157–168, 187–192 Ignatkina, V.A., 89–95
Bogatov, N.A., 163–168
K
D Kapustin, F., 99–106
Deryabin, V., 123–130, 139–146 Karimov, K.A., 51–57
Domanskaya, I., 149–153 Kayumov, A., 89–95
Khotinov, V.A., 27–31
Kolmachikhin, B.V., 59–71
E Kolmachikhina, E., 43–48, 81–88
Erpalov, M., 187–192
L
F Lazutkina, O., 131–137
Farafontova, E., 123–130 Levina, A., 19–25
Farber, V.M., 27–31 Loginov, Yu., 179–184
Finkelstein, A., 33–39
Fomin, A., 179–184
Fomina, I., 117–122 M
Maltsev, V., 89–95
Mal’tseva, L., 19–25
G Mal’tseva, T., 19–25
Gerasimov, S., 11–16 Mamyachenkov, S., 73–79
Gerasimova, E., 107–114 Mamyachenkov, S.V., 43–48

https://doi.org/10.1007/978-3-319-75340-9
206 Author Index
Menshchikov, V.A., 51–57, 59–71 Romanova, K., 3–9

Morozova, A., 27–31 Rozenbaum, M., 195–202
N S
Naboychenko, S., 81–88 Salikhyanov, D.R., 163–168
Naboychenko, S.S., 51–57 Serebryakov, An., 195–202
Neustroev, V.I., 51–57 Sharapova, V., 19–25
Novgorodov, D., 3–9 Shimov, G., 195–202
Spiridonova, A., 99–106
O
Oleinik, V., 99–106, 117–122, 149–153 T
Orlov, G., 171–177 Tochilova, I., 139–146
P V
Paramonova, O., 123–130 Viduetsky, M., 89–95
Pavlov, D.A., 157–162 Voroshilova, I., 131–137
Pavlova, E.A., 157–162
Pomazkin, E., 99–106
Z
Zhukov, V.P., 59–64
R
Riehemann, W., 33–39
Rogozhnikov, D., 73–79
Subject Index
A phase ratio, 19
Activation energy, pearlitic and bainitic quenching temperature, on physical
transformations properties, 21
Avrami equation, 4, 5 structure formation, 22
calculation, 5 tensile strength and yield strength, 24
existing TTT diagrams, 5 03Kh14N10K5M2Yu2T steel’s structure, 19
on supercooling, 9 Avrami equation, 4, 5, 7, 9
temperature dependence, 4
time dependence, transformation
development, 5 B
Adhesion layer, 131, 136 Bimetal pipes, 167
Alloy behavior, Cu-Ni-Zn, 11 Biogenic ash, 150
Alloying addition, Sn and Al, 11, 12, 16 Blowing intensity, 59–64
Aluminum porous filters, 34 Brown coal, 150, 153
API X80 steel
Charpy fracture surface zones, 31
Charpy impact tests, 28 C
fracture zone length, 29 Capillary-crystallization strength
impact load vs. displacement curves, 28, 29 contact duration, 141–144
low-carbon (LC), 28 slip types, 139
Arsenic solid particle adhesion, 140
cakes, OSF matte, 55 typical stages, 140
extraction, 52, 53, 55 Capillary-dispersed system, 140
removal, 54, 55 Capillary force, 129
Austenite, undercooled, see Undercooled Casting bar structure, nickel silver, 15
austenite Casting mold fillability, Cu-15Ni-20Zn alloy,
Austenitic-ferritic steel 11–14, 16
chemical composition, 19 Cement-fly ash-limestone meal, 111
DSC heating curves, 23, 24 Cement-fly ash-marble powder, 111
hardness, 19 Cement-marble powder-limestone meal, 111
heat treatment, 21 Cement stone
hot metal forming, 24 Cа aluminate and alum ferrite hydration, 101
laser surface treatment, 21 composition, 103
microstructure, 20, 22 crystalline hydrates, 101

https://doi.org/10.1007/978-3-319-75340-9
208 Subject Index
Cement stone (cont.) vs. maximum strain amplitude, porous

electron microscope, 101 bending beams, 37
gypsum and clinker minerals, 101 measurement, 36
hydration products, 99 replicated aluminum foam
mechanism, 104–106 pore sizes, 37, 38
preparation, 100 sample preparation technology, 36
water resistance, 99 replicated porous aluminum, 38
Charpy impact testing, 27–29 sample preparation technology, 35–36
Circular fluidized bed (CFB), 150–152 strain amplitude, 37
Coating enamel slip, 141–142, 145 Deformation, 181, 182, 184
Cold drawing and rolling Differential scanning calorimetry (DSC),
calibration, calculation of, 174, 175 23, 24
classical methods, 171 Differential thermal analyses (DTA), 99
computer model, 172–174 Dolomite powder, 124, 126, 129
conventional mill, 176
finite-element method, 172
intermediate profiling, 174 E
matrix, 171, 172 Enamel frit synthesis, 139
mills, 176 Enamel slip particles interaction, 141–145
periodic drawing, 171 capillary-crystallization, 139
sizing pair, 176 contact layers
technological niches, 171 coating enamel slip, 141–142
Cold modeling, 59, 60 ground enamel slip, 143–144
TROF converter, 66, 67 kombi-ground slip, 144, 145
Composite cement, polymer addition crystallization process, water component,
compressive and flexural strength, 109, 145–146
110, 114 Energy dispersive microanalyzer, 136
experimental technique, 109 Equilibrium structure, 22, 24
marble powder, 110
polymer modifiers, 114
raw materials, 108 F
Computer model, 172–174 Fine dust
Concretionary ash, 150 composition, 44
Copper, 65, 66 diffractogram, 44
arsenate, form of, 53 leaching, small-scale tests, 43
arsenic and lead, 51 metallurgical fine dust treatment, 43
deposition, 55 X-ray phase analysis, 43
extraction, 52, 53, 55 Finite element method, 172, 181, 182
smelting, 51 Finite element simulation, 187, 188, 190
sulfate, 54, 55 Fly ash, 108, 110, 114
mattes, treatment of, 56 CFB, 152
Critical micelle concentration (CCM), 84 characteristics, 150, 151
Cu-Ni-Zn alloy Gibbs energy calculation, 152, 153
casting mold fillability, 11–13, 16 overview, 149
lost-wax process, 11–14, 16 properties, 152
mechanical and technical properties, 11 See also Unburnt ash gravel (UAG)
strength and wear resistance, 11 Fracture surface, X80 pipes
Charpy impact specimens, 28
crack propagation mechanisms, 27
D LC steel, 29
Damping, 36–38 separations, 27
bending beam vibrations, 36, 37 temperature dependences, 29
elastic vibration energy, into internal Freundlich isotherm, 85
friction heat, 34 Full-scale experiment, 191
Subject Index 209
G OEDP selective complexation, 44

Gibbs energy change, 73, 76, 77, 79 plant, 53, 56
Glass batch, 127, 128 Lignosulfonate adsorption
chemical composition, 123 characteristics, 83–85
description, 123 experiments, 82
distribution of fractions hydrophilic ionogenic functional
dry dolomite powder, 126, 127 groups, 81
material, 127 hydrophobic skeleton, 81
moistened dolomite, 127 isotherm of adsorption, 86
powder dolomite, 128 method, 82
experimental technique, 124 mineral and sulfur surfaces, 82
preparation, operations, 123 molten elemental sulfur, 81
quartz sand–soda, 124 nickel-pyrrhotine concentrate leaching, 81
raw materials, preparation of, 123 parameters, 87
segregation, 123, 124, 126 pressure leaching processes, 81
“silica sand–soda” mixture, 126 Limestone meal (LM), 108, 110, 114
Glass melting apparatus, 179, 180 Lining pump-compressor pipes
Granulation, 119 advantages, 166
Ground enamel slip, 143–145 field conditions, 167
mandrel, 166
operations, 165
H quality, 166
High-lime fly ash (HLFA) Lost-wax method, 11–13, 16
Hydraulic activity, 149, 152, 153
Hydrodynamics, 59, 64
Hydrometallurgy, 92, 95 M
Marble powder (MP), 107, 108, 110, 114
Matte, 52–54
I composition, 52
Impurities, 46 flowchart, process, 56
Infiltration ash, 150 oxidative sulfuric acid pressure leaching
Instrumented Charpy test, 27 (see Oxidative sulfuric acid
pressure leaching)
pressure leaching, preliminary treatment,
K 54–56
Kamsky lignosulfonate, 85 treatment, copper sulfate, 54, 55
Kansko-Achinsk brown coals, 150 “Maykain B” deposit, 74
Kinematic tension, 160–161 Metal-enamel penetration zone, 136
Kinetics of phase transformations, 21, 24 Metal forming
Kombi-ground slip, 144, 145 defects, 187, 188, 190–192
finite element simulation, 187, 188, 190
full-scale experiment, 191, 192
L oil and gas production, 187
Langmuir model, 85 tool calibration, 188, 191
Leaching upsetting process, 187–189, 191, 192
fine dust, 43 Metal-oxide melt adhesion, enamel coatings
lead and zinc, optimization, 45 advancement rate, oxidation boundary, 133
parameters, 44 equilibrium constants, 134, 135
setup, dust leaching, 45 Fe, Co, and Ni oxidation, 136
Lead, 51, 53–55 mobility of iron ions, 131
extraction of, 44 oxidation boundary, 133
IR spectra, lead phosphonate, 48 oxidation process, 132
leaching optimization, 45 X-ray analysis, 137
210 Subject Index
Microhardness, δ-ferrite, 19, 22 dissolubility, 43

Mineral additions, 107, 108, 110 IR spectra, 45, 47
Multihole stamping pH value, 44
finite element method, 181, 182 phosphorus, existence of, 47
fragment, 181 structural formula, 44
glass melting apparatus, 179
metal flow, 180, 183
metal industry, 179 P
semi-row, 180, 181 Particle capillary-crystallization
simulation, 183 fixation, 126
stamped tip-plate, 179 Pearlitic and bainitic transformations
technologies, 179 activation energy calculation, 5
unique properties, 179 kinetics of, 9
parameters, 4
process activation energy, 4
N on supercooling, 9
Nickel silver temperature dependence, 4
on casting mold fillability, 12 time dependence, 4
Cu-Ni-Zn ternary alloy, 11 TTT diagrams, 3
fine-grained microstructure, 15 Periodic drawing, 171
mechanical and technical properties, 11 Phase composition, austenite and δ-ferrite, 21
melting and casting, 12 Pilot models, 167
perforated plate, 13 Pipe-rolling plants (PRP)
sample microstructure, 15 kinematic tension, 160–161
short-run, 12 plug rolling process, 157
strength and wear resistance, 11 round and oval billets, 158–160
Nitric acid Platinum, 179, 182
Gibbs energy change, 76 Platinum group metals (PGM), 89
leaching reactions, 73 Polymer cement stone strength, 109
and metal sulfides, 77 Polymer modifiers, 108, 109, 114
oxidation, sulfides, 78 Polymetallic raw materials, 51
for sulfide multicomponent middlings Polymetallic sulfide raw material
leaching, 73 flotation, 73
sulfide raw materials leaching, 77 Porous open-cell aluminum production, 33
X-ray diffraction analysis, 74 Portland cement (PC), 117, 118
with ZnS, CuFeS2, FeS2, and PbS, 75 compressive strength, 110
flexural strength, 111
mineral additions, 108
O Pourbaix diagram, 73, 79
Oil industry, 163 Powder wetting, 130
PCP (see Pump-compressor pipes (PCP)) Pump-compressor pipes (PCP)
in Russia, 163 durability of, 164–165
Optimization, leaching, 45 failure of, 163
Ore-smelting furnace (OSF), 51 pilot models, 167
Oxidative sulfuric acid pressure leaching replacement, 164
acid concentration, 53 restoration costs, 163
arsenic extraction, 53 service life of, 163
cakes, 56 worn, 167
copper extraction, 52, 53 Pyrrhotite, 89–91
experimental conditions and results, 53
lead plant, 53
Oxyethylidenediphosphonic acid (OEDP) Q
described, 43 Quartz sand–soda, 124
Subject Index 211
R Supersaturated solid solution, 23

Replicated aluminum foam, see Damping Surface hardening, see Residual stresses
Replication casting technology, 35 Swirling, 60, 61, 64
Residual stresses
finishing operations, 195, 196, 199, 202
heat exchanger tubes, 195 T
materials and methods, 196–198 Thermodynamic features
nuclear power development, 195 sulfide middlings nitric acid leaching
surface peening, 200 reactions, 73
technological operations’ influence, Top submerged lance (TSL), 59, 61, 64
198–199, 201 Torch penetration, 59, 61–64
Reversed austenite TROF (tilting rotating oxy-fuel) converter
austenitic-ferritic 03Kh14N10K5M2Yu2T advantages, 65
steel, 25 blowing, 67
laser surface treatment, 21 cavern, analysis of, 69
precipitations, 21 cold simulation, 66
Widmanstatten pattern, 24 construction of, 65
copper-containing materials, 65
description, 65
S energy balance, 70
Shaft furnace (SF), 51 experimental setup, scheme of, 66
Silica sand–soda mixture, 126 flow trajectory, 68, 69
Silicate-enamel coatings, 131 hydrodynamics, 66
Smelting, 51 TSL furnaces, 59, 61, 64
Soda–sand, 129 TTT diagrams
Sodium hydroxide, 105 and major alloying elements|, 5, 6
Solid Edge software, 12 undercooled austenite, 3
Steam generator (SG), 195
Stub mandrel, 160–161
Sulphide minerals U
butyl xanthate, 91 Unburnt ash gravel (UAG)
butyl xanthogenate, 90 artificial equivalents, 117
chlorine processes, 92 coarse aggregate, 117
contrast, 95 composition and structure, 118
copper and zinc minerals, 90 compressive strength, 119
copper-lead-zinc ores, 92 deterioration of concrete, 121
copper ore and copper-zinc ore fly ash and Portland cement (PC), 117
processing, 91 fuel and energy resources, 122
flotation of ores, 90 high-quality crushed stone and gravel, 117
fractional flotation, 92 hornblendite, 122
hydrometallurgical processes, 90 macrostructure, 119
iron sulphides, 89 manufacture of concretes, 120–121
optimum pH values, 91 microstructure, 119
pyrite copper-zinc ores, 90, 93 physical-mechanical properties, 118,
selective collectors, 90, 92 119, 122
sphalerite depression, 91 physical-technical properties, 117
stepnoe polymetallic ore, 92 steam treatment, 118
sulphide polymetallic lead-zinc, 92 thermal analysis, 119
tennantite, 92 types, 118
treatment, mineral resource, 94, 95 Undercooled austenite
Sulphide minerals kinetics of, 3
“hard” depression mode selection, 91 temperature dependence, 4
treatment, mineral resource, 94–95 TTT diagrams, 3
212 Subject Index
W Z
Water-glycerol emulsion, 60 Zinc, 44
Waterproofing penetrative capillary mixture extraction of, 44
(WPCM), 99–101, 104, 106 response surfaces, 45
temperature and pulp density, 46
X
X80 grade steels, 27
X-ray diffraction (XRD), 99

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Innovation and Discovery in Russian Science and Engineering

More information about this series at http://www.springer.com/series/15790

J. W. Newkirk • A. A. Popov • A. S. Zhilin

Progress in Materials Science

ISSN 2520-8047 ISSN 2520-8055 (electronic)

Library of Congress Control Number: 2018938828

© Springer International Publishing AG, part of Springer Nature 2018

Printed on acid-free paper

Rolla, MO, USA J. W. Newkirk

Part I Structure Formation Analysis of Complicated Alloys

Part II Non-ferrous Metals Metallurgy due to the Reﬁning

7 High-Pressure Leaching Arsenic Containing Polymetallic

Part III Composite Compound Materials Science in Building

18 Study of Enamel Slip Particles Interaction Using

Part IV High-Pressure Treatment of Metals and Alloys

Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205

M. Gervasyev, D. Novgorodov, and K. Romanova

M. Gervasyev (*) · K. Romanova

© Springer International Publishing AG, part of Springer Nature 2018 3

1.2 Calculation Technique Development for Kinetic

Any phase transformation can be represented as a function of two basic parameters,

1.2.1 Digitization of the Existing TTT Diagrams

1.2.2 Establishing the Time Dependence of Transformation

1.2.3 Determining A and n Parameters in the Avrami

1.2.4 Activation Energy Calculation

Fig. 1.1 TTT diagrams and

Fig. 1.2 Time dependence a 120 150

Fig. 1.3 Dependence of ln a 4 150

Table 1.1 Parameter n in the Bainite Perlite

Fig. 1.4 ln А as a function a 0

Fig. 1.5 The value of Q/R a

with temperature, growing in the absolute value as approaching the equilibrium

1.2.5 Discussion of Results

where fbmax depends on the supercooling. Similar to the martensitic transformation

I. A. Gruzdeva and S. S. Gerasimov

2.2 Materials and Methods

I. A. Gruzdeva (*) · S. S. Gerasimov

© Springer International Publishing AG, part of Springer Nature 2018 11

Fig. 2.2 Perforated plate

Fig. 2.4 Nickel silver

quality, and microstructure. We chose Al and Sn as dopants. The conditions of

Fig. 2.5 Nickel silver

Table 2.1 Casting mold ﬁllability depending on casting temperature

Table 2.2 Casting mold ﬁllability depending on dopant alloyage

Table 2.3 Casting mold ﬁllability depending on casting temperature

To summarize, a method of estimating mold ﬁllability has been introduced. The

L. Mal’tseva, A. Levina, T. Mal’tseva, and V. Sharapova

L. Mal’tseva (*) · A. Levina · T. Mal’tseva · V. Sharapova

© Springer International Publishing AG, part of Springer Nature 2018 19

microscope JEM-200CX. Phase composition of steel was studied by X-ray diffrac-

3.2 Results and Discussion

Fig. 3.3 Microstructure of austenitic-ferritic steel 03Kh14N10K5M2Yu2T hardened (a–d)

101.0 Peak 731.4 °C Peak 981.0 °C

100.4 Value 5323 °C -6

the second (620–820 C) is associated with the above-described processes of

Table 3.2 The mechanical properties of the steel at high temperatures

The study of the investigated austenitic-ferritic 03Kh14N10K5M2Yu2T steel

V. Khotinov, V. Farber, and A. Morozova

V. Khotinov (*) · V. Farber · A. Morozova

© Springer International Publishing AG, part of Springer Nature 2018 27

4.2 Materials and Experimental Procedure

4.3 Results and Discussion

Fig. 4.1 Impact load vs. displacement curves of LC steel