Plasma Surface Metallurgy: Zhong Xu Frank F. Xiong

Zhong
Xu · Frank F. Xiong
Plasma Surface
Metallurgy
With Double Glow Discharge Technology
—Xu-Tec Process
Plasma Surface Metallurgy
Zhong Xu Frank F. Xiong
•

With Double Glow Discharge Technology
—Xu-Tec Process
123
Zhong Xu Frank F. Xiong
Taiyuan University of Technology Heaptech Engineering, Inc.
Taiyuan, Shanxi San Jose, CA
China USA
ISBN 978-981-10-5722-9 ISBN 978-981-10-5724-3 (eBook)

DOI 10.1007/978-981-10-5724-3
Jointly published with Science Press, Beijing, China

ISBN: 978-7-03-053693-8 Science Press, Beijing, China
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I would like to dedicate this book to
Dr. German Bernard Berghaurs, the inventor
of plasma nitriding technology and a pioneer
who had been first applying the glow
discharge phenomenon to material surface
alloying technology.
Innovative development of the plasma
nitriding technology made it possible for me
to invent the technology of Double Glow
Discharge Plasma Surface Metallurgy.
David Zhong Xu
@ Taiyuan, China
Foreword
The modification of metal surfaces is used to increase surface hardness, improve

interface interactions between separate surfaces (tribological interactions), and/or
decrease surface chemical activity and degradation. Surface modifications can
improve the performance and extend the life of basic materials, particularly those
that have desirable bulk characteristics such as weight per volume, machinability,
material cost, etc. The reference book, “Plasma Surface Metallurgy with Double
Glow Discharge Technology”, written by my good friend Prof. Zhong Xu and his
colleagues, is to introduce this kind of surface metallurgical technology to our
readers.
I met Prof. Xu in the United States in 1981. It was at this time that he began
serious work on a “new” plasma technique based upon a double glow discharge
process. The process has been shown experimentally and commercially to modify
metal surfaces (and ceramic surfaces) to improve important parameters already
noted. Additionally, the surface treatment alloy elements diffuse into the base metal
to a sufficient depth and the modified surface layer attaches effectively to the base
material such that the interface adhesion is extraordinary.
This book explains and describes the metallurgy, physics, and chemistry of this
new technique and describes current and future application areas. Prof. Xu’s
technique was patented in many countries and is known as Xu-Tec. Numerous
commercial products have been made and implemented using this process. The
technique holds considerable potential for numerous applications, particularly for
sheet steel and for many unique alloys such as titanium, molybdenum, tantalum,
and super alloys, such as NiCrMoCu and NiCrMoNb, as well. Applications are
reported for hardening stainless steel and for plasma surface metallurgy to produce
antibacterial stainless steel surfaces.
The book is also a rather complete in-depth description of surface metallurgy in
general. Chapters are included which describe and explain surface engineering and
alloying technology including conventional techniques and plasma processing
(including nitriding, carburizing, and sulphurizing). Additionally, ceramization on
stainless sheet surfaces and treatment of ceramic surfaces are both described.
vii
viii Foreword
The book is particularly useful in that it describes industrial applications of

Xu-Tec and performance which can be achieved in applications such as band saw
blades and an industrial colloid mill. An application to produce corrosion resistant
steel plate is also described. Double glow plasma surface metallurgy equipment and
laboratory operation and commercial production are also described.
This book will be valuable to those in the general area of surface metallurgy. The
substantial description of the Xu-Tec process is very important and should assist in
expanding the use of this superior technique. The in-depth explanation of glow
discharges and their use in general will also serve as a valuable reference in the
field.
I congratulate Prof. Xu and his colleagues for their extraordinary technical and
application contribution which will serve researchers and manufacturers for the
future.
James E. Thompson
Dean of Engineering Emeritus, LaPierre Professor
of Mechanical and Aerospace Engineering
Fellow of the Institute of Electrical
and Electronic Engineers, University of Missouri
Columbia, MO, USA
Preface
The “Plasma Nitriding” process, invented by German Bernard Berghaus in 1930,

was the first surface alloying technology where nitrogen gas glow discharge plasma
was utilized. It is considered as one of the most important achievements in the
surface metallurgical modification and “the foundation stone of modern plasma
surface engineering”. Today, it has been widely used for surface nitriding treatment
on metals and has generated huge economic profits and social benefits. However, in
more than 50 years after its advent, plasma nitriding can only be applied to non-
metallic elements, such as nitrogen, carbon, sulfur, etc.
Advanced on the plasma nitriding technology, a new surface alloying modifi-
cation method, named the double glow discharge plasma surface metallurgy tech-
nology, has been invented by using the “Double Glow Discharge Plasma Process”.
In 1978, Prof. Zhong Xu discovered the “Double Glow Discharge Phenomenon”
in his laboratory in Taiyuan University of Technology, China. Following this
discovery, the “Double Glow Plasma Surface Metallurgy Technology” for the metal
surface alloying modification was invented in 1980. Further development was
advanced while Xu was visiting the USA and working in Prof. James Thompson’s
Laboratory.
In the double glow discharge plasma surface alloying process, one set of Argon
gas discharge plasma is employed for sputtering of a solid alloying target, while
another set of glow discharge plasma is generated on the substrate surface for
heating and alloying reaction. By this process, many chemical elements in the
chemical element periodic table, including the solid metal elements and gaseous
nonmetal elements, can be utilized for surface alloying on metals. The substrate
surface heating and thermal drive interdiffusion of sputtering deposited alloying
elements into the surface of substrate materials to form a surface alloy layer with
enhanced interface adhesion.
Double glow plasma surface alloying technology was filed for an invention
patent first in the United States of America in 1982 and granted in 1985.
Afterwards, this technology, referred as the “Xu-Tec Process”, had attracted a great
engineering interest in the materials industrial community upon its industrial
application potentials. Several news and appraisal comments on this subject have
ix
x Preface
been reported. Later, the Xu-Tec has also patented world-widely in the United
Kingdom, Canada, Australia, and Sweden et al.
In over almost 40 years after the invention, the experimental research results
have demonstrated that the Xu-Tec process can be utilized with high feasibility for
surface alloying modification of metals, to form many surface alloying layers with
high hardness, wear resistance, resistance to corrosion on the surfaces of low-grade
metal substrates. The substrate materials include titanium and titanium alloys,
copper and copper alloys, intermetallic compounds, and other conductive materials.
A gradient alloy ceramic layer (transferred from metal matrix to ceramic) can also
be formed on the surface of metal material by this technology.
The Xu-Tec process has opened up a new material engineering field of “Plasma
Surface Metallurgy”. With this surface metallurgy process for material surface
modification, it can transfer many low-grade and low-cost solid matrices of
industrial engineering materials to be a “gold” material with a high value and high
grade or special functions. This improved material would be widely used in
industrial production to improve the surface performance and quality of mechanical
parts and manufacturing products, and to conserve expensive alloying elements for
the benefit of all mankind.
Taking many advantages of the Xu-Tec process, several industrial applications
have developed. High-speed steel, stainless steel, nickel based alloys, and more
complex composition alloys on the surfaces of steels have been produced. Surface
alloying modification on cutting tools, chemical valves, colloid mills, large steel
plates, and other industrial products was also demonstrated, with substantial
improvement in their surface properties and quality of components for the
mechanical manufacturing industry. The Xu-Tec process has been developed to be
one of the most advanced, powerful, and practical surface alloying technologies in
today’s world. This technology has broad application prospects in machinery
manufacturing, marine engineering, transportation, food processing equipment,
household appliances, and the aerospace and defense industries.
The Xu-Tec process is a typical physical metallurgical technology, involving a
series of advanced physical subprocesses such as vacuum and pressure control,
double glow discharge and low-temperature plasma, material sputtering and
physical vapor deposition, ion bombardment and plasma heating, thermal driven
interdiffusion, and alloying formation. This technology has no chemical waste and
no pollution (dust, liquid, gaseous). It is an environment-friendly and
resource-saving surface alloying technology.
In addition to using the double glow discharge phenomenon for surface modi-
fication, a series of other new technologies for material treatments have been also
developed, such as double glow plus arc discharge surface alloying, double glow
brazing, double glow sintering, double glow nano-powder synthesizing, double
glow diamond film growth, double glow surface cleaning, and more others.
The purpose of the book publication is to introduce the Xu-Tec technology to the
world and promote further attention and interest for scientific research and engi-
neering development, as well as industrial utilization and product commercializa-
tion. This book summarizes the technology development history, physical
Preface xi
mechanism, and research results of surface metallurgy with double glow plasma
surface metallurgy. To this end, the book has also concentrated additional detailed
understandings and experiences by numerous researchers and developers in this
technology area.
There are numerous researchers and engineers, as well as Ph.D. students and
professors who have given their substantial contributions to this technology
development. We just could not list all their names here to show them our appre-
ciations. However, we appreciate very much that this book has the following
persons contributed in writing:
• Chapters 5 and 13—Pingze Zhang, Ph.D.
• Chapters 6 and 7—Yanmei Zhang, Ph.D.
• Chapter 8—Zhengxian Li and Wen Zhao, Ph.D.
• Chapter 9—Xiaoping Liu, Ph.D.
• Chapter 10—Wenping Liang, Ph.D.
• Chapter 11—Qiang Miao and Hongyan Wu, Ph.D.
• Chapter 12—Jun Huang, Ph.D.
We are especially grateful for the help from Dr. Hongyan Wu and Dr. Jun Huang,
who have spent much time in assisting of proof reading and formatting of this book.
It is also very grateful to Springer and Science Press China to give such an
opportunity to publish this book in time.
Acknowledgements: All figures in this book are reprinted from the related refer-
ences given in each chapter, with written permission from the corresponding
copyright holders in the list below. We acknowledge their permissions and very
much appreciate their support:
1. Advanced Materials Research
2. Applied Surface Science
3. China Science Press, Beijing
4. China Surface Engineering (中国表面工程)
5. Corrosion Science and Protection Technology (腐蚀科学与防护技术)
6. Heat Treatment of Metals (金属热处理)
7. Hot Working Technology (热加工工艺)
8. Journal of China Society of Corrosion and Protection
9. Journal of Rare Earths
10. Rare Metal Materials & Engineering (稀有金属材料与工程)
11. Surface & Coatings Technology
12. Transactions of Materials and Heat Treatment (材料热处理学报)
13. Materials Review (材料导报)
14. Transactions of Nonferrous Metals Society of China (中国有色金属学报)
15. Tribology
16. Vacuum
17. Vacuum Science and Technology (真空科学与技术学报)
xii Preface
18. China Knowledge Resource Integrated Database (CNKI) (中国期刊全文数据

库)
19. Journal of Nanjing University of Aeronautics and Astronautics (南京航空航天
大学学报)
20. Journal of Taiyuan University of Technology (太原工业大学学报)
21. Journal of Wuhan University of Technology-Mater. Sci. Ed (武汉工业大学学
报-材料科学版)
22. https://en.wikipedia.org/wiki/Glow_discharge
Zhong Xu
Taiyuan, China
Frank F. Xiong
San Jose, USA
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Engineering Materials and Its Surface. . . . . . . . . . . . . . . . . . . . . 1
1.2 Surface Engineering and Its Classification . . . . . . . . . . . . . . . . . 2
1.2.1 Concept of Surface Engineering . . . . . . . . . . . . . . . . . . 2
1.2.2 Surface Hardening Technology . . . . . . . . . . . . . . . . . . . 3
1.2.3 Surface Covering Technology . . . . . . . . . . . . . . . . . . . . 4
1.2.4 Surface Alloying/Metallurgy Technology . . . . . . . . . . . 5
1.2.5 Classification Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3 Existing Surface Alloying Technology . . . . . . . . . . . . . . . . . . . . 7
1.3.1 Conventional Surface Alloying Technology . . . . . . . . . 7
1.3.2 Modern Surface Alloying Technology . . . . . . . . . . . . . . 8
1.3.3 Concept of Plasma Surface Metallurgy . . . . . . . . . . . . . 8
1.4 Glow Discharge and Plasma Nitriding . . . . . . . . . . . . . . . . . . . . 9
1.4.1 History of Glow Discharge . . . . . . . . . . . . . . . . . . . . . . 9
1.4.2 Concept of Plasma. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.4.3 Advent of Plasma Nitriding in Germany . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2 Plasma Nitriding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.1 Glow Discharge and Its Characteristics . . . . . . . . . . . . . . . . . . . . 13
2.1.1 Characteristics of Glow Discharge . . . . . . . . . . . . . . . . . 13
2.1.2 Stratified Phenomenon . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.1.3 Interactions Between Ions and Material Surface . . . . . . 15
2.2 Plasma Nitriding Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.1 Basic Principle. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.2 Advantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.3 Industrial Applications . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.3 Other Plasma Surface Alloying Technology . . . . . . . . . . . . . . . . 19
2.3.1 Plasma Carburizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.3.2 Plasma Nitro-Carburizing . . . . . . . . . . . . . . . . . . . . . . . 19
xiii
xiv Contents
2.3.3 Plasma Sulphurizing . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

2.4 Restriction of Plasma Nitriding . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.5 Development of Plasma Nitriding in China . . . . . . . . . . . . . . . . 20
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3 Double Glow Discharge Phenomenon and Its Applications . . . . . . . 23
3.1 What Is Double Glow Discharge Phenomenon? . . . . . . . . . . . . . 23
3.2 Discovery of Double Glow Discharge . . . . . . . . . . . . . . . . . . . . 24
3.3 Double Glow Discharge Modes . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.3.1 Independent Discharge Mode . . . . . . . . . . . . . . . . . . . . 25
3.3.2 Dependent Discharge Mode . . . . . . . . . . . . . . . . . . . . . . 25
3.3.3 Pulse Discharge Mode . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.3.4 Other Discharge Mode . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.4 Double Glow Hollow Cathode Discharge (DG-HCD) . . . . . . . . 26
3.4.1 Hollow Cathode Discharge (HCD) . . . . . . . . . . . . . . . . 26
3.4.2 Concept of DG-HCD . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.4.3 Current Amplification Effect of DG-HCD . . . . . . . . . . . 29
3.5 Advent of Double Glow Plasma Surface Alloying/Metallurgy
(Xu-Tec Process) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.5.1 First Experimental Device . . . . . . . . . . . . . . . . . . . . . . . 30
3.5.2 First Microstructure of Tungsten Surface Alloy . . . . . . . 31
3.5.3 Other Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4 Double Glow Plasma Surface Alloying/Metallurgy Technology . . . . 33
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4.2 Basic Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.3 Diffusion Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4.4 Process Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4.5 Configuration of Working-Piece and Source Electrode . . . . . . . . 38
4.5.1 Plate Type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.5.2 Cave Type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.5.3 Deep Well Type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.6 Technological Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.6.1 Measurable Parameters . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.6.2 Typical Process Parameters . . . . . . . . . . . . . . . . . . . . . . 47
4.6.3 Nonmeasurable Parameters . . . . . . . . . . . . . . . . . . . . . . 48
4.7 Arc Discharge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.7.1 Micro-Arc Discharge . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
4.7.2 Macro Arc Discharge . . . . . . . . . . . . . . . . . . . . . . . . . . 50
4.7.3 Harmfulness of Arc Discharge. . . . . . . . . . . . . . . . . . . . 51
4.7.4 Reasons of Arc Discharge . . . . . . . . . . . . . . . . . . . . . . . 51
Contents xv
4.8 Cathode Power Transmission Device and Gap Protection . . . . . . 53

4.8.1 Requirements of Cathode Transmission Device . . . . . . . 54
4.8.2 Principle of Gap Protection . . . . . . . . . . . . . . . . . . . . . . 54
4.8.3 Example of Cathode Transmission Device . . . . . . . . . . 56
4.9 Advantages of Xu-Tec Process . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.10 Requirements for Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.11 Xu-Tec Process in USA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.12 Xu-Tec Process in China . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
4.13 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5 Physical Basis of Plasma Surface Metallurgy . . . . . . . . . . . . . . . . . . 63
5.1 Glow Discharge and its Discharge Characteristics . . . . . . . . . . . 63
5.1.1 Gas Discharge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.1.2 Glow Discharge Process . . . . . . . . . . . . . . . . . . . . . . . . 64
5.1.3 Stratification Phenomenon . . . . . . . . . . . . . . . . . . . . . . . 66
5.1.4 Glow Discharge Characteristics . . . . . . . . . . . . . . . . . . . 68
5.2 Low-Temperature Plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.2.1 Plasma and Its Generation . . . . . . . . . . . . . . . . . . . . . . . 69
5.2.2 Characteristics of Double Glow Discharge Plasma . . . . 71
5.3 Ion Bombardment and Sputtering . . . . . . . . . . . . . . . . . . . . . . . . 73
5.3.1 General Description of Sputtering Process . . . . . . . . . . . 73
5.3.2 Preferential Sputtering . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.3.3 Alloy Sputtering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.4 Propagation of Glow Discharges. . . . . . . . . . . . . . . . . . . . . . . . . 76
5.4.1 Ionization Degree and Mean Free Path . . . . . . . . . . . . . 77
5.4.2 Propagation of Plasma in Double Glow Discharges . . . 78
5.5 Diffusion Process Under Ion Bombardment . . . . . . . . . . . . . . . . 79
5.5.1 Diffusion Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
5.5.2 Diffusion Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5.6 Prospect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
6 Plasma Surface Metallurgy of Iron and Steel . . . . . . . . . . . . . . . . . . 89
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
6.1.1 Plasma Surface Alloying and Alloying Element . . . . . . 89
6.1.2 Interaction of Alloying Element with Fe and C . . . . . . . 90
6.2 Single-Element Plasma Surface Metallurgy. . . . . . . . . . . . . . . . . 91
6.2.1 Plasma Surface W Alloying. . . . . . . . . . . . . . . . . . . . . . 91
6.2.2 Plasma Surface Ti Alloying . . . . . . . . . . . . . . . . . . . . . . 92
6.2.3 Plasma Surface Cr Alloying . . . . . . . . . . . . . . . . . . . . . 93
6.2.4 Plasma Surface Al Alloying . . . . . . . . . . . . . . . . . . . . . 95
6.2.5 Plasma Surface Mo Alloying . . . . . . . . . . . . . . . . . . . . . 95
6.2.6 Plasma Surface Ta Alloying . . . . . . . . . . . . . . . . . . . . . 97
xvi Contents
6.3 Multiple-Element Plasma Surface Metallurgy . . . . . . . . . . . . . . . 97

6.3.1 Plasma Surface W–Mo Alloying . . . . . . . . . . . . . . . . . . 98
6.3.2 Plasma Surface Ni–Cr Alloying . . . . . . . . . . . . . . . . . . . 99
6.3.3 Plasma Surface Cr–Mo Alloying . . . . . . . . . . . . . . . . . . 99
6.4 Plasma Surface Metallurgy Superalloys . . . . . . . . . . . . . . . . . . . 100
6.4.1 Superalloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
6.4.2 Plasma Surface Ni–Cr–Mo–Nb Superalloys . . . . . . . . . 101
6.4.3 Plasma Surface Ni–Cr–Mo–Cu Superalloys . . . . . . . . . . 102
6.5 Plasma Surface Metallurgy Precipitation Hardening
Stainless Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
6.5.1 Plasma Surface Alloying Process. . . . . . . . . . . . . . . . . . 103
6.5.2 Age Hardening Process . . . . . . . . . . . . . . . . . . . . . . . . . 104
6.5.3 Corrosion and Wear Tests . . . . . . . . . . . . . . . . . . . . . . . 104
6.6 Plasma Surface Metallurgy Antibacterial Stainless Steels . . . . . . 105
6.6.1 Cu-Antibacterial Stainless Steel . . . . . . . . . . . . . . . . . . . 105
6.6.2 Ag-Antibacterial Stainless Steel . . . . . . . . . . . . . . . . . . . 106
6.6.3 Ag–Cu Antibacterial Stainless Steel . . . . . . . . . . . . . . . 106
6.7 Plasma Composite Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
6.7.1 Plasma Titanium and Titanium–Nitrogen Alloying . . . . 107
6.7.2 Brush Plating and Plasma Surface Alloying . . . . . . . . . 107
6.8 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
7 Plasma Surface Metallurgy High-Speed Steel . . . . . . . . . . . . . . . . . . 109
7.1 High-Speed Steels (HSS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
7.1.1 Conventional Metallurgy HSS . . . . . . . . . . . . . . . . . . . . 109
7.1.2 Powder Metallurgy HSS . . . . . . . . . . . . . . . . . . . . . . . . 110
7.1.3 Plasma Surface Metallurgy HSS . . . . . . . . . . . . . . . . . . 110
7.2 Plasma Surface Metallurgy W–Mo HSS . . . . . . . . . . . . . . . . . . . 111
7.2.1 Plasma Surface W–Mo Alloying . . . . . . . . . . . . . . . . . . 111
7.2.2 Carburizing, Quenching and Tempering . . . . . . . . . . . . 112
7.3 Plasma Surface Metallurgy Aging Hardening HSS . . . . . . . . . . . 113
7.3.1 Aging Hardening HSS and Its Excellent Cutting
Performance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
7.3.2 Plasma Surface W–Mo–Co Alloying . . . . . . . . . . . . . . . 113
7.3.3 Decarburization and Its Effect on Microstructure . . . . . . 115
7.3.4 Solid Solution and Aging Treatment . . . . . . . . . . . . . . . 118
7.4 Plasma Surface Metallurgy W–Mo–C HSS. . . . . . . . . . . . . . . . . 120
7.5 Plasma Surface Metallurgy W–Mo–Ti HSS . . . . . . . . . . . . . . . . 122
7.5.1 Plasma W–Mo–Ti Alloying . . . . . . . . . . . . . . . . . . . . . . 122
7.5.2 Carburizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
7.5.3 Quenching and Tempering . . . . . . . . . . . . . . . . . . . . . . 124
Contents xvii
7.6 Plasma Surface Metallurgy Mo–Cr Low Alloy HSS . . . . . . . . . . 124

7.7 Conclusion and Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
8 Plasma Surface Metallurgy of Titanium and Titanium Alloys . . . . . 129
8.1 Introduction to Titanium and Titanium Alloys . . . . . . . . . . . . . . 129
8.1.1 Classification and Properties . . . . . . . . . . . . . . . . . . . . . 129
8.1.2 Effect of Alloying Elements . . . . . . . . . . . . . . . . . . . . . 130
8.1.3 Optimal Alloying Parameters . . . . . . . . . . . . . . . . . . . . . 131
8.2 Plasma Surface Metallurgy Wear-Resistant Alloys . . . . . . . . . . . 132
8.2.1 Double Glow Plasma Molybdenizing . . . . . . . . . . . . . . 132
8.2.2 Double Glow Plasma Molybdennitriding . . . . . . . . . . . . 135
8.3 Plasma Surface Metallurgy Flame-Resistant Alloys . . . . . . . . . . 137
8.3.1 Method for Protecting Titanium Alloy from
“Titanium Fire” . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
8.3.2 Plasma Surface Metallurgy Ti–Cu Flame-Resistant
Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
8.3.3 Plasma Surface Metallurgy Ti–Cr Flame-Resistant
Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
8.3.4 Plasma Surface Metallurgy Ti–Mo Flame-Resistant
Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
8.3.5 Plasma Surface Metallurgy Ti–Nb Flame-Resistant
Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
8.4 Plasma Surface Metallurgy Ti–Pd
Corrosion-Resistant Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
8.4.1 Overview of Corrosion-Resistant Titanium Alloys . . . . 149
8.4.2 Plasma Surface Metallurgy Ti–Pd Alloy . . . . . . . . . . . . 150
8.4.3 Corrosion Resistance of Plasma Surface
Ti–Pd Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
8.5 Plasma Surface Metallurgy Ti–Nb
Corrosion-Resistant Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
8.6 Plasma Surface Carburizing Without Hydrogen . . . . . . . . . . . . . 153
8.6.1 Plasma Carburizing with no Hydrogen . . . . . . . . . . . . . 153
8.6.2 Microstructure and Composition
of Carburized Layer. . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
8.6.3 Tribological Properties. . . . . . . . . . . . . . . . . . . . . . . . . . 157
8.7 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
8.8 Prospect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
9 Plasma Surface Metallurgy of Intermetallic Compounds . . . . . . . . . 163
9.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
9.1.1 Intermetallic Compound and Its Classification . . . . . . . . 163
9.1.2 Conventional Surface Treatment . . . . . . . . . . . . . . . . . . 165
xviii Contents
9.2 Plasma Surface Metallurgy of TiAl . . . . . . . . . . . . . . . . . . . . . . 165

9.2.1 Plasma Surface Metallurgy Nb-Alloy . . . . . . . . . . . . . . 165
9.2.2 Plasma Surface Metallurgy Mo-Alloy . . . . . . . . . . . . . . 169
9.2.3 Plasma Surface Metallurgy Cr-Alloy . . . . . . . . . . . . . . . 172
9.2.4 Plasma Surface Metallurgy Ni–Cr–Mo–Nb Alloy . . . . . 174
9.3 Plasma Surface Metallurgy of Ti2AlNb . . . . . . . . . . . . . . . . . . . 174
9.3.1 Plasma Surface Metallurgy Cr-Alloy . . . . . . . . . . . . . . . 174
9.3.2 Plasma Surface Metallurgy Mo-Alloy . . . . . . . . . . . . . . 175
9.4 Prospect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
10 Plasma Surface Metallurgy of Other Materials . . . . . . . . . . . . . . . . . 179
10.1 Plasma Surface Metallurgy of Copper and Copper Alloys . . . . . 179
10.1.1 Plasma Surface Metallurgy Ti Alloy . . . . . . . . . . . . . . . 180
10.1.2 Plasma Surface Metallurgy Ni Alloy . . . . . . . . . . . . . . . 182
10.2 Plasma Surface Metallurgy of Niobium Alloy . . . . . . . . . . . . . . 182
10.2.1 Plasma Surface Metallurgy Ir Alloy . . . . . . . . . . . . . . . 183
10.2.2 Plasma Surface Metallurgy Mo Alloy . . . . . . . . . . . . . . 183
10.2.3 Plasma Surface Metallurgy Fe–Cr–Mo–Si Alloy . . . . . . 184
10.3 Plasma Surface Metallurgy of Molybdenum . . . . . . . . . . . . . . . . 185
10.4 Plasma Surface Metallurgy of Tungsten . . . . . . . . . . . . . . . . . . . 186
10.5 Plasma Surface Metallurgy of C/C Composite . . . . . . . . . . . . . . 187
10.6 Plasma Surface Metallurgy Ta Alloy . . . . . . . . . . . . . . . . . . . . . 188
10.7 Plasma Surface Metallurgy Fe–Al–Cr Alloy . . . . . . . . . . . . . . . . 191
10.8 Prospect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
11 Gradient Ceramization of Metal Surface and Metallization
of Ceramic Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
11.1 Ceramization of Carbon Steels . . . . . . . . . . . . . . . . . . . . . . . . . . 197
11.1.1 Plasma Surface Metallurgy TiN Ceramic . . . . . . . . . . . . 198
11.1.2 Plasma Surface Metallurgy WC Ceramic . . . . . . . . . . . . 203
11.1.3 Plasma Surface Metallurgy TiC Ceramic . . . . . . . . . . . . 208
11.1.4 Plasma Surface Metallurgy Ti(CN) Ceramics . . . . . . . . 210
11.2 Metallization of Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
11.2.1 Metallization of TiSi30 Ceramic . . . . . . . . . . . . . . . . . . . 211
11.2.2 Metallization of Si3N4 Ceramic . . . . . . . . . . . . . . . . . . . 212
11.2.3 Plasma Surface Metallurgy Ta–C on Diamond
and Cemented Carbide . . . . . . . . . . . . . . . . . . . . . . . . . 214
11.2.4 Surface Metallization of Diamond Films . . . . . . . . . . . . 217
11.3 Plasma Surface Metallurgy Gradient-Function Luminescent
Ceramics Er–ZrO2 on Ti6Al4V . . . . . . . . . . . . . . . . . . . . . . . . . 218
Contents xix
11.3.1 Zirconia Functional Ceramics . . . . . . . . . . . . . . . . . . . . 218

11.3.2 Material Preparation and Processing Parameters . . . . . . 219
11.3.3 Microstructure Analysis . . . . . . . . . . . . . . . . . . . . . . . . . 219
11.3.4 Friction and Wear Properties . . . . . . . . . . . . . . . . . . . . . 221
11.3.5 Special Gradient Luminescent Properties . . . . . . . . . . . . 222
11.4 Prospect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
12 Industrial Applications and Equipment Scaling-Ups of Xu-Tec
Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
12.1 Xu-Tec High-Speed Steel (HSS) Handsaw Blade . . . . . . . . . . . . 227
12.1.1 Xu-Tec HSS Process . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
12.1.2 Working-piece-Source Structure for Xu-Tec Handsaw
Blade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
12.1.3 Production Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
12.1.4 Microstructure and Composition . . . . . . . . . . . . . . . . . . 231
12.1.5 Cutting Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
12.1.6 Industrialization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
12.2 Xu-Tec HSS Treatment of Colloid Mill . . . . . . . . . . . . . . . . . . . 235
12.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
12.2.2 Process of Xu-Tec HSS Colloid Mill . . . . . . . . . . . . . . 236
12.2.3 Workpiece-Source Configuration Setup
for Colloid Mill . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
12.2.4 Surface Alloying, Carburizing, Quenching,
and Tempering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
12.2.5 Assessment and Economic Benefits . . . . . . . . . . . . . . . . 241
12.3 Plasma Surface Metallurgy Ni–Cr Corrosion Resistant Alloy
Plate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
12.3.1 Plasma Surface Ni–Cr Alloying . . . . . . . . . . . . . . . . . . . 242
12.3.2 Workpiece-Source Setup for Steel Plate Alloying . . . . . 242
12.3.3 Corrosion Resistance Test . . . . . . . . . . . . . . . . . . . . . . . 243
12.3.4 The Most Important Industry Application . . . . . . . . . . . 245
12.4 Plasma Surface Metallurgy Chemical Valves and Flanges . . . . . 245
12.5 Xu-Tec Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
12.5.1 Diagram of Xu-Tec Industrial Furnace . . . . . . . . . . . . . 246
12.5.2 Existing Furnaces and Its Applications . . . . . . . . . . . . . 247
12.5.3 Composition and Function of Each Part . . . . . . . . . . . . 248
12.5.4 Technical Specifications . . . . . . . . . . . . . . . . . . . . . . . . 252
12.5.5 Differences Between Xu-Tec Furnace and Plasma
Nitriding Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
12.6 Prospect and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
xx Contents
13 Other Technologies by Double Glow Discharge Plasma

Phenomenon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 257
13.1 Arc Plasma Added Double Glow Surface Alloying
Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
13.2 Double Glow Plasma Brazing Technology . . . . . . . . . . . . . . . . . 258
13.3 Double Glow Plasma Sintering Technology . . . . . . . . . . . . . . . . 259
13.4 Double Glow Plasma Nano-Powder Technology . . . . . . . . . . . . 260
13.5 Double Glow Plasma Thin Diamond Film Technology . . . . . . . 261
13.6 Double Glow Plasma Sputter Cleaning Technology . . . . . . . . . . 262
13.7 Double Glow Plasma Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . 264
13.8 Prospect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
Closing Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
Chapter 1
Introduction
Abstract In the long-term industrial engineering development practice, the

importance of material performance with its surface condition has attracted a great
attention and tremendous development effort. It has been recognized that there are
many differences and contradictions between the substrate material and its surface
requirements. Over the past 2000 years, a variety of surface engineering tech-
nologies has been innovated in order to overcome those contradictions and form an
independent high-performance surface engineering system. In this chapter, the
classification of all of surface treatment techniques is given, with a brief intro-
duction of the traditional and modern surface alloying technologies. The develop-
ment history of innovative research of glow discharge and applications of surface
plasma nitriding technology are specially reviewed.
1.1 Engineering Materials and Its Surface
Engineering material is the basic substance for industrial and agricultural produc-
tion practice in human life. Composition, property, and performance of materials
are the most extensive subjects in the field of natural science and technology.
Industrial engineering material mainly consists of three major categories: metal
materials, polymer materials, and ceramic materials. Among them, metal materials,
especially iron and steel, are the most important and commonly used materials in
industrial and agricultural applications. In modern industry of machinery manu-
facturing for most of the mechanical parts in the working condition, there is a great
difference in the performance and property between the material matrix and its
surface. Generally speaking, the matrix has intrinsically high strength and good
toughness, while the surface is required to have high hardness and high wear
resistance, as well as corrosion resistance and high-temperature oxidation resis-
tance, etc. As early as 2000 years ago, human beings have begun to recognize the
importance and specificity of surface properties of materials. For example, in China,
during the Warring States period, the working men had invented the carburizing
© Science Press, Beijing and Springer Nature Singapore Pte Ltd. 2017 1
Z. Xu and F.F. Xiong, Plasma Surface Metallurgy,
DOI 10.1007/978-981-10-5724-3_1
2 1 Introduction
technology for iron steel to enhance the surface hardness and sharpness of knives
and swords.
A large number of incident facts have proved that the failure of the materials
tends to start from the surface, which fully demonstrated the importance of the
material surface performance. In order to meet the requirements of the surface
properties of materials for certain applications, in the long-term production practice,
a human has been in the search for surface engineering techniques and methods.
Many new surface treatment technologies have been emerged to meet the
requirements of higher surface hardness, wear resistance, corrosion resistance and
high-temperature oxidation. Especially in the past half century, new materials and
new surface treatment technologies have sprung up. Surface engineering of mate-
rials has formed an independent discipline of advanced materials science and
engineering.
1.2 Surface Engineering and Its Classification
1.2.1 Concept of Surface Engineering
In order to meet the requirements of material service and engineering applications,

different heat treatment and surface treatment are often used. For example, a carbon
steel gear requires its steel matrix to have high strength and high toughness, which
can be enhanced by high-temperature quenching and tempering; while the gear
surface requires high hardness and wear resistance for application durability, so the
needs for carburizing and quenching are normally used. Sometimes, the resulting
processing effects on the matrix material and the surface are contradictory or even
cancel each other. Therefore, we must take a unified consideration and compro-
mised actions. That is to say, for the matrix and the surface of the material, we
should put their different performance requirements and the processing technology
for meeting these requirements, as a unified body to be designed and processed.
In 1985, Professor Tom Bell of University of Birmingham, UK, first proposed
the concept of “Surface Engineering”. Its main significance is to treat the matrix and
the surface of the material as an entity system in carrying out on the selection and
design of material surface properties. The physical and chemical basis of the surface
of the material, surface treatment methods and technology, surface structure and
performance testing are unified in the concept of surface engineering. Therefore,
surface engineering includes all related aspects of science and technology about
material surface.
In the following, we are going to discuss the surface engineering techniques and
their classification, mainly for improving mechanical properties of the metal
material surfaces, but not including functional thin film coating technology for
special physical properties on the material surface.
1.2 Surface Engineering and Its Classification 3
In general, the surface engineering system is composed of the following three

areas:
1. Material Surface Engineering Technology, which is the core part of material
surface engineering system.
2. Material Surface Science foundation, including three main parts: surface phy-
sics, surface chemistry, and surface analysis.
3. Material surface engineering application, including special material surface
application, development, and industrialization of the surface technology.
At present, there are many classification methods in the published books in terms
of surface engineering and technology. Upon the composition and microstructure of
the surface after surface treatment, the material surface engineering technology
could be divided into three categories, as described in the following sections.
1.2.2 Surface Hardening Technology
The surface hardening technology, as one of common material surface engineering

technologies, adopts the external heating or the external force to affect the surface of
the matrix material and increase the hardness and wear resistance of the material
surface by modifying its crystalline structure or material compact density. There is
no change of the chemical composition on the substrate surface. Surface hardening
technology is mainly composed of the following two aspects:
1. Transformation hardening technology: By external rapid heating and rapid
cooling, the microstructure of material surface changes, leading to the increased
hardness and strength. The surface hardening techniques use external heating
sources, such as heating flame, electromagnetic induction heating, ion beam,
laser beam, electron beam, arc, etc. Allotropism phenomenon is the basis of
material surface transformation hardening technology. Without allotropism
taking in place, it will be impossible for the material to use this surface
strengthening treatment. The steel material has allotropism characteristics, so the
transformation hardening is an important method to improve the surface hard-
ness and wear resistance.
2. Deformation hardening technology: Under the effect of the external force, the
microstructure and materials packaging density would change at the material
surface and further induce the changes of the surface properties of the material.
The external force can be shot penning, rolling, hole extrusion, severe plastic
deformation (SPD), etc. The surface deformation hardening technique depends
on the cold hardening phenomenon of the material. The cold hardening effect of
most metal materials is not obvious, so there are some limitations in the surface
hardening technology.
4 1 Introduction
1.2.3 Surface Covering Technology
Surface covering technology is used to coat the surface of matrix material with
different layers by a physical or chemical method. The alloy layer or the ceramic
protective layer is formed and covered on the original surface of the substrate by
surface deposition techniques, such as electroplating, chemical vapor deposition,
physical vapor deposition, thermal spray, etc.
The surface covering technology, as one of very important material surface
treatment methods in the surface engineering field, can be divided into the fol-
lowing aspects according to the physical state of the medium material:
1. Physical Vapor Deposition (PVD): Under vacuum conditions, physical vapor
of a special engineering material in various particle forms (atoms, ions, mole-
cules) is generated by physical heating, ion sputtering, e-beam evaporation
and/or other physical methods, then deposits on the surface of the substrate,
forming a protective coating. All of these technologies, such as vacuum evap-
oration deposition, magnetron sputtering deposition, ion plating, etc., are the
line-of-sight processes, that is, vaporized material species can only deposit on
the surface area where is directly seen from the vapor source.
2. Chemical Vapor Deposition (CVD): Under vacuum or atmospheric pressure
condition, the chemical gas or vapor medium deposits on the surface of the
substrate to form a protective film by chemical reactions. It includes several
techniques such as chemical gas phase deposition, plasma-enhanced chemical
gas phase deposition, metallic organic chemical vapor deposition (MOCVD), or
low-pressure CVD thin film deposition, and so on.
3. Thermal spray technology: Using some heating methods, some medium
materials in molten or semi molten state are produced. By a certain speedy
spraying of this molten source, a coating layer is formed on the surface of the
workpiece. By the heating method, it includes flame spraying, plasma spraying,
arc spraying, and explosion spraying. Welding and EDM coating can also be
attributed to such a technology category.
4. Solution plating technology: In a liquid solution, the produced various particles
(atoms, ions, molecules) deposit on the surface of the base working-piece by
electrochemical reaction to form a protective film. It includes techniques such as
electroplating, nonelectric plating, micro arc oxidation, and chemical conversion
coating technology.
5. Thermal immersing technology: The workpiece is immersed in the low
melting point metal, such as zinc, aluminum, tin, and make its surface to form a
coating layer, such as hot dip galvanizing, hot dip aluminizing, hot tin-plating,
etc.
6. Other surface covering technologies: There are other surface alloying tech-
nologies, which are not included in the above surface alloying classification,
such as surfacing, electric spark surface alloying, etc.
In addition, all of the surface covering technology can be also divided into the
two aspects according to the thickness of the coating layer: the surface coating
technology that is widely used for surface property improvement and the thin film
technology that is used in microelectronic semiconductor manufacturing process.
1.2.4 Surface Alloying/Metallurgy Technology
Surface alloying or surface metallurgy technology is to use physical or chemical

processes for transferring and depositing alloying elements on the surface of a
substrate; then under thermal gradient and composition gradient driving, alloying
elements diffuse into the heated substrate material to form a surface alloy layer. The
modified surface alloying layer has a significant change and gradient distribution of
chemical composition from the surface. Different from other surface technologies,
the two main characteristics of surface alloying are the formation of a surface alloy
layer and the composition of surface alloy layer in a gradient distribution.
This surface technology includes conventional chemical heat treatment tech-
nology, gas carburizing, gas nitriding, pack cementation, and surface metalizing. In
addition, laser surface alloying, electron beam surface alloying, and ion implanta-
tion technology can also be attributed to this type of technology.
By their physical and chemical aspects, the methods of heating the substrate and
alloying elements supply, the surface alloying technology can be divided into the
following three aspects:
1. Thermochemical Surface Alloying: Thermochemical surface alloying uses the
conventional approach to heat the substrate material and let foreign chemical
elements deposit on and diffusing into the sub-surface of the substrate to form a
surface alloy layer. The chemical surface heat treatment and diffusion coating
technology belong to this kind of technology, such as pack cementation, gas and
solid carburizing, gas nitriding, sulphurizing, pack chromizing, liquid alu-
minizing, boriding. Among them, carburizing and nitriding are the most prac-
tical technologies in manufacturing industry.
2. High-Energy Beam Surface Alloying: It uses high-energy particle beam, such
as laser beam, ion beam, electron beam, etc., to provide heating energy to drive
the formation of a surface alloy layer on the substrate. It normally includes laser
surface alloying, electron beam surface alloying, ion beam surface alloying, and
ion implantation.
3. Plasma Surface Alloying/Metallurgy: This surface metallurgy process is to
employ low-temperature plasma produced by gas glowing or arc discharge to
generate alloy element vapor, then form an alloy layer on the surface of the
substrate by deposition and diffusion. The technique includes plasma nitriding,
plasma carburizing and double glow plasma surface alloying/metallurgy. This
technology is the main subject to be discussed in this book.
6 1 Introduction
All surface technologies concerning the alteration of surface composition or

structure by the use of energy or particle beam are also called as Surface
Modification. Both the surface hardening and surface alloying belong to surface
modification.
1.2.5 Classification Table
In summary, the classification of surface engineering technology is given in

Fig. 1.1.
Fig. 1.1 The classification of surface engineering technology

It should be noted that some surface technologies, such as cleaning and light
finishing techniques are not incorporated into the above classifications. The above
classification has no absolute strict boundaries. For example, thermal spraying in
material surface by the formation of alloy coating on the surface and in the surface
of matrix materials may also form an alloy diffusion layer; surface metallurgy
technology outside the surface of matrix materials may also form an alloy cover
layer.
1.3 Existing Surface Alloying Technology
Surface alloying technology has a long development history. Back to China’s

Warring States period of 2000 years ago, carburizing technology was invented.
Afterward it has been followed by other new technologies, such as gas nitridation,
solid metallization, and laser surface alloying. In 1930, the invention of the ion
nitriding technology in German had opened a new chapter of modern plasma
surface alloying technology.
Differing from other surface technology, the main feature of surface alloying
technology is about a thermal-driven diffusion of alloy elements into the surface of
the material matrix and the gradient composition change in the surface alloy layer
initiated from the surface of the substrate.
All chemical elements that are specifically added to improve the properties of the
material are collectively referred to Alloying Elements. Both the nonmetallic ele-
ments and the solid metal elements can be used for surface alloying.
1.3.1 Conventional Surface Alloying Technology
The traditional surface alloying technology was known as the chemical heat
treatment in China, while as the diffusion coating technology in the United States.
The conventional surface alloying technology can be divided into the following
categories according to the state of the alloying elements.
1. Solid surface alloying: This technology can form a surface alloy on the surface
of the working-piece by heating the working-piece in the presence of the alloy
powder or particles on the surface and then the alloying element diffused into the
sub-surface. The process is simple and easy to operate, but it has dust pollution
with a poor working condition.
2. Liquid surface alloying: In this method, the workpiece can be immersed in a
molten liquid containing an alloying element to form an alloy layer, such as
liquid aluminizing, liquid zinc surface alloying, etc. The technology can deal
with large-size working objects, but there is chemical pollution with poor
working conditions.
8 1 Introduction
3. Gas surface alloying: The working-piece is treated in an atmosphere containing

alloy elements. Through external heating, chemical reaction and diffusion, a
surface alloying layer is formed on the surface of the working-piece, such as gas
carburizing, gas nitriding and gas sulphurizing.
The above mentioned conventional surface alloying methods have great limi-
tation, as only few individual alloy elements can be used as alloying elements. The
process also has a quantity scale limitation as in only a single, small batch pro-
duction. The production efficiency is low. Most of such processes cause environ-
mental pollution problems and poor working conditions.
1.3.2 Modern Surface Alloying Technology
Since 1970s, the techniques by the methods of the laser, electron beam, or ion beam
have been used to develop a number of modern surface alloying technology pro-
cesses, such as:
1. Laser surface alloying technique: The alloy element powder is placed on the
surface of the working-piece. Then, a laser beam is used to scan on the powder,
inducing heating, melting and diffusion to form a surface alloy layer on the
working-piece surface.
2. Electron beam surface alloying technique: Electron beam is used as a heating
source. The technology is similar to the laser surface alloying.
3. Ion implantation technique: The positive ions of alloy elements, accelerated to
high energy in high voltage electric field, directly bombard the working-piece
surface; then the alloy elements directly “shot” into (not diffusion process) the
surface to form a surface alloy layer on the surface of workpieces. The maxi-
mum thickness of the alloy layer is only less than a micrometer in a keV energy
range.
The above three surface alloying techniques have their own unique advantages
and applications, but there are some common problems:
1. Equipments involved are relatively very expensive, the operation is complex,
and the investment cost is high.
2. It is only able to deal with a relatively small area with low production efficiency.
3. The energy consumption is very large and the thermal efficiency is low.
1.3.3 Concept of Plasma Surface Metallurgy
The concept of Plasma Surface Metallurgy was first proposed by Professor Zhong
Xu in 1982 at an international conference: “The 10th International Symposium on
1.3 Existing Surface Alloying Technology 9
Discharge and Electrical Insulation in Vacuum” held in Columbia, South Carolina,

USA. At the conference, in his paper titled “Metal Ion Source for Metallic Surface
Metallurgy”, Prof. Xu initiated the concept of “Surface Metallurgy” and presented
“Double Glow Discharge Phenomenon” [1]. Based on plasma nitriding process, the
“Double Glow Plasma Surface Alloying Technology” was developed by using
“Double Glow Discharge Phenomenon” for surface alloying.
Surface alloying is also called Diffusion Coating by ASTM. Surface alloying is a
relatively broad concept than surface metallurgy and is a kind of surface alloying
technology that can be used to form many surface alloys on metals. Plasma surface
metallurgy is a surface alloying technique formed by low temperature plasma
produced by glow discharge or arc discharge. However the plasma nitriding tech-
nology is only used with nitrogen gas plasma or a few of other gas elements, such
as carbon and sulfur. While the liquid surface alloying technique can only suit to
low melting point metal elements, such as aluminum, zinc, tin, etc. The double
glow plasma surface alloying technology can apply any chemical elements in the
periodic table of the chemical elements and form countless kinds of surface alloys.
It is one of most efficient processes for surface metallurgy.
1.4 Glow Discharge and Plasma Nitriding
1.4.1 History of Glow Discharge
Glow discharge is a very common phenomenon in our life. When we walk in the
night on the city streets, we see very beautiful colorful neon advertising signs
everywhere. The light emitted by the neon tube is from the glow discharge of neon
gas inside the tube. The lighting color emitted is defined by the gas in the tube, such
as hydrogen for light blue, nitrogen for violet, argon for red, and so on.
In the early 1800s, human beings began to pay attention to the discharge phe-
nomenon in the sky. For example, the thunder and lightning is a discharge phe-
nomenon in the atmosphere condition in the sky.
In 1775, B. Franklin was the first to study the lightning in the atmosphere. After
many experiments, it was confirmed that lightning in the sky is a discharge
phenomenon.
In 1835, in his laboratory [2], M. Faraday first discovered the presence of a
low-pressure gas glow discharge and observed the stratified phenomenon—the
existence of clear and dark areas in the glow discharge.
In 1879, W. Crookes studied the gas discharge characteristics and called the
fourth state of matter as “Plasma”.
In 1928, I. Langmuir discovered the anode column in discharge is neutral, as
density of the electron and positive ion is almost same. He formally named this state
in the anode column as “plasma” [3].
10 1 Introduction
1.4.2 Concept of Plasma
As is normally known, there are three kinds of states of matters in nature: solid,
liquid and gas. A matter can transfer from one state to another under a certain
thermal condition. When a solid is heated to a high temperature, where the average
kinetic energy of atoms is higher than the atomic binding energy in the crystal, the
solid will become a liquid; while the liquid is heated further to its boiling point, the
liquid will translate to a gas state. Furthermore, if the gas is further heated to a much
higher temperature, partial electrons or all electrons in the gas atom will be free
from the bonds of the nucleus. Atoms become positively charged ions with the
same number of electrons around. It is in electric neutral as a whole. We call this
kind of the state as the “Plasma” state, which is known as the fourth state of matter.
Plasma is an ionized gaseous substance, which is composed of electrons, positive
ions and neutral atoms. The numbers of positive and negative charges are equal, so
it is similar to the neutral state.
For the whole universe, plasma is the main form of matter. In fact, in the
universe, the stars (including the sun), the interstellar material, the brilliant flashes
of lightning, and the splendid and magnificent aurora are all in the plasma state.
Plasma can be divided into high-temperature plasma and low-temperature plasma.
Electron temperature and ion temperature is the important characteristics, differing
high temperature and low-temperature plasma. When the two are equal, it is
high-temperature plasma. When the two is not same, it is the low-temperature
plasma. Glow discharge is an important method for producing low-temperature
plasma and has been applied in the field of television, welding, smelting, spraying,
cutting, and rocket propulsion.
1.4.3 Advent of Plasma Nitriding in Germany
Mchlet A. invented the nitriding technology that was granted a US patent in 1913
[4]. In 1930, Berghaus was the first person to use the glow discharge phenomenon
and invented the plasma nitriding technology creating a new direction of the plasma
surface alloying [5].
Before the World War II, Berghaus worked on it intensively in his institute of
research and development in Berlin. More than 40 scientists, engineers, and tech-
nicians worked together on the plasma nitriding. Their work had been succeeded
[6]. During the World War II, the first practical applications were performed on
gearings of the turrets of tanks and gun barrels of several meters in length.
After the World War II, Berghaus continued his research and development work in
Switzerland and established a small laboratory at the power station of Zurich. The
regional government of Northrhine-Westfalia/FRG judged the research results by
Berghaus and showed deep interest in the plasma technology, so they installed a
financial budget for running a research and development institute in Cologne/FRG [7].
1.4 Glow Discharge and Plasma Nitriding 11
In 1972, Germany released the plasma nitriding technology to the world and
heavy promotion in Europe, and start the technology export of plasma nitriding
furnace to other countries.
At that time, China was also interested in introducing plasma nitriding tech-
nology in the country. In several cities such as Beijing, Dalian, Wuhan, Taiyuan,
and Changchun, more than 20 national research institutes and universities, such as
Scientific Research Institute of Ministry of Railway, Beijing Research Institute of
Machine Tools, Beijing Industry University, Taiyuan Industry University and so
on, launched this research and development, promoting of the plasma nitriding
technology applications as well.
References
1. Xu Z (1982) Metal ion source for metallic surface metallurgy. In: 10th international symposium
on discharges and electrical insulation in vacuum, South Carolina, USA, pp 25–28
2. Fite WL (1969) Chemical reactions in electrical discharge. Am Chem Soc, Washington
3. Longmuir I (1928) Oscillation in ionized gases. Proc Natl Acad Sci 14:627
4. Machlet A (1914) Hardening of treatment of steel iron. US Patent 1092925
5. Berghaus B (1932) Process for surface treatment of metallic elements. Germany Patent DRP
6686391932
6. Berghaus B (1939) Vacuum furnace, heated by glow discharge. Germany Patent DRP 851540
7. Hombeck F (1986) Forward view of ion nitriding applications. In: Spalvins T (ed) Proceedings
of an international conference on ion nitriding, Cleveland, pp 15–17
Chapter 2
Plasma Nitriding
Abstract Plasma nitriding technology, developed based on the glow discharge

phenomenon, is reviewed in this chapter, ranging from its basic physical principle,
main processing characteristics and technical advantages, as well as its industrial
applications. Other nonmetal element plasma surface alloying technologies, such as
plasma carburizing, plasma nitro-carburizing and plasma sulfurizing are briefly
introduced. Further discussion is carried out on its limitation of the nonmetallic
element for plasma nitriding technology and advanced technology development in
China.
2.1 Glow Discharge and Its Characteristics
2.1.1 Characteristics of Glow Discharge
Plasma nitriding is a surface alloying technology which is developed based on the

phenomenon and characteristics of the glow discharge plasma.
The phenomenon of glow discharge was first discovered and studied by applying
a DC voltage across two electrodes in a vacuum diode. Characteristics of the
Voltage–Current curve of the glow discharge were shown in Fig. 2.1 [1].
As seen in Fig. 2.1, the discharge can be separated in several regions along the
current level. No visible light can be observed in the vacuum diode at the low
voltage and current (the dotted line in the curve). As the voltage and current are
changed, it goes through several discharge stages: Townsend discharge and normal
glow discharge at low voltage and current, then jumping into abnormal glow dis-
charge where any increase in the voltage gives an increase in the current density.
The current density is uniform around the entire cathode surface, indicated by a
uniform glow. The “abnormal glow discharge” region is used for plasma nitriding
process. However, as the voltage is further raised, the glow discharge/arc discharge
transition threshold point is approached, then the glow discharge collapses and high
current density arc discharge forms.
DOI 10.1007/978-981-10-5724-3_2
14 2 Plasma Nitriding
Fig. 2.1 Voltage–current characteristics of different types of high voltage discharge with Argon
gas [1]
The arc discharge is a severe discharge confined in a small area and would cause
the working-piece ablation. It is critical to control cathode discharge to avoid arcing
discharge and associated ablation-induced damage to the system.
2.1.2 Stratified Phenomenon
Figure 2.2 shows the typical visible glow distribution between the anode and the
cathode. The stratified phenomenon can be observed. From the cathode to the
anode, there exist several glow discharge spaces: Aston dark space, cathode glow,
Crookes dark space, negative glow, Faraday dark, positive column, anode glow,
and anode dark space. The total discharge width Dk is a very important parameter,
including Aston dark, cathode glow, Crokes dark, and negative glow. Dk is also
called as the width of cathode potential drop region. When the anode moves toward
the cathode, only the width of the positive column reduced, but other parts remain
unchanged. However, once the anode comes in the negative glow region, all of the
glow discharge will be immediately extinguished. The higher the gas pressure is,
the smaller the Dk value would be. This is a very important feature for all appli-
cations of glow discharge process.
2.1 Glow Discharge and Its Characteristics 15
Fig. 2.2 Qualitative characteristics (stratified phenomenon) of a dc glow discharge [1]
2.1.3 Interactions Between Ions and Material Surface
In plasma material surface process, the main process is the interaction between ions
and the material surface. The basic physical and chemical interactions between ions
and the substrate surface are schematically shown in Fig. 2.3.
Driven by the electric field, the positive ions from the glow discharge plasma,
such as nonmetallic elements (argon and nitrogen) or metal elements, will bombard
the cathode surface, resulting in some interaction effects as listed here [2]:
Fig. 2.3 Schematic illustration of ion-surface interactions

1. Sputtering: Any material with negative potential in the plasma equipment will
be sputtered by positive incident ions and produce an atomic vapor of the
cathode material. These sputtered-out atoms would deposit on the closed-by
working-piece. We can use any negative electrode made of alloying element as a
target for the alloying element supply.
2. Heating: From the discharge plasma, electrons and ions with high energy would
bombard the surface of the substrate and releases energy for heating the sub-
strate. The temperature of the working-piece can be higher than 1200 °C.
3. Implantation: When high energetic ions bombard the surface, they can jam (or
implant) into the substrate surface to form an implantation layer. The depth of
implantation layer is determined by the ion energy and the characteristics of the
material to be implanted.
4. Diffusion: As is described above, the working-piece can be heated by
electron-ion bombardments or other heating methods to enough high tempera-
ture. Under thermal driving, the incident ions and sputtered-deposited atoms can
diffuse deeply into the surface of the working-piece to form a greater thickness
alloying layer.
5. Cleaning: When the cathode surface is bombarded by ions, its light sputtering
effect can be used to clean the oil stain and impurities at the surface, while
thermal heating effect can induce oxides decomposition at the work object
surface.
6. Defects Creating: Ion bombardment can make the atoms of cathode surface to
be sputtered and creates a defect layer including a large number of vacancies and
dislocations, which can be more active for dissolving and diffusion of alloying
elements.
7. Surface Etching: Similar to the surface cleaning, ion bombardment can erode
and strip off the surface layer of the cathode material through ion sputtering
process. This effect has been used as an important method for the glow dis-
charge analyzer of surface composition distribution.
8. Chemical Reaction Accelerating: Glow discharge plasma contains high energy
in ions and electrons, which would stimulate the activation of chemical species
and acceleration of many chemical reactions that cannot be achieved under the
routine condition. Experiments on the chemical reaction with gas discharge have
been carried on for a hundred years. In 1967, F.K. McTaggart first used the
concept of “plasma chemistry” [3] to stimulate the chemical reactions occurring
in the discharge.
2.2 Plasma Nitriding Process 17
2.2 Plasma Nitriding Process
Plasma nitriding was invented by Berghaus [4]. It is considered as “the Foundation

Stone of Modern Plasma Surface Engineering” and one of “the most important
achievements of surface engineering” in the development of material surface
technology [5, 6].
Nitriding or carburizing is used as an effective method to improve the surface
hardness, wear resistance fatigue strength and corrosion resistance of metal mate-
rials. Plasma nitriding has been used in the fields of mechanical manufacturing,
chemical engineering, aviation, and national defense and so on.
2.2.1 Basic Principle
The schematic diagram of the plasma nitriding process experimental setup is shown
in Fig. 2.4, where the working-piece, anode, and cathode are arranged as shown.
Under the condition of glow discharge, the refilled gases (nitrogen + hydrogen,
or ammonia NH3 gas) are ionized into N+ and H+. Driven by a high voltage electric
field, H+ and N+ ions move to bombard the surface of the working-piece. The
kinetic energy of ions will be converted into heat energy so that the surface of the
working-piece is heated to a required temperature. At the same time, the nitrogen
atom is adsorbed and diffused into the surface of the working-piece to form a
nitriding layer.
Fig. 2.4 Schematic diagram of plasma nitriding experimental setup [1]

Commonly used plasma nitriding process parameter range:

• nitriding temperature, 450–650 °C;
• gas pressure, 1.33 102–1.33 103 Pa;
• discharge voltage, 400–800 V;
• current density, 0.5–5 mA/cm2;
Nitriding processing time can range from a few minutes to more than 10 h,
according to the process condition such as the working-piece material and nitriding
temperature, as well as the required nitriding layer depth.
2.2.2 Advantages
Compared with thermal gas nitriding, plasma nitriding has the following
advantages:
1. High diffusion speed: Driving under plasma energy and high temperature,
nitrogen ions can diffuse into the material subsurface faster and deeper. To
obtain the same thickness of a nitriding layer, the plasma nitriding time is only
about 1/3–1/5 of the time by gas nitriding.
2. Energy saving: Ion bombardment on the surface generates the local heating on
the working-piece surface without heating the whole furnace body, thus the
process can greatly minimize energy consumption.
3. Controllable microstructure of the nitride layer: In contrast to gas nitriding
process, the composition and microstructure of the nitride layer are controllable
during plasma nitriding process. It can be controlled by adjusting the ratio of
nitrogen and hydrogen contents in the feed gas during the plasma nitriding
process.
4. No requirement for any treatment for the passive film of stainless steel:
During plasma nitriding, ion bombardment can destroy the passive film on the
surface, both to simplify the process and save the labor cost.
5. No chemical pollution: plasma nitriding only use a small amount of ammonia
or nitrogen, hydrogen, the environment pollution is negligible.
6. Used as the final step: After plasma nitriding, the part surface is silver gray and
good smoothness. Structure deformation is also very small. They do not need
regrinding, annealing, or another retreatment in the post process.
2.2.3 Industrial Applications
Plasma nitriding has been used for a long time to improve wear resistance and
fatigue strength, with a minimum distortion. It has been widely applied in
2.2 Plasma Nitriding Process 19
machinery, petroleum, chemical industry, metallurgy, automobile, aviation and

national defense and other industrial fields. The application of plasma nitriding for
surface modification is still expanding, such as for various engine crankshaft,
cylinder liner, plastic extrusion screw, aluminum profile extrusion die, gear, etc.,
leading to remarkable economic and social benefits.
Plasma nitriding on nonferrous metals, especially on the titanium alloy, has also
made good applications in significant improvement effect in the wear resistance and
corrosion resistance of the titanium alloy [6].
2.3 Other Plasma Surface Alloying Technology
2.3.1 Plasma Carburizing
Carburizing is the first surface alloying method for improving the surface hardness
and wears resistance of steels. In the late 1970s, the plasma carburizing had been
applied to replace the traditional carburizing process.
Carburizing gaseous medium for the use of the plasma carburizing is methane
CH4 or propane C3H8, with hydrogen or argon as the carrier gas. The volume ratio
of 1:10 is used for propane dilution.
The alloy material treated with the method of plasma carburizing has higher
wear resistance and fatigue strength than that by the conventional carburizing
method. It is commonly used for the carburizing cycle with energy saving and no
pollution.
2.3.2 Plasma Nitro-Carburizing
Plasma nitro-carburizing is processed in the condition of plasma nitriding with

adding a small amount of carbon [3], commonly known as plasma soft nitriding.
This treatment process is usually carried out with the medium of nitrogen or
nitrogen–hydrogen mixture with Ethanol (C2H5OH) or Methane CH4. Plasma
nitro-carburizing is commonly used to improve the gear, shaft, piston rings, valve
plate, mold, tool and so on for surface wear-resisting improvement.
2.3.3 Plasma Sulphurizing
Plasma sulfurizing is processed with H2S or CS2 gas at a temperature of 150–300 °

C. Because of the low solubility of sulfur in the a-Fe (only 0.02%), no diffusion
layer is formed after ion sulfurizing process. The resulting ferrous sulfide
compound surface layer is soft with low shear resistance and easy to slip, good for
friction reducing and anti-bite application [7].
2.4 Restriction of Plasma Nitriding
The invention of plasma nitriding technology has opened up a new direction for the
traditional surface nitriding process and adopted as a major development in the field
of surface alloying. However, in the 86 years since its advent, the plasma nitriding
technology can only be applied to nonmetallic elements. In order to break the limit
of the plasma nitriding technology, people have been trying to apply the glow
discharge phenomenon to the metal elements.
Liquid metal halide was once used as a source of supply material for metal
elements after its gasification. As an example, the mixed gas of TiCl4 with
hydrogen gas as a carrier had been used for plasma surface titanium-alloying.
Another example is surface silicon alloying, the source of silicon is SiCl4 and
hydrogen gas mixture, and the silicon alloying layer on the surface of the steel is
Fe3Si.
The main problem in these above processes is serious corrosion to the process
equipment due to the toxic chlorine produced by the ionization from the metal
halide. Therefore, this method has no practical significance, and it has not been
further developed.
2.5 Development of Plasma Nitriding in China
To its technical advantages and the glow of the beautiful color appearance, plasma
nitriding technology has attracted the great attention and development interest
globally. Scientists and engineers in many countries have devoted their effort to the
research and promotion of this technology. Taking China as an example, since 1972
there are more than 20 universities and research institutions and a few hundreds of
scientific and technological workers have devoted their effort to this technology
research and development. “Academic Committee for Chemical Heat Treatment of
Plasma Bombardment” was once set up, responsible for the promotion of plasma
nitriding technology development, the annual technical meeting, and academic
information exchange. So far, nearly 3000 units of plasma nitriding furnaces and
processing systems have been established in China. However, due to a poor quality
of the early equipment design and fabrication, as well as a lack of good under-
standing of the plasma nitriding process, only about 30% of the equipments can be
used in the application practice.
Starting in 1972, Author’s research group in China had got engaged in the study
of plasma nitriding technology, following the initiative in Germany. A coating
machine in the laboratory was modified as our first small plasma nitriding process
2.5 Development of Plasma Nitriding in China 21
system. In 1975, a 30 kW large plasma nitriding furnace was built. Inspired by the
titanium-plating gas nitriding, the titanium gas nitriding was developed successfully
by placing sponge titanium in the gas nitriding furnace. On the basis of titanium gas
nitriding, we have further developed the titanium plasma nitriding process by
placing a titanium sponge on the anode and the cathode during plasma nitriding
processing. The nitriding layer formation speed of the titanium plasma nitriding is
double of the ordinary plasma nitriding process.
Furthermore, based on the titanium plasma nitriding, we developed a new
technology of “Titanium-carbon plasma nitriding” in 1976. The micro hardness of
carbon alloyed steel resulted from this process has reached up to 1000 HV0.1.
Titanium-carbon plasma nitriding technology has won an award in the Chinese
National Science Conference in 1978 and won the third-grade award of Chinese
National Invention in 1985.
In the 1990s, with the development of the pulsed power supply and the appli-
cation of computer technology, the stability and reliability of the plasma nitriding
system equipment are greatly improved.
References
1. Xu Z (2008) Plasma surface metallurgy. China Science Press, Beijing

2. Spalvins T (1986) Plasma assisted surface coating/modification processes: an emerging
technology. In: Spalvins T (ed) Proceedings of an international conference on ion nitriding,
Cleveland, pp 15–17
3. McTaggart FK (1967) Plasma chemistry in electrical discharge. Elsevier, Amsterdam
4. Berghaus B (1932) Process for surface treatment of metallic elements. Germany Patent DRP
668639
5. Burakowski T, Wierzchon T (1998) Surface engineering of metal. CRC Press, New York
6. Strafford KN (1995) Surface engineering: process and applications. Technical Publishing
Company, Lancaster
7. Dai D (2004) Modern surface science and technology of material. China Metallurgy Press,
Beijing
Chapter 3
Double Glow Discharge Phenomenon
and Its Applications
Abstract The double glow discharge phenomenon has led in the invention of
“Double Glow Plasma Surface Alloying Technology”. This technology has over-
come the limitation of the plasma nitriding technology which can only use non-
metallic gas elements for surface alloying. This chapter mainly introduces the
double glow discharge phenomenon with its discovery, functionalities, discharge
modes, and applications. The double glow hollow cathode discharge and its dis-
charge characteristics are also introduced and discussed. The initial set of experi-
mental setup and the result of the double glow plasma surface alloying technology
have been described.
3.1 What Is Double Glow Discharge Phenomenon?
Plasma nitriding process uses only a single pair of electrodes to realize gas element
plasma for surface alloying. In order to break the limitation of plasma nitriding,
“Double Glow Plasma Surface Alloying Technology” was developed in 1980 based
on the discovery of “Double Glow Discharge Phenomenon” in 1978 by Prof. Zhong
Xu and his research group in China. It was named as the “Xu-Tec” process as it was
first patented by Prof. Zhong Xu and his colleagues in USA in 1983. Using the
Xu-Tec process, all solid-state alloying elements could be evaporated, ionized, and
introduced into the surfaces of base substrate materials, like iron, steel, titanium
alloy, and intermetallic compound, to form new surface alloys with special
properties.
The double glow discharge phenomenon is shown in Fig. 3.1. In a vacuum
chamber, there are three electrodes: the grounded anode, the cathode, and the
second negatively electrode. Two DC power supplies are applied to the cathode and
the second negatively electrode separately. The power supplies provide an output
voltage of 0–1200 V using a silicon-controlled rectifier. The vacuum chamber is
first pumped to a base pressure below 0.1 Pa and back-filled with pure argon gas to
a process pressure of 10–100 Pa. Under the electric field induced by two
high-voltage power supplies, argon gas will be electrically broken down and
DOI 10.1007/978-981-10-5724-3_3
24 3 Double Glow Discharge Phenomenon and Its Applications
Fig. 3.1 Double glow

discharge phenomenon [1]
ionized, so that two sets of glow discharge plasma zones are generated, one near the
cathode surface and the other surrounding the second negatively electrode. This is
the so-called “Double Glow Discharge Phenomenon” [1].
3.2 Discovery of Double Glow Discharge
Since 1972, during a long-time study of plasma nitriding, it was thought that, in
order to break the restriction of plasma nitriding for nonmetallic element applica-
tion, we could apply glow discharge to realize surface alloying for solid metal
elements. It was recognized that vaporizing solid metal elements is the key issue.
During the technology development experiments in Prof. Xu’s laboratory,
occasionally they observed that a spark and/or local micro arc discharge emitted
from the surface of the working-piece. It was also observed that there are more and
more steel fine powders on the stove chassis. These observations had made one to
realize that, under the glow discharge condition, the solid metal elements in the
cathode electrode could be sputtered off by positive ion bombardment from plasma.
The sputtered off metallic atomic species move into the glow discharge space, then
deposit on the surface of the working-piece. One can employ this phenomenon to
realize gasification of solid alloy elements.
3.2 Discovery of Double Glow Discharge 25
Professor Xu’s team managed to set up a second cathode (as a source electrode,
made of the desired alloying elements) between the anode and cathode in plasma
nitriding equipment. Driven by two DC power supplies, two glow discharge
(plasma) zones would be established, respectively, between the anode and cathode
as well as the anode and second cathode. Ion bombardment at the second cathode
makes the desired solid alloying element to be sputtered and gasified into glow
discharge space. This is described as “Double Glow Discharge Phenomenon”.
In this regard, they have been continuing research on double glow discharge
phenomenon and its engineering applications since 1979 [2].
Shortly thereafter, the “Double Glow Plasma Surface Alloying Technology” was
invented in Prof. Xu’s lab based on the “Double Glow Discharge Phenomenon”. It
was discovered that the double glow plasma surface alloying technology can be
applied to any solid chemical element such as nickel, chromium, tungsten, and their
combination to conduct surface alloying modification. With this method, surface
alloys with gradient concentration of alloying elements have been produced on the
surfaces of steels, titanium alloys, intermetallic compounds, etc. [3, 4].
3.3 Double Glow Discharge Modes
For more than 30 years, many experiments have been conducted to understand the
Xu-Tec process. It has been found that the “Double Glow Discharge Phenomenon”
has several modes of discharging characteristics.
3.3.1 Independent Discharge Mode
When the distance between source electrode and cathode (substrate) is much larger
than 2 times of the width of cathode potential drop region (2Dk) introduced in Chap. 2,
the glow discharge is in independent mode. Both the DC power supplies of the cathode
and source electrode can operate independently. There is no interaction between the
glow discharges surrounding the cathode and source electrode. The glow discharge
surrounding the cathode and source electrode would not affect each other.
3.3.2 Dependent Discharge Mode
When the cathode and source electrode are brought closer to less than 2Dk, a much
higher current density and stronger discharge are initiated and sustained by DC
power supplies. Two glow discharge spaces start to overlap. The luminance
intensity of the glow increases abruptly as the current density increases. That is
a dependent double glow hollow cathode discharge mode (to be discussed in detail
in the next section). Under this condition, the glow discharge intensity of the
working-piece and the source electrode can be increased by a dozen times to a

hundred times. Actually, this mode cannot be completely independently operated.
There seems a cross talk between two discharge zones. When the source voltage
increases or decreases, the cathode current and source current are also increased or
decreased together accordingly. This mode arrangement greatly enhances double
glow discharge intensity.
3.3.3 Pulse Discharge Mode
The pulse discharge mode is developed using the controllable DC pulse power
suppliers. The pulse power supply is mainly used for the working-piece only,
though it can be used for both the working-piece and the source cathode. Pulsed
discharge can be also used in the hollow cathode discharge mode. In this case the
electric potential and output power can be adjusted flexibly by altering the duty
cycle, and temperature adjustment on the working-piece surface is separated from
other processing parameters. Another advantage of using pulsed power is its
function to suppress the development of arc discharge. As a result, the discharge is
more homogeneous than that of conventional DC power supply and improves the
stability of surface alloying process and quality of surface alloy. A pulsed DC
power supply is strongly recommended for the Xu-Tec process.
3.3.4 Other Discharge Mode
The use of high-frequency microwave discharge power supply can increase the
ionization rate and can also be applied to nonconductive target materials.
In some cases, we can also use one DC power supply for both the workpiece
surface and the source electrode to realize plasma surface alloying. In this case, it is
easy to operate with a DC adjustable power supply, but the composition of the
surface alloy is difficult to control.
It should be stressed here that, for all the above discharge modes, the cathode
potential can be higher, equal, and lower than the source electrode potential. In
most cases, in order to increase sputtering rate and alloying elements supply, the
source electrode potential should be lower than that of cathode potential.
3.4 Double Glow Hollow Cathode Discharge (DG-HCD)
3.4.1 Hollow Cathode Discharge (HCD)
As discussed in Sect. 3.3.2, the hollow cathode discharge (HCD) is a special

dependent double glow discharge mode. The typical hollow cathode discharge
3.4 Double Glow Hollow Cathode Discharge (DG-HCD) 27
Fig. 3.2 General diagram of a hollow cathode discharge device
device is shown in Fig. 3.2. The system includes an anode, a cylinder cathode, and
a DC power supply in a vacuum chamber.
When the inner diameter of the cylinder cathode (D) is larger or the internal gas
pressure is relatively high, the cathode glow ignites from the cathode inner surface.
The negative glow will appear inside the cylinder, the Faraday dark area and the
positive column region appear in the center of the cylinder without HCD. If the
inner diameter of the cathode is reduced, the Faraday dark area and the positive
column region are also reduced. When the inner diameter of the cylinder cathode is
close or less than two times of the width of cathode potential drop region (2Dk) and
larger than one Dk, HCD phenomenon occurs, and the Faraday dark zone and the
positive column region disappeared completely in the center of the cylinder. At this
time, the cathode current density and the negative glow intensity of the area will be
greatly enhanced. The occurrence of HCD is due to the oscillation of electrons
inside the cylinder. The electrons from one point A at the inner wall of the cylinder
are accelerated and moved to another opposite point B. But the electrons will be
rejected by the electric field of point B. In this way, the electrons will be bouncing
back and forth between A and B many times, which greatly increases the chances of
the electron collision with atoms and greatly causes the neutral atoms excited and
ionized. As a result, the glow discharge will be much stronger. The feature of the
hollow cathode discharge is that the luminance intensity of the glow and the dis-
charge current density increase simultaneously and abruptly.
Hollow cathode discharge (HCD) has been widely used in the fields of spectral
analysis, vacuum coating, surface treatment, gas laser, etc. If the hollow cathode is
made into a micro structure (submillimeter), it can be used in the high pressure, and
the HCD can be also used in the ultraviolet light source, the plasma display, and
other fields.
Fig. 3.3 Experimental setup for DG-HCD of double glow discharge. 1 and 5 power supplies, 2
and 3 two cathodes, 4 argon gas inlet [1]
3.4.2 Concept of DG-HCD
The hollow cathode discharge described above is only a special type of discharge
with a single cathode. The Double Glow Hollow Cathode Discharge (DG-HCD) is
formed by two sets of cathodes (i.e., the working-piece and the source) driven with
two different electric potentials [5]. Experimental apparatus for the formation of a
hollow cathode discharge in double glow discharge is shown in Fig. 3.3.
The experimental device of DG-HCD is set in a sealed vacuum container,
including the first cathode (2) and the second cathode (3, the source electrode), two
power supplies (1 and 5). Two cathodes, made of a low-carbon steel plate with size
of 100 100 4 mm, are placed in parallel with a relative distance adjustable in
the range of 10–l00 mm. The supply output voltage can range between 0 and
1000 V. The working discharge gas is industrial-grade pure argon and the working
gas pressure ranges between 10 and 100 Pa.
The DG-HCD is similar to the HCD. When two power supplies (1 and 5) are
switched on, the glow discharges are, respectively, generated along the surface of
cathodes 2 and 3. At first, the negative glow region of the two cathodes is
well-defined and shown by the curve 2 in Fig. 3.4, and the mutual does not
intersect. Then, with the decrease of the argon pressure, the thickness of the neg-
ative glow region increases. When two negative glow regions are overlapped with
each other in the space between two cathodes, the glow brightness is significantly
enhanced. The brightness of the curves 1 and 3 are shown in Fig. 3.4. If further the
pressure is reduced or the two cathode voltages are increased, the two cathode glow
regions mutually overlap and cross together, the brightness of the glow discharge
and two cathodes’ current density will increase sharply, shown as Curve 4. This is
3.4 Double Glow Hollow Cathode Discharge (DG-HCD) 29
Fig. 3.4 Intensity of double glow discharge. 1 and 3 intensity on cathodes 2 and 3, 4 total glow
discharge intensity where two glow discharge zones overlap [1]
Fig. 3.5 Current

amplification effect of the
unequal DG-HCD [1]
the Double Glow Hollow Cathode Discharge (DG-HCD). Since the discharge
potentials of the two cathodes are not equal, this phenomenon is referred as the
unequal potential hollow cathode discharge.
3.4.3 Current Amplification Effect of DG-HCD
The current amplification effect of the double glow hollow cathode discharge is
shown in Fig. 3.5. It is shown that when the cathode voltage Uc is increasing to
400 V, then both the main cathode current Ic and the source electrode current Is
will sharply increase.
3.5 Advent of Double Glow Plasma Surface

Alloying/Metallurgy (Xu-Tec Process)
3.5.1 First Experimental Device
In our first experiment in 1978, we used a modified vacuum glass bell jar coating
machine and a mercury vapor high-voltage DC power supply. The structure of the
device is shown in Fig. 3.6. In the bell jar (5) as a vacuum chamber, it encloses
components including an anode (6), cathode (8) for placing the working-piece,
another cathode (7) as a source electrode of the tungsten wire for providing
tungsten, which is connected to a power supply (12) through sliding resistor (11).
At that time, we only had one DC power supply. In order to give the power to the
two cathodes, respectively, we used a shunt resistance (11) to be a voltage supply
Fig. 3.6 Schematic diagram of double glow plasma surface alloying experiment setup unit [1]
3.5 Advent of Double Glow Plasma Surface Alloying/Metallurgy … 31
for supporting the source power potential. The voltage is transferred to the source
by an intermediate active tap on the shunt resistance device. Anode (6) and cathode
(8) are, respectively, connected to the ends of the DC power supply. The potential
difference between the anode and the cathode is the same as the potential difference
between the two ends of the DC power supply.
When the DC power is switched on, the double glow discharge phenomenon
appears. Both the specimen on the working table and the source electrode are
surrounded by glow discharges. The alloying elements in the electrode are sputtered
out by ion bombardment with Ar plasma, then travel toward the working-piece and
deposit on its surface. The alloy elements adsorbed on the surface of the
working-piece will diffuse into the subsurface of the workpiece. As a result, a deep
alloy layer is formed on the surface of the working-piece. The other main effect of
the cathode glow is the working-piece sample heating by ion bombardment; the
required high temperature provides a driving force for the diffusion of alloying
elements.
3.5.2 First Microstructure of Tungsten Surface Alloy
The first microstructure of tungsten alloy layer generated by double glow plasma
alloying technology is shown in Fig. 3.7. The tungsten content in the top surface
alloying layer is about 10%, with the thickness of 70 lm. The success of surface
alloying with tungsten of high atomic weight and high melting point indicates that
this technology could be applied to all solid-state alloying elements. Afterwards, we
had applied nickel, chromium, aluminum, titanium, and other metal elements
successfully to diffuse into the surface of steel materials, forming a wide variety of
alloy layers.
Fig. 3.7 Microstructure and

indentations of W-alloyed
layer generated by Xu-Tec
process [1]
3.5.3 Other Considerations
In the previous experimental design, we not only use ion bombardment and plasma
sputtering to generate alloy element vapor source, but also adopt a tungsten filament
resistance heating coil to enhance the supply of alloying elements. After this surface
alloying process, the experimental testing result shows that the cross section of
sample has a very clear white bright tungsten alloy layer.
At the beginning, the electric potential used on the working-piece cathode is
lower than that of the source electrode. Later on, we considered that the alloy
elements are sputtered out, and most of them are neutral atoms rather than positive
ions. In order to strengthen the ion bombardment and increase the supply of the
alloy elements, we have changed the source electrode potential to be lower than
the working-piece. In 1984, we introduced the hollow cathode discharge into the
double glow plasma surface alloying technology, which further strengthened the
glow discharge and the source sputtering rate.
In addition to the Xu-Tec process, we have also applied the double glow dis-
charge phenomenon to invent a series of new innovative technologies, such as
• Arc plasma added double glow surface alloying technology,
• Double glow plasma brazing technology,
• Double glow plasma sintering technology,
• Double glow plasma nanopowder technology,
• Double glow plasma thin diamond film technology,
• Double glow plasma sputter cleaning technology,
• Double glow plus high-frequency plasma surface alloying technology,
• Double glow plasma chemistry.
All of these technologies mentioned above will be explained in detail in
Chap. 13.
References

2. Xu Z, Wang ZM, Fang BH (1981) Research on the phenomena and characteristics of double
layer glow discharge in ion nitriding equipment. J Taiyuan Inst Technol 1:78–89
3. Xu Z (1982) Metal ion source for metallic surface metallurgy. In: 10th international symposium
on discharge and electrical insulation in vacuum, South Carolina, USA, pp 25–28
4. Xu Z, Wang ZM (1982) Double layer metallic cementation. Trans Metal Heat Treat 3(1):71–83
5. Xu Z (1997) Surface alloying simplified. Adv Mater Processes 152(6):33–35
Chapter 4
Double Glow Plasma Surface
Alloying/Metallurgy Technology
Abstract This chapter introduces the double glow plasma surface metallurgy
technology, ranging from its basic principle for surface alloy formation and
mechanism of alloy element inter-diffusion, to the operation processing and results.
The hardware configuration for the working-piece, the source electrode, gap pro-
tection and cathode power transmission device are described. The influence of the
main process parameters on the surface alloying layer and the discharge modes, arc
discharge and its causes are discussed in detail. In addition, some collective pro-
cessing experience and the operational requirements are also introduced and dis-
cussed. The advantages of the Xu-Tec process for surface alloying treatment and its
development history in China and in the USA are briefly presented.
4.1 Introduction
The plasma nitriding technology was invented by Berghaus in 1930s as the first
example of applying glow discharge to realize plasma nitriding on the surface of
metal materials. It is an effective way to improve surface hardness, wear resistance
and fatigue strength. However, the application of this technology was limited on
applying only with nonmetallic gaseous elements, such as nitrogen, carbon, sulfur
for plasma surface modification. To break that restriction of plasma nitriding, the
technology development to use solid alloy elements for surface alloying has been a
focus of engineering interests for a long time. The key issue to realize the surface
alloying with solid alloy elements is how to generate a vapor supply source of solid
alloying elements.
As is introduced in the last chapter, double glow plasma surface alloying tech-
nology was initially invented by Professor (David) Zhong Xu and his team along
their discovery of “Double Glow Discharge Phenomenon” [1, 2] in 1980. This
invention is a breakthrough in generating a vapor supply source of solid alloying
elements with glow discharge plasma. A set of invention patents of this process,
known as the Xu-Tec process, has been granted in the USA and worldwide [3].
DOI 10.1007/978-981-10-5724-3_4
34 4 Double Glow Plasma Surface Alloying/Metallurgy Technology
In this process, two sets of Argon gas plasma zones are generated through gas
glow discharge. Plasma ion sputtering of a solid target by one plasma zone is used
as a physical means to generate the metallic vapor of solid alloying elements.
Another plasma set is used to drive the inter-diffusion of deposited metallic alloying
elements into the substrate. The Xu-Tec Process can be utilized with any solid
metallic elements, such as Ni, Cr, W, Mo, Al, Ti, Nb, Zr, Pd, and their mixtures as
alloying elements. Numerous experimental results by the Xu-Tec process have
demonstrated that countless surface alloys, such as high-speed steel, nickel-base
alloy, wear-resistant alloys and corrosion-resistant alloys, have been produced on
the surfaces of carbon steels, titanium and its alloys, copper and copper alloys, as
well as Ti–Al intermetallic compounds.
The invention of the double glow plasma surface alloying technology (Xu-Tec
Process) inaugurated a new field of “Plasma Surface Metallurgy” in the science and
engineering of materials processing.
4.2 Basic Principle
The schematic diagram of the initial experimental hardware setup for double glow
discharge plasma surface alloying technology (Xu-Tec) is shown in Fig. 4.1.
In a vacuum chamber there are three electrodes: one ground anode and two
cathodes. One cathode is the substrate or working-piece, biased with a negative
elective potential. The other is the source electrode, further negatively biased and
used as a sputtering target of the desired alloying element(s). Physically, the source
electrode is arranged between the cathode and the anode. Two controllable DC
power supplies are arranged for a negative bias on the source electrode and the
working-piece to the grounded anode [4].
Fig. 4.1 Schematics of the initial basic hardware setup for Xu-Tec process
4.2 Basic Principle 35
Plasma generation: The Xu-Tec Process uses inert gas argon (Ar) as a working
gas. Under the condition of glow discharge at a certain vacuum pressure and electric
biases on cathodes, Ar atoms would be excited and partially ionized into a plasma
state. In this case, two groups of glow discharge are generated, one near the
working-piece surface (the first cathode) and the other near the source electrode
surface (the second cathode). So it is named as “Double Glow Discharge”.
Source Sputtering and Deposition: Driving under the electric field, the positive
charged Ar ions move toward negative-biased cathodes and bombard the
working-piece and the negative potential source electrode. Alloy elements from the
source electrode surface are sputtered off by energetic Ar ion bombardment,
transported through vacuum space with its remaining momentum and a neutral
charge state, and deposited on the surface of the working-piece.
Substrate (cathode) Heating: At the same time, massive electrons in the plasma
move towards the anode. However, due to bias voltage difference of about −400 V
at the source cathode (*−900 V) and the working-piece cathode (*−500 V), the
working-piece cathode is acting as a quasi-anode. Thus, driven by an electric field
between the source electrode and the working-piece, massive electrons together
with some ions of argon and alloying elements bombard the working-piece surface
and heat it to preselected high temperature. This temperature can be controlled by
the bias power and Ar gas partial pressure.
Diffusion and Alloying: At this high temperature, the alloy elements deposited
on the working-piece surface undergo through thermal-driven diffusion process into
the substrate of the working-piece and form a sub-surface alloy layer with special
physical and chemical properties. This is the distinct merit from common surface
coating process of metal materials.
It can be imagined that the glow discharge space in physical picture is very
complicated. Under the influence of the electric field, all the particles with negative
charge (such as electrons) will have directional movement towards the anode; all
positively charged particles will travel to the working-piece and the source elec-
trode. All neutral particles follow a free movement with their initial energy and
momentum. However, high-energy ions and particles moving at high speeds cause
multiple collisions and ionization, gaining more energy, and momentum from the
local electric field. Test measures have proved that, under the common glow dis-
charge condition, the ionization rate (a population ratio of positive ions to the
number of all particles) is low, mostly still in neutral atomic forms.
Positive ions of argon and neutral particles of alloying elements bombard the
working-piece, leaving all of its kinetic energy to heat the working-piece. Positive
argon ion bombardment heats the source electrode on the one hand, and makes the
source material to be sputtered for providing alloying elements on the other hand.
Alloying elements through the glow discharge space, travel to the working-piece
and deposited or adsorbed on the surface of the working-piece. Under ion bom-
bardment, the working-piece is heated to a high temperature, then the alloying
elements diffuse into the interior surface of the working-piece by thermal diffusion
and form a surface alloy in situ. In most cases, the source electrode potential is more
negative than that of the working-piece. Although the metal element at the
working-piece surface is also sputtered under ion bombardment conditions, the

higher negative potential of the source electrode is subjected to a more intense ion
bombardment. Therefore, much more alloying elements from the source electrode
to be sputtered, and a large number of alloy elements aggregates to the
working-piece surface and form a surface alloy layer therein.
4.3 Diffusion Mechanism
As is described above, the double glow plasma surface alloying process is involved
two important physical processes with Ar plasma generated by two glow discharge
zones in the vacuum condition. One is by plasma at the source-cathode surface.
Ar-ion bombardment induces sputtering of source material (solid vaporization),
leading to deposition of alloying elements on the working-piece cathode. The other
process is thermal diffusion of deposited alloy elements into the working-piece sur-
face at high temperature (>½ of the melting point) to form a surface alloy layer.
Compared with that of the conventional solid, liquid, and gas surface alloying
technologies, the formation speed of the alloy layer here is generally 1–3 times
higher, and the depth of diffusion or the thickness of the alloying layer is much large.
It is commonly believed that high diffusivity and reactivity of plasma surface
alloying is mainly driven by element concentration gradient and thermal gradient on
the surface. However, Xu proposed, in 1979 [5], a new diffusion mechanism about
high concentration vacancy defect layer which is formed on the substrate surface by
ion bombardment. In the double glow plasma surface alloying process, it was further
proposed in 1982 [6, 7] that “Vacancy Gradient” at the surface forms a diffusion
channel for surface absorbed alloying elements to diffuse into the substrate. In 1988,
they further discuss the vacancy diffusion mechanism and some diffusion model
under ion bombardment in his book “Plasma Surface Metallurgy” in Chinese [8].
The vacancy diffusion mechanism under the condition of ion bombardment can
be summarized as follows:
1. Ion bombardment can effectively remove oil stain and oxides on the surface of
the working-piece. After the working-piece surface cleaning, the exposed fresh
and activation surface is beneficial to adsorb incoming alloying elements and
drive alloying elements diffusing, by the concentration gradient and thermal
gradient on the surface, into the working-piece sub-surface without any barriers.
2. Under the bombardment of large number positive ions, a defect layer will be
formed on the surface of the working-piece with a large number of vacancies
and dislocations. The defect layer will dissolve more alloying element atoms; so
that the solubility of alloying elements at the substrate surface would be
over-exceed the solubility of the alloying element in the alloy phase diagram.
Therefore, a higher concentration gradient formed on the surface will accelerate
the diffusion process of alloying elements into the working-piece at high
temperature.
4.3 Diffusion Mechanism 37
3. Much high vacancy concentration in the surface defect layer will enhance the
vacancy diffusion into the matrix. A vacancy gradient layer will be formed by
vacancy diffusion into the matrix. The high vacancy concentration gradient at
the surface would provide a fast path for the alloying elements to diffuse into the
matrix.
The above points are reasonably explained that the double glow plasma surface
metallurgy is faster than other traditional surface alloying processes (such as solid,
liquid, gas surface alloying technology, etc.). It is a major merit of the plasma
surface metallurgy technology.
4.4 Process Operation
Here, the processing operation steps of the Xu-Tec process are listed below:
1. Cleaning the working-piece: All working-pieces should be cleaning carefully
to remove possible contaminants, such as oils or greases, and with final cleaning
in a vapor degreaser. It is particularly important to remove traces of metal
particles which might act as masking elements.
2. Vacuuming the chamber: The ultimate base vacuum should be reached at
lower than 1 Pa or better.
3. Gas refill: Refilled with argon gas to the working pressure. The working air
pressure can range normally at 20–60 Pa.
4. Starting the first plasma for cleaning and preheating: Starting the
working-piece power supply to generate the first discharge plasma. Ar ion
bombardment will help clean the surface of the working-piece through sput-
tering, also preheat the working-piece to an elevated temperature. Meanwhile,
slowly raise the working-piece power supply voltage to the 300–600 V, increase
the working-piece current, so that the working-piece will be gradually heated up
to about 400 °C.
5. Starting the second plasma for source sputtering and deposition: In the slow
heating process above, switch on the source power supply to generate second
discharge plasma zone near the surface of source cathode by gradually raise the
source voltage and current. Adjusting the working-piece voltage and the source
voltage, so that the working-piece voltage is gradually decreased to the 300–
500 V, but the voltage of the source is constantly increased to 800–1200 V.
(a) Control the temperature of the working-piece heating up to the required
temperature range of 900–1100 °C.
(b) Source sputtering, deposition and diffusion of alloying elements at the
working-piece surface starting. For the required thickness of the alloy layer,
the holding time range could vary usually 1–8 h.
6. Plasma off and Cooling: At the predefined process time, turn the power sup-
plies off and get the workpiece cooled down. Upon the vacuum chamber seal
condition, equipment leakage rate and working cycle and other factors, the
cooling can go through one of the following three ways:
(a) Ambient cooling: Power off two suppliers. Stop gas filling and vacuum
pump, the working-piece slowly cooled in the furnace.
(b) Slow cooling: Power off source supplier, decrease the working-piece current
to maintain the glow and slow cooling.
(c) Quick cooling: Power off both supplies, increase the plentiful supply of
argon to drive for a rapid cooling.
4.5 Configuration of Working-Piece and Source Electrode
In the double glow plasma alloying technology, the shape and structure design of
the source electrode is an important matter as the source shape will affect the results
of the surface alloying of the working-piece. The structure and configuration of the
source electrode are usually varied with the shape and structure of the
working-piece.
4.5.1 Plate Type
A flat plate source shape and structure, such as one shown in Fig. 4.2a, are com-
monly used. The working-piece is flat, so the source electrode is flat. They are
Fig. 4.2 Planar type of

working-piece and source
cathode: a two parallel plates
and b the rod array to a plate
4.5 Configuration of Working-Piece and Source Electrode 39
placed in parallel to each other and the setup configuration is relatively simple.
When the distance between the working-piece and the source ranges from 10 to
30 mm, the hollow cathode discharge between them is generated. The discharge
mode can greatly raise the current density of the glow discharge, so as is increasing
in the plasma intensity and sputtering efficiency. In order to increase the vapor
supply of alloying element, the source can be made into a rod and a filament to
increase the surface reactive area, as shown in Fig. 4.2b.
If it is necessary, the working-piece and source electrode can be heated by the
same power supply. When the independent discharge mode is used, the distance
between the working-piece and the source is large, ranging in 30–100 mm.
4.5.2 Cave Type
The structure and configuration of the cave type is shown in Fig. 4.3. The structure
is characterized by placing the working-piece inside a cylindrical source electrode,
so that the entire surface of the workpiece can be treated. The electric potential of
the cylindrical source cathode and the working-piece is different. A plate is placed
on the top of the working-piece and the cylindrical source electrode can be also as
an auxiliary electrode to prevent the escape of alloying elements. The distance
between the source electrode and the working-piece is arranged to ensure that the
double glow hollow cathode discharge is formed. When the surface alloying is
processing, the hollow cathode discharge is formed between the working-piece and
the cylindrical source electrode. The working-piece is surrounding by cylindrical
electrode, it can reduce surrounding radiation of the working-piece, rapidly heat
working-piece and ensure the uniformity of heating of the working-piece; on the
other hand it can restrict the sputtered alloying elements atoms within the cylin-
drical electrode and increase the sputtered alloying elements density and ionization
rate, in order to improve the efficiency of surface alloying.
The cave and plate type are the main configurations for the study on the plasma
surface alloying in the laboratory.
Fig. 4.3 Schematics of cave

type configuration of
cathode
Fig. 4.4 Deep well type

configuration of
cathode
4.5.3 Deep Well Type
The structure and configuration of a deep well type is shown in Fig. 4.4. Similar to
the cave type electrode structure, the working-piece is placed in a cylinder as an
auxiliary electrode and has the same potential with the auxiliary electrode. This
configuration is good for alloying the inner surface of long tube. A long alloy rod as
source electrodes is suspended in the tube, and the double glow hollow cathode
discharge is formed between the tube and the rod.
These three types shown above are mainly used in our experimental study in the
laboratory. However, its basic principle can be applied for the surface alloying
treatment in a large industrial furnace.
4.6 Technological Parameters
There are many technological parameters for double glow plasma surface metal-
lurgy technology, such as argon pressure, cathode voltage, source electrode voltage,
currents of cathode and source, distance between substrate and source, temperature,
maintain time and so on. To illustrate the optimization of the processing parameters,
low-carbon Steel-1020 is selected as substrate material and alloy Ni80–Cr20 is used
as the source material to conduct plasma surface alloying.
The technological parameters can be mainly divided into two groups: measur-
able parameters and nonmeasurable parameters [9].
4.6.1 Measurable Parameters
According to the previous experimental results, we obtained the typical process

parameter ranges as follows:
4.6 Technological Parameters 41
• Argon gas pressure (P): 20–50 Pa,

• Source voltage (Vc): 800–1200 V,
• Working-piece voltage (VS): 300–600 V,
• Distance between the working-piece and the source (D): 10–30 mm,
• Alloying temperature (T): 900–1000 °C,
• Holding time (t): 3 h.
After the plasma surface alloying treatment, the following data can be obtained
through the observation and measurement of the surface alloying layer by optical
microscope and the analysis and calculation of the composition of the alloying
layer.
• Total surface alloy depth: L = Ld + Lc,
• Diffusion layer depth: Ld,
• Covering (deposition) layer depth Lc,
• Concentration of alloying element in alloying layer: C,
• Alloying element supply: Mi,
• Source current: Is.
These data can be used to evaluate the surface alloying layer. Among them, C,
Ld, Mi, and Is are selected as the major evaluation parameters.
1. Argon Gas Pressure (P)
Argon gas pressure is one of the most important processing parameters of double
glow plasma surface metallurgy process. It is a basic condition to maintain glow
discharge and to form hollow cathode discharge. The gas pressure P has a very
important influence on the current density, ion bombardment strength, and trans-
portation of the active atoms in space, as well as the supply of alloying elements,
adsorption and diffusion of alloying elements at the working-piece surface. The
amount of alloying element sputtered from the source electrode is determined by
the energy and density of ions. The average energy e of ion at the surface of the
source electrode can be expressed as [10]:
e ¼ 2Vs ðk=Dk Þ
where k is the mean free path of ions, which is influenced by the gas pressure P, Dk
is the width of cathode potential drop region, and Vs is the source electrode potential
drop approximately equal to the total discharge voltage. Since k and Dk are
anti-proportional with the gas pressure P, respectively, it is comprehensively
understood that the air pressure P has no effect to the average energy e of ions. The
average energy e and ion bombardment energy at source electrode surface is mainly
determined by the source voltage.
Argon gas pressure can change the ion density at the source material surface.
The sputtering yield S of source electrode is inversely proportional to the power of
argon gas pressure:
S11=Pn
where n is the empirical value between 2 and 5, approximately. It seems that low
pressure is favorable to the sputtering yield of source material, but the surface of
working-piece is also strongly sputtered under the low pressure, which is unfa-
vorable to the deposition on the surface of working-piece and formation of high
concentration of alloying element. High argon pressure is unbeneficial for the
source electrode to increase the sputtering yield due to the “Back Scattering”. The
so-called back scattering effect (BSE) refers to the sputtered particles in glow
discharge due to other particle collisions and back to the sputtering target. At low
vacuum discharge conditions, the free path of a particle is much less than the
distance between the sputtering target and the working-piece. The higher the argon
pressure is, the stronger the back scattering effect would be. When the pressure
reaches 133.3 Pa, the particles can back to the target as high as 99%. The pressure
drop to 17.3 Pa, the proportion is still as high as 50%. The back scattering effect can
be neglected only when the pressure is lower than 1.33 Pa. The argon pressure
range of the double glow plasma surface alloying is generally in the 20–60 Pa, so
the back scattering effect is relatively strong, and its influence cannot be ignored.
The argon gas pressure can affect the ion density at the working-piece surface in
a certain range of Ar partial pressure: the higher the argon pressure, the higher the
ion density. Ion bombardment on the surface of the working-piece has the two
functions: (1) it causes dis-absorption of the deposited atoms at the working-piece
surface, usually referred the “Anti-sputtering” phenomenon; (2) it could produce a
sub-surface layer of 5–10 µm thick with a high vacancy density, that provides a
diffusion channel to accelerate diffusion of alloying atoms into the working-piece.
The combined effects of argon gas pressure will eventually lead to the change of
supply amount of alloying element, and then affect the formation of alloying layer.
Figure 4.5 is shown the effect of the argon pressure on a surface alloy layer.
A sample of Steel-1020 was plasma surface alloyed by using Ni80–Cr20 alloy as a
source material at 1000 °C for 3 h. As shown in Fig. 4.5a, as the argon gas pressure
P increase, the source-cathode current (Is) increases, while the alloying element
0.75 600
alloying element supply M I /mg
Is
(a) (b)
Source-cathode current Is /A
0.70 MI
0.65 550
0.60
0.55 500
0.50
0.45 450
0.40
0.35 400
20 30 40 50 60 70
Gas Pressure P/Pa
Fig. 4.5 Effects of gas pressure P on a source-cathode current (Is) and alloying element supply
(MI), b concentration (C) and case depth (Ld) [11]
supply (Mi) decreases. This behavior is due to the back scattering effect enhanced at
higher pressure. As a consequence, the alloying element concentration C in the
working-piece surface decreases and the thickness of the alloy layer decreases.
A lot of studies have shown that when the argon pressure is too high or too low,
both them are not good for the formation of the alloy layer [11, 12]. A large number
of experimental studies show that the better gas working pressure is about 25–50 Pa
for steels. Figure 4.5b shows that, at this time the surface alloy layer thickness (the
case depth) Ld and the alloy element concentration C of the surface alloy are
reached to maximum.
2. Source Electrode Voltage and Current
The source electrode voltage (Vs) and current (Is) are key control parameters to
plasma density and ion energy near the source electrode surface in the Xu-Tec
process. The source current is generally affected by the source and working-piece
bias voltages, as well as the gas pressure, in turn, control the supply of the alloying
elements. The higher the source voltage is, the higher the density and energy of ions
would be. In turn, the higher the ion density, the more alloying element would be
provided by ion sputtering.
Figure 4.6 shows the influence of source voltage on the surface alloying layer.
The ion density and the supply of alloy elements Mi increase with the source
voltage, leading a higher alloying element concentration C and higher diffusion
alloy depth Ld at the working-piece. Along the source voltage Vs is increasing, the
source current increases relatively slow, but it can obviously increase the supply of
the alloy element, which would be beneficial to the formation of the surface alloy
layer. In most case, the source voltage must be higher than 800 V. Low source
voltage is not conducive to the result of the plasma surface alloying. However, the
source voltage may not be too high due to the fact that the high source voltage and
current will cause the large supply rate. The fast deposition may hinder the diffusion
of the alloy elements into the working-piece, so that the depth of the surface
diffusion alloy layer is reduced. The range of the source voltage is generally from
800 to 1200 V.
Fig. 4.6 Effects of source-cathode voltage Vs on, a concentration C and case depth Ld, b alloying
elements supply MI and source-cathode current Is [11]
Fig. 4.7 Correlations

between temperature, bias
voltages of the cathode and
source [13]
3. Workpiece Voltage and Current

The working-piece voltage Vc and current Ic are another two parameters in con-
trolling plasma density near the working-piece surface. The working-piece current
is the indication of the ion density at the working-piece surface—the higher the
working-piece current, the higher the ion density at the surface of the
working-piece. The working-piece current density is the main factor for heating the
working-piece and can be controlled by the working-piece voltage and source
voltage, and the gas pressure as well.
Experimental studies on the relationship of the temperature, voltages of two
electrodes and the pressure are shown in Fig. 4.7 [13]. It is worth noting that the
temperature will increase greatly if the potential difference between the cathode and
the source electrode is kept above the level of 250 V. This indicates that the hollow
cathode discharge effect produces the crosslinking function between the source and
the working-piece, thus the provided ion energy is much increased. This is due to
the fact that the hollow cathode discharge produces a larger current density, leads to
the increase of the sputtering yield of alloying elements as well as the surface
vacancy concentration of the working-piece substrate.
The working-piece voltage can play an important influence on the formation of a
surface alloy layer. On the one hand, ion bombardment can produce a high population of
vacancy defects at the surface, inducing inter-diffusion of alloy elements into the
working-piece. On the other hand, ion bombardment on the surface of the working-piece
could cause sputtering of both the chemical element of the working-piece and the
adsorbed alloying elements at the surface of the working-piece.
Figure 4.8 shows the influence of working-piece voltage on the surface alloy
layer. A relative better working-piece voltage range is 350–500 V. When the
working-piece voltage Vc below 350 V, the plasma density is low and not conducive
to the formation of the surface vacancy and diffusion of alloying elements. When Vc
is higher than 500 V, the ion bombardment is enhanced and the anti-sputtering
becomes significant, so that the working-piece surface is difficult to maintain a high
concentration of the alloying elements, and the alloy layer thickness Ld decreases.
Fig. 4.8 Effects of the working-piece cathode voltage Vc on, a concentration C and case depth Ld,
b alloying elements supply MI and source-cathode current Is [11]
The working-piece voltage Vc has little influence on the source discharge current
Is and the supply MI of the alloying element.
4. Distance between Working-piece and Source
In the double glow hollow cathode discharge (DG-HCD) mode, the distance d be-
tween the working-piece and source is one of the main controllable factors to the
formation of DG-HCD. In order to generate and maintain a DG-HCD mode, the
distance d would be about in 10–30 mm. Considering the space transport and a loss
of alloying elements, a large distance will result in a loss of alloying elements due
to the increased number of collisions in the transport space. A smaller distance is
conducive to the formation of the alloying layer. However, if the distance between
electrodes is too small, there is a risk of the arc discharge.
Figure 4.9 shows that, when distance d increases, the concentration C of the
surface alloy and the thickness Ld of the diffusion layer are reduced. The optimized
distance between the working-piece and source is about 14–25 mm.
The distance d between the working-piece and the source electrode has little
effect on the source electrode current Is and supply MI of the alloying element.
Fig. 4.9 Correlation effects of distance d between two cathodes on, a concentration C and case
depth Ld, b source cathode current Is and alloying elements supply MI [11]
Fig. 4.10 Effect of process

temperature on the case depth 120
Pure iron
Diffusion layer depth / µm

20 steel
100
45 steel
T8 steel
80
60
40
20
0
800 850 900 950 1000 1050 1100
Process temperature / °C
5. Alloying Temperature T
Based on the alloy phase diagram of the matrix element and alloying elements,
alloying temperature should be lower than the melting point of the matrix material.
The temperature on the working-piece surface has a major impact to the diffusion
rate, the composition and microstructure of the surface alloy layer. To selecting
working alloying temperature, one must consider its effect on the growth rate of the
surface alloying layer, microstructure and properties of matrix material.
The diffusion coefficient (D) of alloying elements in the matrix has the Arrhenius
relationship with alloying temperature (T) as following:

Q
D ¼ D0 exp ;
RT
where Q is the activation energy for diffusion, a physical parameter determined by

the matrix material.
From the above relationship, it was shown that the diffusion coefficient
D exponentially increases with alloying temperature T, the higher the alloying
temperature T, the faster diffusion would be. Figure 4.10 is shown the effect of the
temperature on the surface alloy layer thickness, including the diffusion layer and
the deposited layer. The alloying temperature is controllable by adjusting the gas
pressure, the work voltage and the source voltage. The range of alloying temper-
ature is higher than 900–1100 °C for iron and steel materials.
6. Holding Time
Under a certain condition, the thickness (x) and diffusion time (t) display the
following relationship based on the equation of diffusion [14]:
Fig. 4.11 Effects of the holding time on surface alloy depth, a the diffusion layer depth at 1000 °C,
b the deposition layer depth at 850 °C
pffiffiffiffiffi
x ¼ K Dt
where t is the holding time and K is a constant. The equation implicated the
diffusion distance of atoms (the thickness of the alloying layer) is proportional to
the square root of time. The longer the time lasts, the thicker the alloyed layer
would be.
Figure 4.11 shows one example of the influence of the holding time on the
thickness of the diffusion layer and the deposition layer. In this experiment, the
surface alloyed materials are pure iron, 1020 steel, 1045 steel and 1080 steel. To
take surface alloying with Mo80–W20 alloy as a source material, the thickness of
the diffusion layer with the increase in the holding time shows a parabolic rise and
the deposit thickness is straight up as well.
4.6.2 Typical Process Parameters
In most cases, the double glow hollow cathode discharge mode is used for double
glow plasma surface alloying. In this kind of a discharge mode, all kinds of dis-
charge parameters influence each other, and the interaction is complicated.
According to the above experimental results, it is recommended that the typical
operational process parameters for the Xu-Tec process should be set as:
• Argon gas pressure: 25–50 Pa
• Source voltage: 800–1200 V
• Working-piece voltage: 300–600 V
• The distance between the working-piece and the source: 10–30 mm
• Operation alloying temperature: 900–1000 °C
• Holding time: 1–10 h.
In the actual operation of the surface alloying process, the typical setup is: argon
gas pressure—35 Pa, the distance between the working-piece and the source—
20 mm, the alloying temperature—1000°, and the holding time depends on the
thickness of the alloy layer. The working-piece voltage and source voltage are the
main adjustable operating parameters. In the DG-HCD discharge mode, they are
mutually influenced each other.
It is noted here that in the most common cases for the Xu-Tec Process, it is to set
the working-piece bias at a potential higher than the source potential, such as the
working-piece voltage of 400–600 volts, and the source voltage of 800–1000 volts.
In order to further increase the supply of alloy elements and accelerate the diffusion
process of alloy elements, hollow cathode discharge was introduced into the
Xu-Tec Process. Because the working-piece and the source potential are not equal,
it is called the no equal potential hollow cathode discharge phenomenon. In some
cases, the working-piece and the source can be equipotential, which depends mainly
on the temperature required for the working-piece. A large number of experimental
studies have shown that alloy layers can be formed on the working-piece surface
regardless of the working-piece voltage above or equal to or below the source
voltage. But in order to obtain high alloy content and better control the composition
of the surface alloy layer, we mostly set the source electrode potential more neg-
atively than the working-piece potential.
4.6.3 Nonmeasurable Parameters
1. Argon Gas Purity

In most case, argon gas in the industrial grade can be used. However, for some
active metal materials, such as titanium and aluminum, high chemical purity argon
should be used. Impurities in industrial grade argon gas normally consist of some
gas elements from air, such as oxygen, nitrogen, carbon oxide, and hydro-oxide.
During the plasma process, those impurity elements easily form metal oxide and
nitride on the working-piece surface, inhibiting the diffusion of the alloying element
and prevent the alloying process.
Caution should be taken to prevent air contamination in the pipeline when we
use a new gas tank, especially with industrial purity grade of Argon. It is noted here
that the top and bottom of the industrial argon gas cylinder often contain more
impurities from air. Therefore, when a new bottle of argon gas cylinder is used, we
need to purge the preline to remove the top containing impurities before use. When
argon gas is used up to the bottom, a new argon bottle must be replaced quickly.
2. Source Materials
In normal cases, the source material target is used in a pure metal plate or rod. For
the surface alloy with two or more alloy elements, the source material target is
fabricated through powder metallurgy sintered plate or rod. For example, to form
high-speed steel (HSS) in carbon steel hacksaw blade teeth, powder materials of
Mo80–W20, Mo60–W40, Mo40–W60, and Mo20–W80 are respectively adopted
as the source material for processes. While Mo80–W20 material was approved as
an optimal source material for plasma surface metallurgy HSS.
Often, the existing standard alloy material can be used as the source material for
producing a required surface alloy with complex composition. For example, to
produce a nickel-base alloy layer on the surface of carbon steel plate, Inconel-625
can be used as the source materials. After plasma surface alloying process, the
composition of the alloyed surface alloy layer is similar to the composition of
source materials.
3. Structure and Arrangement of Source Materials
As the double glow discharge plasma surface alloying process has a physical vapor
deposition process with a feature of “line-on-sight”, the source material with var-
ious shapes and types should be distributed around the working-piece. As was
discussed in Sect. 4.5, the shape of the source target needs to be designed according
to the shape of the working-piece. The source material may be plate, cylinder,
article, block, wire and others. For example, Ni–Cr alloy plate can be used for
surface alloying of carbon steel plate as the source material. For the saw blade, we
will arrange saw blade tooth upwards into a plane, and then set up an opposite plate
of powder metallurgy alloy Mo80–W20 as a source material. For large complex
shape working-pieces such as colloid mill, we adopt a carbon steel cylinder. Its
diameter is bigger than colloid mill for about 40 mm. We drill many small holes
evenly distributed in the cylinder wall, then insert tungsten or molybdenum bars in
the diameter of 6 mm into holes to form a source electrode.
4. Workpiece Placement
Depending on their shape, the working-pieces can be stacked or suspended. But, it
should avoid the formation of double glow hollow cathode discharge between the
working-pieces.
4.7 Arc Discharge
As is discussed in Chap. 2, arc discharge is a kind of electrical breakdown of gas

discharge with very high current density at a low voltage. The characteristic cur-
rent–voltage curve of glow discharge has been shown in Chap. 2 (see Fig. 2.1). The
arc plasma creates a local short circuit, where the cathode voltage is suddenly
reduced to a few tens of volts, while the current rise drastically. In an arc discharge
mode, normally all discharge power is concentrated in a small region. In turn, a
large current induces a sharp rise in temperature of the small surface on the
working-piece, even leading to local melting. As a consequence, a local material
gasification and vaporization take in place, leading to the arc damage on the
working-piece and the cathode power transmission device.
Arc discharge could be possibly occur in double glow discharge and can be
classified mainly in two forms: micro-arc discharge and arc discharge.
4.7.1 Micro-Arc Discharge
Micro-arc discharge could take place on some oil stains and oxides on the
working-piece surface. Oil stain is not conductive and could be easily charged up
with electrons from Ar plasma. Those charges quickly build an intensified electric
field on the surface of this thin oil stain layer. When the electric field strength
reaches the electric intensity breakdown point of nearby gas molecular, initial gas
discharge takes place. Positive ions in the plasma are attracted to focus on the stain
spot. This discharge and ion bombardment will lead to a physical destruction,
decomposition and gasification of oil stains. A vapor steam of H–C–O gas
molecular is released into the plasma zone and arises the local partial pressure
momentarily. It further intensifies the plasma and ion bombardment and increases
the current density. However, due to a material quantity limitation from a small
stain spot, this arc discharge would not be able to maintain and would be quickly
dismissed by itself.
The grease spots may distribute the full of the working-piece surface. By using
the continuous discharge, oil stains will be either evaporated or sputtered off, the
surface of the working-piece will be thoroughly cleaning. In the initial stage of glow
discharge, we can observe the continuous discharge with changing position light on
the working-piece surface. This micro-arc discharge is not a terrible process and it is
not sustainable in time. As long as the all grease spots on the surface of the
working-piece disappear, a uniform distribution of stable glow discharge will
appear on the all surface of the working-piece.
Similarly, nonconductive oxide on the surface of the working-piece would also
induce the arc discharge. Oxide spots disappear as the arc discharge with oil stains.
4.7.2 Macro Arc Discharge
Different from micro-arc discharge, macro arc discharge is more severe and
destructive. Characteristic of arc discharge is the cathode voltage sag, while the
current rises sharply to tens of amps or even hundreds of amps and the voltage can
plummet from hundreds of volts to a few tens of volts. If there is a large and thick
greasy dirt spot on the surface of the working-piece, concentrated discharge in the
sludge can take place for a longer time and cause its material vaporization, resulting
in local partial pressure increase and developing to arc discharge. Once the arc
discharge is initiated, it leads to local surface temperature dramatically increasing
4.7 Arc Discharge 51
and melting of the surface of the working-piece. Consequently, it will make arc
discharge further intensified and the working-piece surface damage, even destroys
the equipment. Therefore, a special attention must be taken in the design of furnace
structure, cathode power transmission device and a power supply, and various
measures to prevent the generation of arc discharge.
The cathode transmission device is the most important part in plasma surface
alloying equipment. The design of the cathode power transmission device with the
gap protection structure will help to prevent the arc discharge occurrence.
4.7.3 Harmfulness of Arc Discharge
Arc discharge in double glow plasma surface alloying occurs more easily than the
plasma nitriding, the consequences are more serious. Taking iron and steel material
as an example, the nonmetallic elements C, N, S atomic radius is small and can pass
through the gap of the iron atoms into steel materials. Metal elements Ni, W, Mo,
Cr, and other atomic radius are much larger and can only diffuse into a steel
material through mutual replacement diffusion. Therefore, the solid alloy elements
diffuse into the surface of the steel material is much more difficult than the diffusion
of nonmetallic elements. We know that the general treatment of ion nitriding
temperature range from 500 to 600 °C, while the double glow plasma surface
alloying of the working-piece temperature is as high as 900–1100 °C, closed to the
melting point of steel. Therefore, in the double glow hollow cathode discharge
mode, the double glow plasma surface alloying is relatively much easy to make the
steel surface melting and then causes arc discharge. The arc discharge tends to
happen easily due to the evaporation of iron and steel materials and intensified,
resulting in destruction of the working-piece or equipment, the consequences are
very serious. In addition, due to the high temperature, the requirements for the
cathode transmission device, the gap protection device and the materials for internal
structure of the equipment, as well as the power supplies, are all more stringent.
4.7.4 Reasons of Arc Discharge
Under the double glow discharge conditions, there are many factors for arc dis-
charge to happen, and the specific situation is very complex. To prevent the gen-
eration of arc discharge in the operation process, we must clearly understand what
factors may induce a change from glow discharge to arc discharge. When the arc
discharge phenomenon appeared, what should we do? Based on our long-term
industrial application experiences on the plasma surface alloying technology, we
summarize here our understanding of the phenomena and causes of glow discharge
to arc discharge.
(1) Surface Contaminations on Working-piece

On the surface of the working-piece after machining, there are always left with
contamination of sticky oil grease stain and oxide patches. Normally, these con-
tamination patches would be cleaned by ion sputtering at the early step. At the same
time, there may produce massive micro-arc discharge spots through oil stain
breakdown, as we can see the beautiful scene of a micro-arc flashing on the
working-piece surface. After all grease spot on the surface of the workpiece was
eradicated by micro-arc discharge and the working-piece surface will enter a stable
and uniform glow discharge.
In order to avoid and reduce the occurrence of micro-arc discharge, we should
carefully clean the working-piece and eliminating surface oil stains and oxides of
the workpiece before placing it in the vacuum chamber.
(2) Surface Roughness of Workpiece: Holes and Grooves
Surface structural roughness features, like small holes and small-width grooves, on
the working-piece may cause hollow cathode discharge (HCD), leading to arc
discharge. For example, in micro-size holes, HCD may be initiated along the inner
surface. Two of the opposite surfaces in the trench may also possibly form HCD.
This partial HCD will cause a sharp rise in temperature and produce a local melting
inside the holes. Due to discharge heating induced the grease volatilization, local
partial pressure increases and causes arc discharge cascade growing. Therefore, the
inner cavity of small holes and grooves must be carefully and thoroughly cleaned.
(3) Cross Discharge between Working-pieces
In order to improve the production efficiency, the vacuum furnace is often loaded
with many of the same or different shapes of parts. All kinds of parts in the furnace
and its relative position need to be carefully arranged. Due to poor electric con-
nection or different surface condition, some parts may be electric static-charging in
different potential from the neighboring parts. This potential difference may initiate
addition HCD between parts. These HCDs by the different working-pieces may
cause uneven local temperature. Eventually it leads to partial melting and arc
discharge.
(4) HCD between Working-piece and Source Electrode
In most cases, the bias potential of the workpiece and the source is different in a few
hundred of volts. When two objects are placed close to each other (the distanced
<10 mm), any irregular points as mentioned above on the surface of either electrode
may initiate a direct-macro arc discharge between two electrodes. This situation
would be very chaotic and severe.
In 1995, we use our own design and manufacture large horizontal furnace to
alloy ten thousand pieces of handsaw blades. The furnace is hanging tungsten and
molybdenum alloy plates as source materials, Each face of source plate is opposite
to set up one thousand pieces of handsaw blades. The distance of saw tooth tip and
the source electrode surface is 15–20 mm. When the blade temperature reaches
4.7 Arc Discharge 53
1000 °C shortly after, we found that the arc discharge continuously takes place in
the rear. We opened the stove and found that about 10 saw blades had been melted
by arc discharge. The reason is found out at a place where the distance between the
saw blade and source is too close, only 5 mm. There the hollow cathode discharge
is much stronger than other places, and so is the local temperature. When the blade
temperature reaches melting point, those saw blades will cause melting and gasi-
fication, and the local pressure suddenly increased as well, leading to arc discharge.
(5) Cathode Transmission Device without Reliability
Cathode power transmission device is the most important part of plasma surface
metallurgy equipment. If the design of transmission device of cathode is unrea-
sonable, the gap protection is not reliable, or insulation and sealing materials are
unqualified, it will lead to the arc discharge at cathode power transmission device
and even produce disastrous consequences.
In 1990, when we operated the large plasma surface metallurgical industrial
furnace, the failure of the ceramic tube was caused by the poor quality of the
insulating ceramic tube, which resulted in the arc of the cooling water pipe in the
transmission device. If arcing due to water pipe leak, liquid water enters the furnace
at a temperature of 1000°, the consequences will be unbearable to contemplate.
(6) Arc Discharge in Double Glow Plasma Surface Metallurgy
Double glow plasma surface metallurgy will lead to high temperature at more than
1000 °C while ion nitriding processing is at 560 °C. Compared with the ion
nitriding processing, double glow plasma surface metallurgy are more likely to
produce arc discharge, the consequences may make the working-piece local melt-
ing, also may make the cathode power transmission device destroyed.
4.8 Cathode Power Transmission Device and Gap

Protection
The cathode power transmission device is a high voltage electric feedthrough for
the bias supply. It is one of the key hardware components in the plasma alloying
process equipment. As both the cathode and the source electrode in Double glow
plasma surface alloying equipment are biased in a negative potential, their cathode
transmission devices are facing the same problem.
4.8.1 Requirements of Cathode Transmission Device
The main function of the cathode transmission device is to introduce the high
voltage DC electric power into the vacuum chamber. It also needs to have a means
to prevent glow discharge and ion bombardment nearby to destroy insulating
ceramic. Therefore, the cathode transmission device must meet the following
requirements:
(1) Electric Conducting: Cathode power transmission device has a conductive
metal rod, usually made of copper-plated low-carbon steel.
(2) Vacuum Sealing: In order to keep the sealing of the vacuum furnace, the
high-temperature resistant silicone rubber can be used for vacuum sealing ring.
(3) Electric Insulation: In order to have a reliable insulation between the conductive
rod and the vacuum furnace body, high quality, high-temperature resistance and
high density of insulating ceramics are usually used as insulation material.
(4) Temperature Cooling: In order to prevent the vacuum rubber ring aging or
damage due to high current induced high temperature, usually circulating
chilling water should be used to cool the device.
(5) Gap Protections: This is the most critical issue for the cathode transmission
device. In order to meet those requirements mentioned above, the cathode
transmission device is made with several sub-components within a limit space
(—a gap). There exists a hug high electric field drop from the center cathode
rod across this gap, through surrounded ceramic insulator collar tubes to the
grounded furnace body. If lack of a caution, severe arc discharge may take
place in any small gaps, rough points and sharp edges, leading to local material
melting and evaporation, eventually destroy the device. In order to avoid the
problem above happen, a gap protection device must be included in the cathode
transmission device.
4.8.2 Principle of Gap Protection
More than 100 years ago, people have found, as shown in Chap. 2 (see Fig. 2.2),
the stratified phenomenon in the cathode glow discharge: starting from the cathode
surface, followed by Aston dark region, cathode glow region, cathode dark region,
and the negative glow region. The above four areas are referred to as the width of
cathode potential drop region, which is expressed by the Dk value. It was found that
the change of the distance between the anode and the cathode in the large discharge
space did not affect the glow discharge of the cathode. However, if the distance
between the anode and the cathode surface is less than the Dk value, the glow
discharge around the cathode will be extinguished immediately. We can call this
kind of glow discharge phenomenon as Dk phenomenon. This is the basic principle
of the gap protection in the glow discharge.
4.8 Cathode Power Transmission Device and Gap Protection 55
Fig. 4.12 Schematics of gap protection structure map: a axial gap, b radial gap, c double gaps
Dk and gas pressure P have the following relationship:

1
Dk ¼ 0:82 ln 1 þ =AP;
B
where A is a constant, B is the second electron emission factor, and P is the gas
pressure.
From the above formula, it can be seen that Dk is inversely proportional to the
gas pressure P. In Reference [15], it has indicated that some corresponding normal
glow cathode fall thicknesses PDk are given in Torr-cm. When the cathode material
is iron and the working gas is argon, PDk is equal to 0.33 Torr-cm. The general
range of argon pressure for the Xu-Tec process of steel material is from 20 to 40 Pa,
therefore Dk is from 2.2 to 1.1 cm. The most simple structure of the gap protection
device between the cathode rod and the ceramic tube is shown in Fig. 4.12a.
An annular step with a gap groove ring in a width of 1 mm and a depth of
10 mm is formed between the cathode rod and the insulating ceramic tube, as
shown in Fig. 4.12b. Thus, due to the width of the ring groove is much less than the
Dk value, the glow discharge nearby the surface of the cathode is disappeared. The
ring groove has also isolated the ceramic material and prevent from the ion bom-
bardment. Three ring grooves on the outer surface of the insulating sleeve prevent
from the sputtered metal powder which is covered on the surface of the sleeve and
loss of the insulation function. There are two basic types of gaps: axial and radial
gaps. Figure 4.12c presents both axial and radial gaps.
Fig. 4.13 Cross section of

cathode and source power
transmission device. 1
Cathode plate; 2 gap
protection ring; 3 insulating
sleeve; 4 ceramic tube; 5
conducting rod; 6 support; 7
furnace body; 8 water
cooling; 9 cathode lead
column; 10 insulating pad; 11
and 12 robber sealing ring; 13
water cooling pipe
4.8.3 Example of Cathode Transmission Device
One typical cathode power transmission devices is shown in Fig. 4.13. The device
is capable of meeting all requirements of conducting, sealing, insulation, cooling,
and gap protection. This cathode power transmission device was designed and
fabricated by Chinese Wuhan Lide Company. There is an axial gap protection. The
device has gone through a long-term test with a simple structure and reliable
performance.
4.9 Advantages of Xu-Tec Process
Double glow plasma surface metallurgy technology (the Xu-Tec process) is a very
important breakthrough of material surface alloying modification process. It is a
complex integration involving low vacuum condition, double glow discharge and
the low-temperature plasma, the processes of ion bombardment, sputtering, space
transport, deposition, diffusion, and formation of an alloy layer with special
4.9 Advantages of Xu-Tec Process 57
physical and chemical properties on the surface of metal materials. There are many
unique advantages as are listed below:
1. Universal Materials Application
Comparing with the plasma nitriding technology which can be only applied for the
gas nonmetallic element, the Xu-Tec process can be applied with all chemical
elements, including solid alloy elements and gaseous nonmetallic elements for
plasma surface alloying. This technology has produced numerous surface alloys
with high hard, wear-resistant and corrosion-resistant on the surfaces of steels,
titanium alloys, intermetallic compounds and other materials. In addition, gradient
ceramics layers can be formed on the surface of the metal material. It can also form
a metal layer on the surface of the ceramic substrate, and realize the welding
between the metal and the ceramic.
2. Process Flexibility and Versatility
Since the Xu-Tec process was invented in 1980, it has been demonstrated to be one
of the most advanced surface alloying technologies with technical flexibility and
application versatility. Since powder metallurgy alloys can be used to make the
source material target, the composition of surface alloys is almost unrestricted. The
concentration of the alloying element in the surface alloy can be varied in a wide
range from a few percents up to 95%. The depth of the surface alloy can be formed
from a few micron-meters to a few hundred micron-meters.
3. Conserve Natural Resource
Through the Xu-Tec process, a thin surface alloy layer is built up on the surface of
working-piece, then to be used as a whole bulk replacement with special alloy
functions. This is a big material saving. The surface alloy layer thickness only about
0.1–1% of the thickness of the matrix working-piece, and its alloy elements con-
sume very little, just about 1% of the whole working-piece. By using this tech-
nology for material surface modification, it can save a lot of precious alloys
resources.
4. Zero pollution
The Xu-Tec technology is a typical physical process. The entire process of the
technology includes the vacuum, glow discharge, ion bombardment, deposition,
diffusion, etc. No chemical pollution would be generated during this process, thus it
is a typical environment-friendly technology.
5. Energy Saving
Diffusion rate of metal element of this technology is about 1–3 times faster than that
of traditional solid, liquid and gas surface alloying. The equipment has no tradi-
tional heat treatment furnace insulation materials and components. Heating of the
working-piece is directly applied by plasma on the local surface. So the plasma
surface metallurgy technology can save energy, about 30%.
6. Excellent Interface Bonding

Composition of the alloyed layer gradually changes in the depth direction of the
working-piece. There exist no distinct boundary between the surface alloy and the
matrix. And the risk of interface delamination is greatly reduced and/or eliminated.
7. Easy Scaling up for Large Area
According to the characteristic of glow discharge, the area of glow can be enlarged
with the increase of the area of cathode. Theoretically, the area of the glow dis-
charge is basically unlimited. Today, we have reached the surface alloying area of
6 m2.
4.10 Requirements for Operators
Double glow plasma surface alloying technology involves many aspects of tech-
nical operations relating to vacuum system, glow discharge, arc discharge, DC
adjustable pulse power supply, gap protection, and a series of complex technical
problems. Therefore, it is required to have all operators to understand the vacuum
and glow discharge knowledge, especially understand the possible change from
glow discharge to arc discharge, and know the possible factors and elimination
methods of arc discharge. They all need to carry out special study and training.
4.11 Xu-Tec Process in USA
During September 1981 to August 1983, Zhong Xu, as a visit scholar of China, was
conducting research at the University of South Carolina in the USA. He joined a
high voltage technology research team led by Professor James Thompson working
on a project related to the glow discharge. Xu’s research project which was pursued
earlier in China was introduced to the team in the USA. Upon the encouragement
and recognition from Professor Thompson and financial support from Dr. Roland
Lau, a Chinese-American investor, Xu and Lau applied for a USA patent for double
glow plasma surface alloying technology in 1982. This patent was formally granted
in May, 1985. This is the first U.S. patent granted to a Chinese scholar (Zhong Xu)
from the mainland as the inventor in the United States.
This technology, in USA, was quickly referred as the “Xu-Tec Process”. On July
24, 1989, an article entitled “A BREAKTHROUGH IN MAKING METAL
TOUGHER” was reported in the famous US magazine “Business Week”. The
article pointed out: “the so-called Xu-Tec process can create a stainless steel layer
on low-cost carbon steel. It can also make high-strength surfaces by using metals
such as molybdenum or tungsten.” On August 6, 1989, US newspaper “THE
STATE” published the article “local firm marketing technology—Xu-Loy system
4.11 Xu-Tec Process in USA 59
creates a metal alloy on surface.” These newspapers reported the results of professor
Xu and his invention of double glow plasma surface alloying technology.
With the solid support in Professor Thompson’s lab, Xu continued his devel-
opment work on this technology. In 1990, the Xu-Tec Process was granted a
research funding support in USA, “Energy Related Invention Program” (Contract
Number: DE-FG01-92CE15503, 1990) sponsored by U.S. Department of Energy
and from the “Small Business Innovation Research Program” (Funding Number:
F08635-90-C-0366, 1991) by the U.S. Department of Defense.
In addition, the state of South Carolina contributed $300,000 in research and
development funding. Dr. Lau and Xu together founded Plaur Company in USA
and established a laboratory in the science city of Philadelphia.
The research goal of the US Department of Energy project was to form a nickel
based alloy on the surface of carbon steel and to explore applications. Using Inconel
625 alloy as the source material, a surface alloy layer successfully formed on the
carbon steel surface with similar composition and characteristics to the Inconel 625
alloy. The objective of the US Defense Department’s research project was to form a
tantalum alloy layer on the surface of alloy steel and to explore applications. The
two projects were completed in early 1993.
Since then, Professor Thompson has shown great interest in the development of
the Xu-Tec process. As Dean of the College of Engineering of the University of
Missouri in the United States, Professor Thompson has repeatedly invited Professor
Xu to visit the University of Missouri. Xu delivered seminars and was invited to
talk at the University of Missouri, 3 M Research Center, Boeing Company and
Southwest Research Institute in the USA.
4.12 Xu-Tec Process in China
The double glow plasma surface alloying technology was applied an invention
patent in the USA in 1982 by Professor Xu, as the scholar from the mainland of
China for the first time. A reporter from China newspaper “Guangming Daily”
made a special interview with Xu in Columbia of South Carolina, USA. On January
15, 1983, Guangming Daily published an interview report in the front page, titled as
“The Central Leadership Instructs the Establishment of Patent Law as soon as
possible—An important invention in our country delay patent application”. This
made a big push to establish the patent system in China.
The Xu-Tec process has attracted great attention in China. Under the support of
Mei Liu, Dean of Taiyuan University of Technology, in the end of 1983, “Research
Institute of Surface Engineering” was formally founded by Professor Xu, focusing
on science research and technology development of double glow plasma surface
alloying technique.
Initially, carbon steel plates and handsaw blades were chosen for the industry
application demonstrations. In 1986, the surface of carbon steel plate in a size of
0.50 1.00 m has been treated successfully with nickel–chromium alloy for
anti-corrosion and hardness enhancement. A high-speed steel layer has been formed
in low-carbon handsaw blade teethers for anti-wear and service lifetime extension.
At the same time, we also developed an industrial-scale furnace which is able to
process large plates or 10,000 handsaw blades at once. In 1992 this technology won
China’s National Invention Award—Second Class.
The State Science and Technology Commission of China identified the double
glow plasma technology as one of “key” technologies in National 863 projects in
1994. Under the support of the 863-plan founding, we established a production line
with an annual output of 800,000 plasma surface metallurgical HSS handsaw blade.
The acceptance evaluation meeting for the project, held on February 1996 by the
State Science and Technology Commission, highly appraise the progress made in
this project and pointed out that double glow plasma surface alloying technology is
a novel plasma surface engineering technology invented in China, with merits of
innovative, advanced and practical. The saw cutting performance for the production
treated handsaw blade has over-reached the international standard for bi-metallic
high-speed steel hack saw blades. This technology could save resources and reduce
energy consumption, but also can greatly reduce the production cost. The detail
technical information will be introduced in Chap. 12 in this book.
Since 1995, we have been engaging in the study of titanium and titanium alloy
surface alloying. The surface alloying of TiAl intermetallic compound, copper and
copper alloy have been carried out. In addition, we also use this technology to
produce gradient ceramic material on the surface of steel material. It is also formed
on the surfaces of tungsten, molybdenum and zirconium with high hardness, wear
resistance and high temperature oxidation resistance. In 2004, colloid mills from
Beijing general machine factory were successful treated in this system for surface
hardness enhancement. The service lifetime of treated colloid mills is increased for
five times.
In the late 1990s, Xu-Tec had been entered in Taiwan. Professor Xu was invited
to give seminars at Taiwan University of Science and Technology, Taiwan Huaxin
Lihua Company, Taiwan Industrial Research Institute, National Cheng Kung
University. In 1999 he carried out cooperative research in the double glow tech-
nology, with the Huaxin Lihua company funding, Taiyuan University of
Technology, and the University of Science and Technology of Taiwan.
4.13 Summary and Outlook
This chapter had introduced some of the most important and basics of the Xu-Tec
process, including the basic principle and the surface alloy forming mechanism,
process configuration and process parameters, discharge mode and existing arc
problems, and so on.
In summary, our experiment results have demonstrated that countless types of
surface alloys could be produced by the Xu-Tec process, including nickel-base
alloys and high-speed steels (HSS) on the surface of carbon steels. Plasma surface
4.13 Summary and Outlook 61
metallurgy HSS has been accounted as the third generation of HSS, in addition to
the chemical metallurgy HSS (the first generation) and the powder metallurgy HSS
(the second generation of HSS). Various alloys such as Ti–Mo, Ti–Nb, Ti–Cu, Ti–
Cr, and Ni–Cr–Mo–Nb alloys have been formed on the surfaces of titanium and
titanium alloys. Many alloying layers with high hardness and wear resistant are
produced on the surface of TiAl and Ti2AlNb intermetallic compounds. A gradient
ceramic layer can be produced on the surfaces of metals. Metal layers can also be
prepared on the surfaces of ceramics. We are going to introduce those developments
and results in the following chapters.
In addition to materials resource and energy saving, the entire process is a
physical process without any pollution. As commercial enterprises are facing
increased pressure from the government and social responsibility of “clean up”, the
environment protection and industrial pollution reduction, the Xu-Tec process will
become more and more attractive.
The plasma surface metallurgy technology is an interdisciplinary technique,
involving materials science, surface physics and surface chemistry, vacuum and gas
discharge, low-temperature plasma, phase transformation, mechanical design and
computer control etc. The mechanisms and detailed physical image of this tech-
nique is still not fully understood due to the complexity of the plasma environment
and particle interaction. A series of fundamental issues are still unresolved, such as
precise control of surface alloy composition, solid alloying element transferring
process, diffusion under ion bombardment, characteristics, stability of the plasma,
etc. The solution to these challenging problems would further release the potential
power of this technology.
We confidently believe that as the double glow technology becomes more
mature and completed, the technology will have broad application prospects in
machinery manufacturing, chemical, marine, petroleum, energy, aviation and
aerospace, and other industrial fields.
References
1. Xu Z (1981) Research on the phenomena and characteristics of double layer glow discharge in
ion nitriding equipment. J Taiyuan Inst Technol 1:76–89
2. Xu Z (1982) Metal ion source for metallic surface metallurgy. In: 10th international
symposium on discharge and electrical insulation in vacuum, Columbia, South Carolina,
USA, 25–28 Oct 1982, pp 368–374
3. Xu Z (1985–1989) Method and apparatus for introducing normally solid materials into
substrate surface, 1. US patent 4520268, May 28, 1985. 2. US patent 4731539, March 15,
1988. 3. Gt. Britain patent 2150602, May 24, 1984. 4. Canada patent 1212486, Oct. 7 1986. 5.
Australia patent 580734, May 23, 1989. 6. Sweden patent 8500364-8, March 16, 1989. 7.
Japanese patent 1872-305
4. Xu Z (1997) Surface alloying simplified. Adv Mater Process 152(6):33–35
5. Xu Z, Wang ZM (1979) Research on plasma Ti–N–C co-diffusion alloying. Weapon Technol
1:13–15
6. Xu Z (1982) Double layer metallic cementation. Trans Metal Heat Treat 3(1):71–83
7. Li CJ, Xu Z (1987) Diffusion mechanism of ion bombardment. Surf Eng 3(4):310–312

8. Xu Z (2008) Plasma surface metallurgy. China Science Press, Beijing, pp 79–98
9. He ZY (1990) A study on the optimum process parameters of double glow plasma
nickel-chromizing. Trans Met Heat Treat 3:64–73
10. Braithwaite N, St J (2000) Introduction to gas discharges. Plasma Sour Sci Technol 9(4):
307–517
11. He ZY, Zhao JX, Gao Y (1999) Study on absorption ratio of alloy elements in plasma Ni–Cr
alloying by double glow plasma process. J Chin Soc Corr Prot 19:345–350
12. Wu HY, Zhang PZ (2009) The role of process parameters in plasma surface chromising of
Ti2AlNb-based alloys. Appl Surf Sci 256:1333–1340
13. Wu HY (2008) Research on plasma surface alloying and the tribological behavior of
Ti2AlNb-based alloys. Nanjing University of Aeronautics and Astronautics, Nanjing
14. Fick A (1855) Uber diffusion. Poggendorff’s Annalen der Physik und Chemie 94:59
15. Lieberman A, Lichtenberg J (1994) Principle of plasma discharge and materials processing.
Wiley, New York, p 462
Chapter 5
Physical Basis of Plasma Surface
Metallurgy
Abstract The plasma surface metallurgy is a new discipline field in materials

science and engineering. The newly developed surface metallurgy technology,
Double Glow Plasma Surface Metallurgy Technology, or the Xu-Tec process,
applies a series of physical processes, such as vacuum, gas discharge,
low-temperature plasma, ion sputtering, surface adsorption, and atomic diffusion, to
realize a surface alloying layer into the surface of the substrate matrix. This chapter
introduces some basic knowledge and physics about the double glow discharge and
the processing characteristics as well. Some preliminary discussion is presented on
the related physical fundamental issues that involved in the Xu-Tec process.
5.1 Glow Discharge and its Discharge Characteristics
The double glow discharge process is a complex surface metallurgy technology,

involving a series of physical phenomena, such as vacuum, gas discharge,
low-temperature plasma, sputtering, adsorption, and diffusion, and realizes surface
alloying as a new surface alloying technology. The Xu-Tec process, a newly
developing surface metallurgy technology, adopts positive ion bombardment to
source material within the plasma formed by double glow discharge under a vac-
uum condition, resulting in the alloying element vapor by sputtering from the
source electrode. Subsequently, the sputtered-off metal atoms and ions deposit on
the substrate surface, and diffuse into the subsurface of the working-piece to form a
pre-designed modified surface alloying layer.
In this chapter, we are going to introduce some basic knowledge about glow
discharge and its characteristics, mainly focusing on the gas discharge and gener-
ation of plasma, ion bombardment and sputtering, transport of alloying elements in
glow discharge space, reactions between particles and surface of substrate,
adsorption and diffusion of alloying elements into the surface of the workpiece.
Some preliminary discussion is presented on the related physical fundamental
issues that involved in the Xu-Tec process.
DOI 10.1007/978-981-10-5724-3_5
64 5 Physical Basis of Plasma Surface Metallurgy
5.1.1 Gas Discharge
Gases are usually made of neutral diatom molecules or inert atoms, and normally
nonconductive. However, the electrical conductivity of the gas could change dra-
matically in a high electrical field where the gas ionization is taking place.
Ionization is the physical process of ion–electron generation, by which an atom or a
molecule acquires a negative or positive charge to become an ion. Driving by an
electric field, ions–electrons would be separated, moving toward anode or cathode
electrode, respectively; thus an electric conduction current is formed. Gas electric
discharge occurs when electric current flows through a gaseous medium due to
ionization of the gas. Depending on several factors (e.g., the gaseous medium type
and the electric field intensity), the discharge may radiate a different visible light.
High-temperature heating, photonic irradiation (ultraviolet rays, X-rays), or
radioactive rays can trigger gas ionization. These factors are referred to as the
ionization agent. This gas conduction maintained by an ionizing agent is called
excitation conduction or non-self-electrical conduction. In the presence of the
electric field, when the voltage is increased to a certain value, the conduction
current increases sharply in gas. At this condition, the conductive can be maintained
even if removed from the ionization agent. This situation is called self-electrical
conduction or self-excitation discharge. The transition process from excitation
conduction to self-electrical conduction is often referred to as the gas breakdown or
the gas discharge ignition. The corresponding voltage is called breakdown voltage.
In the breakdown voltage condition, there are still a lot of charged particles (ions
and electrons) in conductive to sustain the discharge after removing the ionization
agent.
The characteristics of gas self-electrical discharge are related to its gaseous
medium type and pressure, electrode material and shape, temperature, distance, and
some various physical parameters. Gas discharge often associates with sound,
lighting, and other phenomena [1, 2].
5.1.2 Glow Discharge Process
Glow discharge is facilitated by electrons striking the gas atoms and ionization. The
simplest type of glow discharge is a direct-current glow discharge at low pressure
(0.1–10 torr; about 1/10000–1/100 of atmospheric pressure). An electric potential
of several hundred volts is applied between the two electrodes. A small fraction of
the population of atoms in the cell is initially ionized through random processes
(e.g., thermal collisions between atoms or molecules). Driven by electric field, ions
move toward the cathode and electrons move toward the anode. In this way, ions
and electrons collide with other atoms, ionizing them. As long as the potential is
maintained, a population of ions and electrons remains.
5.1 Glow Discharge and its Discharge Characteristics 65
Fig. 5.1 a A schematic of the setup and b Volt–Ampere characteristic curve for gas discharge [4]
Figure 5.1a shows the principle diagram of gas discharge experiment

setup. A pair of a cathode and an anode is disposed in the vacuum container that
filled with a gas at a certain partial pressure, and biased with a DC power supply
equipped outside. Figure 5.1b shows the volt–ampere characteristic curve of gas
discharge. The OABC segment is non-self-electrical conduction area where gas
discharge cannot be maintained by itself and must have an external electric field to
maintain the gas discharge. At these points when the supply voltage is very lower,
there is not any visible current between the cathode and anode. When the biasing
voltage is increased to Us at the point C, a large current is dramatically increased
and followed with a large voltage drop, when a glow discharge is produced on the
surface of the cathode. After the point D, the current continuously increases while
the voltage across the electrodes is almost current independent. Even increasing the
surface glow area of the cathode, the voltage between the two electrodes remains
unchanged. Meanwhile, the area of the electrodes covered by the glow discharge is
proportional to the current, until reaching the point E. Subsequently, at a higher
current the normal glow turns into abnormal glow, the voltage gradually increases,
and the glow discharge covers more and more of the surface of the electrodes. After
the point F, the current increases sharply, while the voltage between the two
electrodes drops. At this point, the glow extinguishes and a strong arc discharge
phenomenon appears on the cathode surface [3].
To form the glow discharge, the mean free path of the electrons has to be
reasonably long, but shorter than the distance between the electrodes. Glow dis-
charges therefore do not readily occur at both too low and too high gas pressures.
The mean free path of electrons and many other properties of gas discharge are a
function of the E/N ratio, where E is the electric field defined by the bias voltage
and electrode distance, and N is the concentration of neutral particles defined by the
partial pressure. Increasing the electric intensity E by some factor q has the same
consequences as lowering gas density N by factor q.
The Us is the ignition voltage or the breakdown voltage for the glow discharge,
which depends nonlinearly on the product of gas pressure and electrode distance
according to Paschen’s law. As shown in Fig. 5.2, for the product of a certain
Fig. 5.2 Paschen curve— the

breakdown voltage for the
glow discharge on the product
of gas pressure and electrode
distance [4]
pressure and distance value, there is the lowest breakdown voltage. The increase of
strike voltage for shorter electrode distances is related to the long mean free path of
the electrons in comparison with the electrode distance.
The CE segment in Fig. 5.1 is a normal glow discharge region. In this segment,
the glowing area is enlarged with increasing the current, while the surface current
density of the cathode maintains as a constant. The EF segment is abnormal glow
discharge zone. In this segment, the surface of the cathode is completely covered by
the glow, so that an extra current contributes to electrode heating evenly. It is noted
here that the ion nitriding process is carried out in this segment, where the
parameters of the plasma nitriding process can be controlled by changing the
voltage drop and the cathode surface current density.
At the point F, both the current and the voltage are very high. The cathode under
ion bombardment could be heated to very high temperature and produce significant
thermal electron emission or metal gasification. The current in the area is surge in
equivalent to a short circuit, while the bipolar voltage drops to a few tens of volts or
less. The area after the point F in Fig. 5.1 is called the arc discharge zone. At this
moment, the glow goes out and arc discharge is taking place in a small area on the
cathode surface. Severe arc discharge sometimes could lead to melting and physical
damage to the cathode electrode.
5.1.3 Stratification Phenomenon
Gas glow discharge normally gives some visible light emissions. It has been
observed that the distribution of the glow between the electrodes is not uniform. As
shown in Fig. 2.2 of Chap. 2 and represented in Fig. 5.3, several distinct lighting
regions may be present in a glow discharge. Regions described as “glows” emit
significant light; regions labeled as “dark spaces” do not. As the discharge becomes
more extended (i.e., stretched horizontally in the geometry of the figures), the
positive column may become striated. That is, alternating dark and bright regions
may form. Compressing the discharge horizontally will result in fewer regions. The
positive column will be compressed while the negative glow will remain the same
size, and, with small enough gaps, the positive column will disappear altogether.
Fig. 5.3 Crookes gas discharge tube illustrating the different glowing regions and a diagram with
names. https://en.wikipedia.org/wiki/glow_discharge
In an analytical glow discharge, the discharge is primarily a negative glow with

dark regions shown above and below. From the cathode to the anode, the glow can
be divided into eight regions:
(1) Aston dark region
(2) Cathode glow region
(3) Cathode dark region
(4) Negative glow region
(5) Faraday dark space
(6) Positive column region
(7) Anode glow space region
(8) Anode dark space region.
The first four zones, including Aston dark, cathode glow, cathode dark, and
negative glow, are important region for maintaining gas discharge. The total dis-
charge width (Dk) of these four zones is called as the width of cathode potential
drop region. It has been observed that in order to maintain the glow discharge, the
electrode distance has to satisfy the condition of d > Dk. When the condition of
(d > Dk) is satisfied, the cathode part of the discharge (the first five zones) is
unchanged. In other words, with the shortening of the distance d, the anode column
region is gradually shortened. When the condition of d < Dk is reached, the dis-
charge would be distinguished immediately.
In the glow discharge, the Dk is not only related to the pressure, but also related
to the current density. When the gas pressure is higher, the Dk is suppressed and the
Glow layer is thinner. When the gas pressure is reduced, the Dk will be expanded
wider, and the current density will be reduced [4].
5.1.4 Glow Discharge Characteristics

(1) The color of the glow discharge is different upon the different gaseous medi-
ums. The glow of argon is pale blue; the nitrogen is purple; the ammonia is blue
purple. In the process of plasma surface metallurgy, the purity of the gas
medium can be estimated roughly according to the color of the glow emission.
(2) Glow discharge is the gas discharge at high voltage and low current. For
example, in the process of double glow plasma surface metallurgy, the glow
discharge voltage is 500–1100 V, and the current density is 0.5–15 mA/cm2.
(3) The gas pressure of glow discharge is relatively low in order to maintain the
electron free path length in a qualified range. For example, the gas pressure is
1.33 l02–1.33 103 Pa in ion nitriding. In the double glow process, the gas
pressure is relatively lower at 1–100 Pa, under the medium vacuum condition
(see Table 5.1).
(4) The glow discharge process is mainly maintained by the secondary electron
emission of the electron emission process from the cathode.
(5) Diffraction. The diffraction phenomenon is shown in Fig. 5.4 and conducive to
the uniform surface treatment of the working-piece in a complex shape. It is a
not a line of sight process and very important character for complex shape
Table 5.1 Pressure ranges of Atmospheric pressure 1.013 105

vacuum (Pa)
Low vacuum 1 105 to 3 103
Medium vacuum 3 103 to 1 10−1
High vacuum 1 10−1 to 1 10−7
Ultra-high vacuum 1 10−7 to 1 10−10
Extremely high vacuum <1 10−10
Perfect vacuum 0
Fig. 5.4 Schematic

illustration of diffraction of
glow discharge
processing in Double Glow Plasma Alloying Technology. With this feature, a

uniformity alloying layer can be made on the surface of large size and complex
shape in the double glow plasma surface alloying process [5].
5.2 Low-Temperature Plasma
5.2.1 Plasma and Its Generation
Plasma is often called the fourth state of matter after solid, liquids, and gases,
despite plasma typically being an ionized gas. Figure 5.5 represents four aggre-
gation states of matter. Plasma is an electrically neutral medium of unbound pos-
itive and negative particles (e.g., ions and free electrons), so that the overall charge
of plasma is roughly zero. Plasma has properties unlike those of the other states and
is distinct from these and other lower energy states of matter. Although it is closely
related to the gas phase that has no definite form or volume, it differs in a number of
ways, as some are listed in Table 5.2.
Plasma is the most abundant form of ordinary matter in the universe as 99% of
matter in the universe exists in the plasma state, such as stars, galaxies, nebulae and
lightning, the Aurora, ionosphere near the Earth, and so on. The sun itself is a hot
plasma ball of fire. There are also many artificial plasma types created by physical
methods through ionizing neutral particles.
Although there are several means to generate plasma, one principle is common
to all of them: there must be an energy input to produce and sustain it. In one case,
plasma could be generated when an electric field is applied across an electric
nonconductive material such as a dielectric gas or fluid. Under an electric field,
Solid Liquid Gas Plasma

Ice Water Steam Ionized Gas
H 2O H 2O H2O H2
H++H++2e-
Cold Warm Hot Hotter
T<0 0<T<100 T>100 T>100000
Molecules Molecules Molecules Ions and electrons

fixed in lattice Free to move Free to move, move independent,
Large spacing Large spacing
Fig. 5.5 Four states of matter

Table 5.2 Different ways of gas and plasma

Property Gas Plasma
Electrical Very low: Air is an excellent Usually very high: For many
conductivity insulator purposes, the conductivity of plasma
may be treated as infinite
Independently One: All gas particles behave in a Two or three: Electrons, ions,
acting species similar way, influenced by gravity protons, and neutrons can be
and by collisions with one another distinguished by the sign and value of
their charge so that they behave
independently in many circumstances
Velocity Maxwellian: Collisions usually lead Often non-Maxwellian: Collisional
distribution to a Maxwellian velocity distribution interactions are often weak in hot
of all gas particles plasmas and external forcing can
drive the plasma far from local
equilibrium and lead to a significant
population of unusually fast particles
Interactions Binary: Two-particle collisions are Collective: Waves, or organized
the rule, three-body collisions motion of plasma, are very important
extremely rare because the particles can interact at
long ranges through the electric and
magnetic forces
electric polarization is taking place. The bound electrons are pulled toward the
anode (positive electrode), while the cathode (negative electrode) pulls the posi-
tively charged nucleus. As the voltage increases, the current stresses the material
more beyond its dielectric strength limit into a stage of electrical breakdown, where
the material transforms from being an insulator into a conductor as it becomes
increasingly ionized. The underlying process is the Townsend avalanche, where
collisions between electrons and neutral gas atoms create more ions and electrons,
and the number of charged particles increases rapidly (in the millions only “after
about 20 successive sets of collisions”).
Here are the listed methods for plasma generation:
(1) Electron collision method. There are natural electrons exist in low-pressure gas.
Under the action of external electric field, these electrons would get accelerated
and have enough energy to collide with the neutral particles and generate
ionization. Electrons produced by ionization would accelerate in the electric
field, collide with other neutral particles, generate avalanche ionization, and
generate plasma. Gas discharge plasma is in this category. This method is used
in “technological plasma” for materials processes, such as plasma-assisted PVD
or CVD for thin film deposition, the material surface treatment, such as
nitriding, carburizing and boronizing, and the Xu-Tec surface alloying process
as well.
(2) Particle thermal motion method. Heating the neutral gas to a high-temperature
intensifies the thermal motion of molecules and atoms to generate collision,
then dissociate into ions and electrons, further into the plasma state.
5.2 Low-Temperature Plasma 71
(3) Using electromagnetic wave energy such as light, X-ray, and c-ray to ionize
gases to generate plasma.
(4) Using high-energy particles such as nuclear fusion to generate plasma.
Plasma temperature is one of the important physical parameters defining features
of plasma. It is a measure of the thermal kinetic energy per ion, in Kelvins (k) or
electronvolts (eV). High temperatures are usually needed to sustain ionization. At
low temperatures, ions and electrons tend to recombine into the bound states—
atoms, and the plasma will eventually become a gas.
Based on the relative temperatures of the electrons, ions, and neutrals, plasmas
are classified as “thermal” or “non-thermal”. Thermal plasmas have electrons and
ions at the same temperature, i.e., they are in thermal equilibrium with each other.
Non-thermal plasmas on the other hand have the ions and neutrals at a much lower
temperature (sometimes room temperature), whereas electrons are much “hotter”
(Te Ti).
A plasma is sometimes referred to as being “hot” if it is nearly fully ionized, or
“cold” if only a small fraction (for example 1%) of the gas molecules are ionized.
Even in the “cold” plasma, the electron temperature is still high typically in several
thousand degrees of Kelvins. Plasmas utilized in “plasma technology” are usually
cold plasmas in the sense that only a small fraction of the gas molecules are ionized.
Plasma utilized in the double glow discharge plasma alloying process is falling into
the category of low-temperature plasma.
5.2.2 Characteristics of Double Glow Discharge Plasma
The plasma parameter distribution in the double glow discharge zone has been
diagnosed by Langmuir probe. The results indicate that the plasma behavior
between the double cathodes cannot be considered as a simple addition of two glow
discharge plasmas, and there may be enhanced discharge between the double glow
discharges. Due to the continuous changes of plasma density in a geometric space
required, therefore, there is an edge effect of a sharp decline in the plasma density in
a border area.
Experimental results also show that the higher the cathode voltage is, the higher
the plasma density in the center region would be, so that the larger the ratio of the
background plasma density would be. Figure 5.6 shows that the plasma density
changes with the cathode voltage Vc, when the source voltage Vs = 800 V is fixed.
When the cathode voltage is less than 400 V, plasma density increases linearly with
the cathode voltage increasing. When the cathode voltage is at 400 V, the plasma
density has a first step increase, indicating that the enhanced power is produced
between two cathodes. When the cathode voltage is over 400 V, plasma density
increases exponentially along the cathode voltage which continually increases.
Fig. 5.6 Plasma density

changes with the cathode
voltage
Fig. 5.7 Plasma density 8

changes with gas pressure
7
Plasma Density / 1011 cm-3
0
40 60 80 100 120
Gas Pressure / Pa
A change of the plasma density with gas pressure is shown in Fig. 5.7. It is
shown that the work pressure should be controlled in the best range to strengthen
the enhanced discharge. It is found that the double glow discharge within the
40–100 Pa gas pressure range is abnormal glow discharge, between the normal
glow discharge and arc discharge. As shown in Fig. 5.8, in the voltage range of
700–1000 V, electron temperature increases with the cathode voltage, also with the
increase of gas pressure, and consists with what shown in Figs. 5.7 and 5.8. The
value of electron temperature varies between 1 and 15 eV.
5.3 Ion Bombardment and Sputtering 73
Fig. 5.8 Electron

14
temperature changes with the 80Pa
Electron Temperature / eV
cathode voltage 40Pa
12
10
0
500 600 700 800 900 1000
Cathode Voltage Vc / V
5.3 Ion Bombardment and Sputtering
Sputtering is a physical process whereby particles are ejected from a solid target
material due to ion bombardment of the target by energetic particles, particularly
gas ions. This process can lead to significant erosion of materials at the surface, thus
it can be used for surface cleaning. More often, it is commonly utilized for evap-
orating solid materials for thin film deposition.
Physical sputtering is driven by momentum exchange between the ions and
atoms in the target materials due to collisions. The incident ions set off collision
cascades in the target. When such cascades recoil and reach the target surface with
its kinetic energy greater than the surface binding energy, an atom would be ejected,
known as sputtering. The primary particles or ions for the sputtering process can be
supplied in a number of ways, for example, by an ion source, an accelerator or
plasma.
In the Xu-tec process, ions from glow discharge plasma are utilized for sput-
tering the source target of alloy elements. Therefore, it is of great significance to
study the sputtering regularity of the source electrode.
5.3.1 General Description of Sputtering Process
The sputtering process can be quantitatively described by the physical quantity of

sputtering yield Y; it is defined as the average number of atoms ejected from the
target per incident ion, that is,
Fig. 5.9 Diagram of the 3.5

sputtering yield curve, and
changes of sputtering yield 3.0
with incident ion energy [4]
Sputtering Yield
2.5
2.0
1.5
1.0
0.5
0.0
102 103 104 105 106 107
Energy of incident ion / eV
Ns
Y¼ ;
Ni
where Ns is the number of sputtered atoms and Ni is the number of incident

particles. Based on mechanics of two-body interaction, the sputtering yield depends
on the ion incident angle, the energy of the ion, the masses of the ion and target
atoms, and the surface binding energy of atoms in the target.
Figure 5.9 shows a simple diagram of the changes of sputtering yield Y with the
incident ion energy E, referred to as the sputtering yield curve. From this curve, we
can see that there is a sputtering threshold, generally at 20–100 eV. The sputtering
yield can reach a maximum value when the energy of the incident ion is 1–10 keV.
When the energy of the incident ion is more than 10 keV, the sputtering yield starts
to decrease with the increase of the energy of the incident ion.
In most of ion-beam sputtering experiments, the incident energy of ions is
relatively low. At this energy level, it is mainly elastic collisions between ions and
nuclei, especially the metal target material. This kind of sputtering is also known as
knock-on-sputtering. There are three types of knock-on-sputtering:
(1) Single knock-on-sputtering. In the course of the ion–target collision, the
energy of the recoil atom is relatively low to be directly sputtered out, but with
no enough energy to produce new recoil atoms further. Single
knock-on-sputtering is in the range of tens of electron volts of the incident ion
energy, and the ion energy is lost completely in one or several collisions.
(2) Linear collision cascade sputtering. When the energy of the initial recoil atom
is relatively high, it can further collide with the other stationary atoms, resulting
in a series of new cascade motions. For the linear collision cascade, the energy
range of the incident ions is generally in keV–MeV, and the cascade motion is
mainly generated along the path of the ion.
(3) Thermal pinning sputtering. The density of the recoil atom is very high, so
that most of the atoms in a certain area are in motion. Pinning sputtering is
usually caused by medium energy heavy ion bombardment of solid surfaces.
5.3 Ion Bombardment and Sputtering 75
For the single knock-on-sputtering, the number of recoil atoms is proportional to

the collision cross section; while in the linear collision cascade, the number of recoil
atoms is proportional to the ion energy deposited in the unit path, namely, the
nuclear stopping power. For the thermal pinning sputtering, the number of recoil
atoms is proportional to the energy of the ion deposited in the unit volume. The
sputtering yield is directly proportional to the nuclear stopping power, so it has a
tendency to change with the energy of the incident ion: when the energy is low, the
sputtering yield is almost linearly increased with the change of the ion energy, and
then gradually increases slowly, and after reaching the maximum, it decreases with
the increase of the energy of the incident ions.
5.3.2 Preferential Sputtering
As mentioned earlier, the sputtering yield is related to the elemental mass in the
target and their surface binding energy. The heavier the elemental weight is, the
lower the sputtering yield would be. The metal elements in the target with a high
sputtering yield include Au, Cu, Cd, and Ag; while smaller ones are with Bi, Ni, Sb,
and Sn; even very smaller with heavy elements Pt, Ta, W, Zr, etc. Preferential
sputtering can occur when the target consists of multielements, when the energy
transfer through ion bombardment is more efficient to one of the target elements
than to another. This preferential sputtering would lead to elements with a low
sputtering yield “enrich” in the surface and cause a composition unbalance in the
deposited film with a multicomponent target, thus tailoring that the target compo-
sition is needed to compensate this issue.
Sputtering only takes place from a few atomic layers near the surface. Therefore,
the depth of surface composition unbalanced due to preferential sputtering would be
only a few atoms thick. However, from the experimental observation, the alloying
layer depth of the surface composition variation due to the preferential sputtering
can be comparable with the range of the ions. This would be caused by the recoil of
the atom, the mixing of the cascade, and the diffusion of atoms.
5.3.3 Alloy Sputtering
In the double glow plasma surface alloying process, the experimental results have
shown that the chemical composition of the deposited film sputtered from an alloy
target is very close to that of the target. This suggests that sputtering is not governed
by the thermal process, but by a momentum transfer process. However, on the
substrate surface, when the temperature is so high, the surface composition of the
alloy target would change due to the thermal diffusion. As a result, the deposited
films result in slightly different chemical compositions. At even higher substrate
Concentration of alloying elements / wt%

Fig. 5.10 Composition in
Ni–Cr-alloyed surface of 80
1020 steel
Ni
60 Cr
40
20
0 10 20 30 40 50 60 70 80
Distance from the surface / µm
temperature, the resulting films also show different chemical compositions because
of the re-evaporation of the deposited films.
It suggests that the sputtered film should have the same composition as the target
in the steady state when the solid-state diffusion in the target is neglected. At
ordinary temperature (a few hundred degrees centigrade), such diffusion is unim-
portant. Figure 5.10 shows the composition depth distribution of a Ni–Cr alloying
layer deposited by the double glow plasma surface alloying process. The source
cathode (target) is made by Ni80Cr20 alloy. It is clearly showed that composition
near the surface is close to the target, and with Cr concentration is slightly lower
than 20%.
5.4 Propagation of Glow Discharges
As introduced earlier, the double glow discharge plasma involves two sets of glow
discharge: one set is at the source target surface and another one is at the substrate
cathode. Plasma is composed of not only ions and electrons from gas discharge, but
also with metal atoms sputtered from the source and produced in the collision. All
charged particles in the plasma will move intricately under the electric field. The
movement in the process is complex as it involves both the macro-particle transport
and the collision among the electron, metal ion, metal atom, and argon atom in
the micro-aspect. During the transition from the non-equilibrium state to the
quasi-balanced condition, there is one or more “flows” in the plasma, which make
the plasma undergo an irreversible process, known as “plasma propagation”. The
“flows” in the plasma include energy flux, mass flow, momentum current, velocity
flow, and so on.
During the alloying process, the spatial uniformity of plasma density will
increase with the action of the source voltage and cathode voltage as they are
parallel with each other. When the source is not parallel to the cathode,
5.4 Propagation of Glow Discharges 77
inhomogeneity of the plasma density increases accordingly. At the same time,

electron temperature and dispersion of the plasma potential rise up. With the
decrease of the distance between the source and the cathode, the plasma density
increases.
5.4.1 Ionization Degree and Mean Free Path
Ionization is the process by which an atom or a molecule losses one or more

electrons to form ions, often in conjunction with other chemical changes. Ionization
can result from the loss of an electron after collisions with other atoms, molecules,
and ions, or through the interaction with light.
For plasma to exist, ionization is necessary. The degree of ionization of a plasma
is the proportion of atoms that have lost or gained electrons, and is controlled
mostly by the temperature. The degree of ionization, a, is defined as
a = Ni/(Ni + N0),
where Ni is the number density of ions and N0 is the number density of neutral
atoms. The term “plasma density” usually refers to the “electron density”, that is,
the number of free electrons per unit volume. The electron density Ne is related to
this by the average charge state <Z> of the ions through Ne = <Z> Ni.
In physics, the mean free path (MFP) is the average distance traveled by a
moving particle (such as an atom, a molecule, an ion, or a photon) between suc-
cessive impacts (collisions) [6], which modify its direction or energy or other
particle properties. The magnitude of the MFP depends on the characteristics of the
system. An expression for the MFP is k = 1/nS, where k is the mean free path, n is
the number of target particles per unit volume, and S is the effective cross-sectional
area of collision. When the velocities of the identical particles have a Maxwell
distribution, the following relationship applies:
k ¼ pffiffi1ffi ;
2nS
with n = N/V = p/(kBT) (ideal gas law, kB is the Boltzmann constant) and
S (effective cross-sectional area for spherical particles with radius r), it may be
shown that the mean free path is
k ¼ pkffiffiBffi T :
4 2pr 2 p
Table 5.3 gives MFP values for atoms in air at different pressures at room
temperature. At a low vacuum, the MFP is at micrometer range, while at medium
vacuum, it is at a millimeter range where most gas discharge can take place.
Table 5.3 Mean free path for air at different pressures at room temperature
Vacuum range Pressure Pressure Molecules Mean free
hPa (mbar) mmHg (Torr) #/ cm3 path
Ambient pressure 1013 759.8 2.7 1019 68 nm
Low vacuum 300–1 225–7.501 10−1 1019–1016 0.1–100 lm
Medium vacuum 1–10−3 7.501 10−1– 1016–1013 0.1–100 mm
7.501 10−4
High vacuum 10−3 – 7.501 10−4– 1013–109 10 cm–1 km
10−7 7.501 10−8
Ultra-high vacuum 10−7 – 7.501 10−8– 109–104 1 –105 km
10−12 7.501 10−13
Extremely high <10−12 <7.501 10−13 <104 >105 km
vacuum
According to the He Zhiyong’ s calculation [7], when temperature T is 1273 k

and air pressure p is 40 Pa (in the medium vacuum range), the mean free path of Ar
is as follows:
k ¼ pkT 1:38 1023 1273

ffiffiffi ¼ pffiffiffi
4 2pr 2 p 4 2 3:14 ð1:54 1010 Þ2 40
¼ 1:04 103 m
It is seen that, in this condition, the MFP is at about 1 mm, much larger than
atomic radius and ionic radius. So it means the plasma gas is rare.
5.4.2 Propagation of Plasma in Double Glow Discharges
In the double glow surface alloying process, the plasma concentration, velocity, and
the temperature vary in different regions. The nonuniformity of the plasma is
eliminated by the transportation, that is, plasma diffusion. The process should be
treated as a special case of motion in general. The particles not only collide with
each other eliminating the uneven but also move up to the cathode as the
macro-stance by an electric field. After a long time, the plasma is a process of
dynamic equilibrium in general [8].
To provide a high concentration of metal plasma around the working-piece, that
is, to maintain a high bias potential and high temperature, a heat preservation cover
(a metal shield) is applied to the source and the cathode. In this way, the stability of
the plasma and the homogeneity of the temperature are guaranteed. But there is still
velocity gradient and density gradient around.
5.5 Diffusion Process Under Ion Bombardment 79
Fig. 5.11 Schematic illustration of vacancy generation by ion bombardment that supports the
quick diffusion path and stores large mass of alloying elements
Fig. 5.12 Experimental data

exponential fitting results of 100 Experimental
Chromium Concentration / wt%
Exp Fitted
Cr diffusion in ion bombarded
Steel-1020 [11] Equation: y = A1*exp(-x/t1) + y0
80
y0 2.7568 ? .74153
A1 176.63756 ? 7.66844
t1 5.059 ? .59567
60
40
20
0
0 10 20 30 40 50 60
Distance From Surface / µm
5.5 Diffusion Process Under Ion Bombardment
Double glow plasma surface metallurgy technique is the process that the sputtered
atoms adsorbed to the surface of the working-piece cathode and then diffuse into the
substrate, all driving by ion bombardment. One of its features is the infiltration
elements in the matrix diffuse fast. In 1979 [9], Xu Zhong first proposed the
diffusion mechanism that, under ion bombardment conditions, there forms a
defect-contained layer with a high concentration of vacancy at the surface of the
working-piece. Later, he further proposed that vacancies in surface would diffuse
inward and form a vacancy gradient and diffusion channel, as can be seen in
Fig. 5.11.
It has great scientific values to systematically study the various factors affecting
the diffusion and establish diffusion model to reveal the mechanism of diffusion
under ion bombardment conditions.
5.5.1 Diffusion Model
In the double glow plasma surface alloying process, metal atoms in the source
cathode are continuously sputtered off by ion bombardment and deposited onto the
surface, and then move by diffusion into the subsurface of the working-piece
substrate at an elevated temperature and certain vacancy concentration. Eventually,
the deposition rate and the diffusion rate reach a balance. At the final, a layer of
metal elements is deposited on the surface, with a modified alloying subsurface
layer formed through thermal-driven solid diffusion [10]. If we imagine the process
of diffusion, metallization is equivalent to a metal diffusion annealing process, and
the working-piece can be treated as a half of the infinitely long diffuser. The
ingredients at the end of the film away from the source keep the original concen-
tration, and cannot be affected by diffusion [11]. The concentration C change with
the distance x and time t can be described as

x
Cðx; tÞ ¼ Cs 1 erf pffiffiffiffiffi :
2 Dt
Taking TC11 chroming alloy as an example, the diffusion layer compositions

examined by EDS analysis are shown in Table 5.4. The content C was fitted by
C ¼ 2:7568 þ 176:63758 ex=5:059 :
As shown in Fig. 5.12, the simulation curve is well consistent with the test data.
Table 5.4 The distribution of Cr element in permeation layer

Distance from the surface(lm) Cr content Distance from the surface (lm) Cr content
(wt%) (wt%)
2.7649 98.0650 30.4831 5.6238
5.5417 80.9556 33.2499 5.2614
8.3144 33.0382 36.0331 4.8744
11.0888 10.6633 38.7913 4.5275
13.8623 8.9738 41.5663 3.6210
16.6210 8.0211 44.3500 2.2035
19.3923 7.4298 47.1169 1.4495
22.1693 6.9544 49.8935 1.7481
24.9349 6.5359 52.6615 0.9908
27.7229 6.0543 55.4453 0.4208
0
Table 5.5 Calculated ln½Cx ðx; tÞ x2 relationship
0 0
x2 ln½Cx ðx; tÞ x2 ln½Cx ðx; tÞ
0.644672 3.006400 929.2194 −2.472588
30.71044 2.457517 1105.556 −3.019495
69.12924 1.909444 1298.384 −3.569643
122.9615 1.361035 1504.765 −4.114850
192.1634 0.8128046 1727.757 −4.663376
276.2577 0.2674991 1966.922 −5.213623
376.0613 −0.2802967 2220.002 −5.760550
491.4779 −0.8292195 2489.362 −6.309394
621.7493 −1.375889 2773.233 −6.856537
768.5592 −1.926986 3074.181 −7.406804
Fig. 5.13 Relationship of 4

0
ln½Cx ðx; tÞ x2 [11]
2
0
ln(-C )
'
-2
-4
-6
-8
0 500 1000 1500 2000 2500 3000 3500

x2
Taking a derivative on the fitted curve function, we have
dC 176:63756 x
¼ e5:059 :
dx 5:059
By taking a log of the above function, the calculated data are shown in
Table 5.5. Using the data in Table 5.3 to draw a curve shown in Fig. 5.13, one can
see that, except for the test points close to x ¼ 0, the rest of the various points fall in
a straight line very well. This is because the cathode sputtering effect is stronger on
the top surface, while the cathode sputtering effect can be neglected at the sub-
surface. Removing several points close to x ¼ 0 and linear fit for the rest data, we
find the slope of the line is −0.00251 = −1/4Dt, with t = 7200 s. The calculated
diffusion coefficient is
Fig. 5.14 Depth distribution

of Cr in the layer [11]
D ¼ 1:383 102 lm2 s1 :
Substituting −1/4Dt = −0.00251 into the diffusion equation, one can notice that,
under the premise of a thin deposited layer existed on the surface and Cs ¼ 100%,
the diffusion concentration distributions of Cr elements in the matrix are obtained:
Cðx; tÞ ¼ 100 ð1 erf ð0:05xÞÞ:
As shown in Fig. 5.14, using semi-infinite diffusion model to calculate the

concentration, distribution curves are well coincident with the test results, except
for individual deviant points. This is associated with the precipitation of TiCr2
intermetallic in the layer under certain concentration.
5.5.2 Diffusion Mechanism

(1) Vacancy Mechanism
The metal substrate exists a balance vacancy concentration under a certain tem-
perature. The experimental results show that, in the process of the double glow ion
bombardment, each square centimeter surface will be bombarded by positive ions in
a magnitude of 1017/s. The average energy of positive ions is about 100–160 eV
when it reaches the surface of the work piece. According to relevant data, to knock
the atoms out a metal lattice position and form an isolated vacancy and interstitial,
the needed energy is about 25 eV. Hence, the surface would form a defect layer that
contains a large number of vacancies when it was bombarded by high-energy ions.
The concentration of vacancy in the defect layer is much higher than balance
concentration, and decreases with the depth, resulting in a high vacancy concen-
tration gradient [12].
The existence of vacancy concentration gradient makes the metal atom diffusion
under an inward force, so that the diffusion coefficient of double glow plasma
surface technology is much larger than ordinary metal infiltration.
From the angle of vacancy migration, the driving force of the vacancy diffusion
consists of two parts: vacancy formation energy and vacancy migration energy.
Under the condition of the ion bombardment, there would form a lot of vacancy,
and these vacancies migrate when it contains certain migration energy. Hence
vacancy migration is easier.
(2) Solute-vacancy Complex Mechanism
If the size of a solute atom is bigger than that of a solvent atom, or if they have a
higher valence, there will be mutual attraction between solute atoms and vacancies.
As the result, solute-vacancy pairs will be able to diffuse in the lattice.
The working-piece surface will be distorted after ion bombardment. To reduce
distortion energy, vacancies and solute atoms will form pairs. It was proposed the
vacancy complex diffusion coupling model in the substitutional solid solution: The
diffuse speed of substitutional solutes is far below vacancies in the crystal, and the
forming of the complex would accelerate solute atoms’ diffusion. Aust further
proposed the formation condition of complex as Eb > KT, where Eb is the binding
energy of a vacancy-solute pair. According to the experimental rule as well as
theoretical research, Zongsen Yu proposed the condition of substitutional solute
atom-vacancy’s diffusion as [13]
Eb [ H1 H0 þ KT ln 10;
where H1 is the activation energy of vacancies around the solute atoms and H0 is the
diffusion activation energy of vacancies. When H1 = H0, the above condition would
turn into Eb > KT ln10, which is the same as or similar to Aust’s theory.
Whether the solute and vacancy are able to diffuse in the complex depends on
the binding energy of solute atoms and vacancies. For example, tungsten and
molybdenum’s binding energy with a vacancy can be estimated by using elastic
mechanic. Vacancy formation energy, Ef, can be expressed as
1
Ef ¼ Zð2EAV EAA Þ;
2
where EAA is the interaction energy between atom pairs and EAV is the interaction
energy between atom-vacancy pairs. Obviously, Ef is connected with crystal’s
bonding energy. Ecoh is the average bonding energy or sublimation heat of each
atom pair, so
1
Ecoh ¼ ZEAA ;
2
where Z is the coordination number of crystal structure:

EAV ¼ ðEcoh þ Ef Þ=Z:
For Ef = −0.29Ecoh, the atom-vacancy pair’s binding energy is
1 1
EAV ¼ ðEcoh 0:29Ecoh Þ ¼ 0:071Ecoh :
Z Z
Tungsten and molybdenum are both body cubic-centered structure, and their
sublimation heats are 8.8 and 6.15 eV; so tungsten and molybdenum’s binding
energies binding with vacancy are
EWV ¼ 0:77 eV; and EMoV ¼ 0:38 eV:
According to solute-vacancy complex diffusion energy, condition

Eb > H1−H0 + KT ln10 and
qffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffi
H1 =H0 ¼ 3=4 þ 3:73 Tm0 =Tm ð Rr =R0 0:933ÞðR0 =Rr Þ;
where Rr and R0 are the atom radiuses of the solute and matrix, and Tm′ and Tm are
melting points of the solute and matrix. Attention atom radius RFe ¼ 1:293 Å,
RW ¼ 1:41 Å, RMo ¼ 1:4 Å and melting point TFe ¼ 1813 K,
TW ¼ 3903 K; TMo ¼ 3168 K, and Fe atom’s vacancy migration energy H0 ¼
1:4 eV we can get, for the tungsten-vacancy complex:
Eb ¼ 0:77 eV [ H1 H0 þ KT ln 10 0:44 eV:

For the molybdenum-vacancy complex:Eb ¼ 0:538 eV [ H1 H0 þ KT
ln 10 0:34 eV:
As the result, in the double glow plasma W–Mo alloying process, the solute
atom-vacancy binding energy is higher than complex diffusion energy; a certain
amount of the solute-vacancy complex would take part into diffusion. In the dif-
fusion process, the complex can be regarded as an independent component; how-
ever, the complex’s formation and dissociation are also taking place along with the
process.
On the basis of above analysis, the diffusion mechanism of double glow plasma
alloying is the combination of vacancy exchange mechanism and solute-vacancy
complex mechanism. At high alloying temperature, the solute-vacancy complex
diffusion accounts relatively low; but when the alloying temperature gets lower, the
amount of vacancy would grow at an exponential rate. In turn, the amount of
solute-vacancy complex would steep rise, so the solute-vacancy complex diffusion
is becoming relatively larger.
When the temperature is relatively low, complex diffusion plays a leading role
for large atoms like tungsten and molybdenum; when the temperature gets higher,
the impact of vacancy diffusion would become significant. Meanwhile, the
solute-vacancy complex diffusion mechanism also explains why after the double
glow plasma W–Mo alloying process, a large number of supersaturated vacancies

were formed in the alloying layer under ion bombardment. During the cooling
process, when cooling velocity gets lower, W/Mo solute atoms would form a
significant amount of the complex with velocity and non-equilibrium segregation in
the grain boundary. When complexes get resolved, vacancies would annihilate in
the grain boundary, W/Mo solute atoms gathering in the grain boundary, by the
nucleation and growth mechanism, to form intermetallic compounds. Accordingly
by controlling cooling velocity, we can restrain grain boundary’s precipitation.
5.6 Prospect
The double glow plasma surface alloying technology is based on low-temperature

plasma produced by glow discharge. It is a surface alloying technology with
complex physical processes, such as vacuum, glow discharge, sputtering, and dif-
fusion. In this chapter, many physical phenomena like gas glow discharge,
low-temperature plasma, interaction between particles and surface of material,
transmission of alloying elements particles, diffuse mechanism of alloying ele-
ments, etc. have been discussed.
However, our discussion is still based on some hypothesis and applying existing
knowledge, some viewpoints should be further studied and experimentally con-
firmed. Especially, under ion bombardment, the alloying element diffusing into the
matrix material, interaction between alloying elements or between alloying ele-
ments and matrix elements, formation mechanism of alloy layer structure, etc., are
all complicated theoretical research topics. The related basic theory research actu-
ally lags far behind its application and development research, which has severely
restricted its further development and industrial application.
The demonstrated research results of the various chapters of this book give a
number of examples to present the potential and development prospects of the
Xu-Tec process. For any surface alloying technology, it is a key issue to realize the
control of the composition and distribution of the surface alloy. Among the many
research topics, there are three most important core research topics listed below:
(1) Establishment and quantification of “metal potential”
In order to realize the control of the surface-alloy composition, the concept of
“metal potential” should be established, as referring to the concept of “carbon
potential” in the carburizing process.
The basic idea is that, under the condition of various process parameters, the
plasma parameters are diagnosed by the Langmuir probe diagnosis, optical spec-
trum, mass spectrometry, and so on. The quantitative relationship between
surface-alloy composition and process parameters and plasma parameters can be
established. Then according to the alloying elements and their ion density and
energy in the glow discharge space, the concept and quantification of metal
potential are established. The physical and mathematical model of the metal
potential lays the foundation for the controllability and intelligent control of the
Xu-Tec process.
(2) Diffusion mechanism under ion bombardment
It has been proposed that under ion bombardment, the formation of a large number
of vacancies on the surface of the working-piece sample can increase the solubility
of the surface, and the surface vacancy can be diffused into the substrate. However,
the formation of gradient vacancy diffusion channel needs to be confirmed in the
experiment. According to the relevant reference, the number of surface vacancies
can be measured by the method of positive electron annihilation technique, which
can further calculate the solubility of alloy elements on the surface of the sample. In
addition, the vacancy concentration gradient in the surface of the sample can be
calculated according to the surface vacancy concentration. By comparing the above
results with the actual composition and thickness of the alloy layer, we can further
calculate the diffusion coefficient and understand the diffusion mechanism and its
control.
(3) Formation of surface-alloy layer and mechanism of reaction diffusion
Plasma surface metallurgy is a complex process for the formation of surface alloys
by diffusion of alloying elements into the specimen. In this study, the crystal
structure and thermodynamic parameters between the alloy elements and the matrix
elements must be studied; then a suitable thermodynamic model would be estab-
lished to understand the reaction diffusion mechanism. In addition, many analytic
methods, like GDS, XRD, XPS, and electron microscopy, can be used to detect the
composition, phases composite, and thickness of the surface alloy, as well as the
composition distribution and phase structure of the surface-alloy layer. By com-
paring the above theoretical prediction and actual test results, one can study the
reaction diffusion and alloy phase formation and change rules, providing the the-
oretical basis for the prediction of surface-alloy layer composition and structure,
and the new surface alloy.
It is conceivable that the above assumptions and research are very complex. We
should first conduct a study of the diffusion of the simplest single alloying elements
into a single-element substrate. With the accumulation of a large number of
single-element cases as a foundation, one can enter the multielement case research.
Plasma surface alloying engineering is a multidisciplinary emerging application,
which involves material science, surface physics, surface chemistry, vacuum, gas
discharge, plasma, computer, etc. In order to further take advantages of plasma
surface alloying engineering development, it is urgent to promote this emerging
discipline for industrial applications. Meanwhile, we should conduct further rele-
vant plasma surface alloying theories research and lay a solid theoretical foundation
for the support of this technology of large-scale industrialization and commercial
benefits.
References 87
References
1. Bechstedt F (2007) Surface physics. Science Press

2. Kittel (2005) Introduction to solid state physics, 8th edn. Chemical Industry Press
3. Li D (2006) Plasma physics. Higher Education Press
4. Xu Z (2008) Plasma surface metallurgy. China Science Press, Beijing, pp 79–98
5. Coburn JW, Chen L (1992) Surface treatment by partially ionized plasma. Adv Mech 4:
527–541
6. Wasa K, Kitabatake M, Adachi H (2003) Thin film materials technology. William Andrew,
Inc. and Springer-Verlag GmbH & Co. KG
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Vacuum 1:29–35
8. Zhang G (2004), Research hydrogen-free carburizing and hydrogen–free carbonitriding on
titanium alloy Ti6Al4 V by double glow plasma discharge Taiyuan University of
Technology, Taiyuan
9. Xu Z (1997) The present situation and development of double glow plasma alloying process.
Surf Technol 3:13–51
10. Li C, Xu Z (1987) Diffusion mechanism of ion bombardment. Surf Eng 4:310–313
11. Zhang Pingze (2004) Double glow plasma surface alloyed burn-resistant titanium alloy.
Taiyuan University of Science and Technology, Taiyuan
12. Li Z, Liu X, Xu Z (2000) Effect of concentration gradient of vacancies on diffusion in double
glow plasma surface alloying. J Appl Sci 6:183–185
13. Li C, He Z, Xu Z (2000) Diffusion mechanism of ion bombardment W-Mo surface alloying.
Trans Nonferrous Met Soc China 2:185–188
Chapter 6
Plasma Surface Metallurgy of Iron
and Steel
Abstract Iron and steel materials are the most widely used engineering materials
with the largest amount of metal materials in modern production and application.
To enhance the surface physical and mechanical performance of iron and steel
materials, surface engineering modification is applied to coordinate the different
performance requirements between the substrate and surface of iron and steel
materials. This chapter introduces both the single-element and multiple-element
plasma surface metallurgy processes, to form various surface alloys on iron and
steel material. In addition, the plasma surface metallurgy superalloys, precipitation
hardening stainless steel, and plasma surface metallurgy antibacterial stainless steel
formed on the surface of steels is also introduced. The plasma surface alloying
parameters, microstructures, composition distribution, and properties of above all
surface alloys are presented.
6.1 Introduction
6.1.1 Plasma Surface Alloying and Alloying Element
Iron and steel are the most widely used engineering materials. Steel is a kind of
material with iron as the matrix element and carbon as the main doping element for
alloying. Some other elements, such as nickel, chromium, tungsten, molybdenum,
and so on, could also be used to form alloy steels like stainless steel, Mo steel, and
W steel.
To enhance the surface physical and mechanical performance of iron and steel
materials, surface engineering modification is applied to coordinate the different
performance requirements between substrate and surface of iron and steel materials.
Surface alloying processing is a surface technology which specifically adds other
chemical elements to the material surface, leading to a change in the surface
composition, structure, and properties. Any chemical element used for surface
alloying is called “Alloying Element”. Plasma surface alloying is a surface alloying
technology using low-temperature plasma and its interaction with the surface.
DOI 10.1007/978-981-10-5724-3_6
90 6 Plasma Surface Metallurgy of Iron and Steel
6.1.2 Interaction of Alloying Element with Fe and C
Upon the interaction mechanism with carbon in iron and steel, alloying elements
can be divided into the following three types:
1. Strong carbide-forming element, such as Ti, V, Zr, Ta, Nb, and so on. These
elements have a very strong affinity with nitrogen, carbon, and oxygen, easily
forming very stable chemical compounds. When carbon in the surface layer of
iron and steel material interacts with carbide-forming elements, the resulting
carbide-contained layer will greatly affect the microstructure of the
surface-alloyed layer with high hardness, wear resistance, and corrosion resis-
tance. By using the Xu-Tec process, carbon in the iron and steel substrate will be
attracted to the surface and combined with the alloying element to form carbide
on the surfaces of high-carbon and medium-carbon steels. However, on the
surfaces of industrial pure iron and low-carbon steel, carbide forming is difficult
since the low-carbon content is not enough to fully combine with
carbide-forming element to form carbides. Carbide-forming elements can also
be dissolved in austenite or ferrite to form an alloy diffusion layer with gradient
distribution.
2. Medium carbide-forming element, such as W, Mo, Cr, and so on. The
carbide-forming ability of medium carbide-forming elements is relatively weak.
In the alloying process, they would partly diffuse into austenite or ferrite in
atomic states, or into the cementite by replacing Fe atoms, forming a new
cementite. When these carbide-forming elements and carbon in iron and steel
surpass a certain amount, they can form their own special carbide, such as (Fe,
Cr)7C3, (Fe,W)6C, etc. When the contents of some alloying elements are rel-
atively high, they can also form intermetallic compounds, such as FeCr, Fe2W,
Fe2Ti, FeSi, and so on. These intermetallic compounds are the intermediate
phase in the alloy phase diagram of the alloying element and iron.
3. Non-carbide-forming element, such as Al, Si, Ni, Cu, Co, and so on. When
plasma surface alloying with non-carbide-forming element on carbon steel,
non-carbide-forming elements would diffuse and dissolve in austenite or ferrite
to form an alloy solid solution. These alloying elements in the alloy solid
solution tend to gradiently distribute along the depth from the sample surface,
which is usually called alloying element diffusion layer.
Some more active alloying elements can also combine with nitrogen and oxygen
in the steel, forming stable nitride and oxide, such as Al2O3, AlN, TiN, ZrN, etc.
The necessary condition for successfully forming a surface alloying process is
that the alloying element can dissolve and diffuse into iron and steel matrix. For
plasma surface alloying, it is needed to refer to the alloy phase diagram of the
alloying element and iron to analyze technological feasibility.
The solubility of all above alloying elements in iron is normally defined in their
alloy phase diagram. However, under the conditions of ion bombardment, the
surface layer can dissolve more alloying element since the surface layer is defected
6.1 Introduction 91
by ions and contains a large number of vacancies. Therefore, the saturation solu-
bility of the surface dissolved alloy elements can go much higher beyond the
solubility in the standard alloy phase diagram.
6.2 Single-Element Plasma Surface Metallurgy
6.2.1 Plasma Surface W Alloying
Tungsten (W) is the first alloying element to be used in plasma surface alloying
modification of iron and steel materials by double glow plasma surface metallurgy
technology. Tungsten possesses heavy atomic weight and the highest melting point
(3380 °C). Due to its very high melting point, tungsten alloys can be used to
increase its high-heat strength and red hardness of steel. Tungsten and carbon can
combine to form its own special carbide WC, which has good wear resistance. The
success of tungsten alloying in the surface of iron and steel predicts the success of
other elements alloying [1, 2].
Using a tungsten plate or tungsten wire as the source material, tungstenizing was
conducted by the Xu-Tec on low-carbon steel, medium-carbon steel, or low-alloy
steel as the substrate. The typical plasma surface alloying parameter ranges are the
following [3]:
Source material: Tungsten plate,
Argon gas pressure: 25–50 Pa,
Source voltage: 800–1200 V,
Workpiece voltage: 300–600 V,
Distance between the workpiece and the source: 10–30 mm,
Alloying temperature: 900–1200 °C,
Alloying time: 1–6 h.
Figure 6.1a shows an optical cross-sectional micrograph, showing the
cross-sectional microstructure of an alloyed layer on Steel-1010 by plasma surface
alloying with tungsten element at 1000 °C for 4 h. There are many black
micro-hardness indentation marks in the picture. They indicate the hardness of
surface alloy and the hardness of matrix is almost same as low-carbon steel base
material when tungsten atoms are dissolved in the solid solution of the alloy layer of
iron. Figure 6.1b shows two depth profiles of tungsten distribution in an alloyed
layer after plasma tungstenizing for 3 h at 900 and 1000 °C, respectively. It is seen
that a W diffusion layer was formed at the surface with a thickness of 70 lm at
1000 °C and 40 lm at 900 °C. With the same processing time, the higher the
alloying temperature, the thicker the diffusion layer is. The maximal tungsten
content of the alloyed layer can reach to 10 wt%. The line between the diffusion
layer and the matrix is the phase boundary caused by solid-state phase transfor-
mation and separation at cooling down.
Fig. 6.1 a Microstructure and b tungsten distribution of alloyed layer on steel 1010 after plasma
tungstenizing [1]
The corrosion resistance contrast experimental tests show that after surface
plasma tungstenizing treatment, corrosion resistance of the carbon steel is greatly
improved in a strong acid medium test, even better than that of stainless steel.
6.2.2 Plasma Surface Ti Alloying
Titanium (Ti) is one of the most active metal elements. It has a strong affinity with
nitrogen, carbon, and oxygen. Titanium nitride (TiN) coating by nitrogen/argon
plasma sputtering of Ti target has been widely used on steel cutting tools for
hardness enhancement. Here, titanium carbide (TiC) alloy layer has been formed on
the surfaces of Steel-1045 and Steel-1080 after plasma titanizing by the Xu-Tec
plasma process. The process condition is similar to that used for W material given
in the last section [4].
Figure 6.2 shows the microstructure and titanium distribution of an alloyed layer
on the surface of Steel-1080 after titanizing at 950 °C for 4 h. The white bright
layer of the surface is a titanium carbide (TiC) alloy layer formed by deposited and
diffused Ti atoms with C atoms diffused over from the substrate during the plasma
alloying process. The layer thickness is about 20 lm. Ti content in the carbide layer
is over 90 wt%. The hardness of titanium carbide alloy layer surpasses 1000HV.
Figure 6.3 shows the Ti content depth distribution in the alloyed layers on three
different carbon steels after plasma surface titanizing. Titanium carbide alloy layer
has been formed on the surfaces of Steel-1045 and Steel-1080. The maximum
titanium content in a carbide alloy layer is 94 and 98 wt%, respectively. On the
surface of low-carbon Steel-1010, titanium carbide-alloyed layer was not formed,
but only a Ti diffusion layer with the maximal 4.3 wt% of Ti content was found.
High-carbon content in the substrate means that the diffusion of Ti atom can be
greatly inhibited by carbide formation.
6.2 Single-Element Plasma Surface Metallurgy 93
Fig. 6.2 b Microstructure and b titanium content of the alloyed layer on Steel-1080 after
titanizing at 950 °C for 4 h [5]

of titanium element on
different carbon steels
6.2.3 Plasma Surface Cr Alloying
Chromium (Cr) in iron and steel materials can significantly improve the corrosion
resistance and oxidation resistance of the steel. Cr is a medium carbide-forming
element. Chromium carbide (CrC) alloy layer was directly formed on Steel-1080
surface by Xu-Tec plasma surface chromizing. Figure 6.4 shows the cross-sectional
microstructure with several micro-hardness indentations (black) of Steel-1080 after
1000 °C 5 h chromizing [5, 6]. The resulting CrC-alloyed layer is shown as a
white bright layer with a thickness of about 35 lm. Black diamond-shaped marks
are from micro-hardness indentation test. It shows a substantial difference and
gradually reduced of micro-hardness from the CrC surface layer (about
1000HV0.2) to the steel matrix. The chemical corrosion test shows its excellent
corrosion resistance improvement from the steel substrate.
The CrC-alloyed layers with high hardness are also formed on the surface of
Steel-1020 and Steel-1045 by Xu-Tec plasma chromizing, followed with the
Fig. 6.4 Microstructure of an

alloyed layer on Steel-1080
after 1000 °C 5 h
chromizing [5]
Fig. 6.5 Chromium depth

distribution in three alloyed
steel samples
additional carburizing treatment. The mass fraction of chromium carbide in

surface-alloyed layer is more than 40 wt%, surpassing the carbide content of the
general high-speed steel. The surface hardness is over 1000HV0.2. The wear
resistance raises 8.6 times compared with GCr15 hardened steel.
Figure 6.5 presents Cr element distribution curves in alloyed layers on different
carbon steel samples at the same alloying parameters. Cr content of Steel-1080
surface is much higher than that of Steel-1020 and Steel-1045, which means that
chromium carbide alloy layer was formed on Steel-1080 and Cr diffusion layer was
formed on Steel-1020 and Steel-1045. The alloyed layers on Steel-1020 and
Steel-1045 are thicker than that on Steel 1080. The results indicate that carbon in
the substrate can greatly hinder the diffusion of Cr atoms. Meanwhile, the higher the
carbon content in the substrate, the more difficult the Cr atoms diffuse.
6.2.4 Plasma Surface Al Alloying
Aluminum (Al) has a strong affinity with oxygen and nitrogen, but Al is not a
carbide-forming element as carbon content in the substrate will not affect the dif-
fusion of Al atoms. Al diffusion layer can be formed on the surface of various
carbon and alloy steels by plasma aluminizing through Xu-Tec processing.
Figure 6.6 gives Al content profiles in three samples made of Steel-1020,
Steel-HW3, and Steel 52100 prepared by such plasma aluminizing process. The
thickness of Al diffusion layer can reach a few hundred microns [7].
Figure 6.7 presents the cross-sectional microstructure of Steel-1045 after alu-
minizing and plasma nitriding. In this photo, there is a series of gradual increase of
micro-hardness indentations (black), which shows that the micro-hardness in the
surface is the highest and gradually reduced deep into the substrate. Figure 6.8
shows the cross-sectional microstructure and aluminum content distribution of the
alloyed layer on Steel-HW3 after 1000 °C 3 h aluminizing. An Al-alloy layer
with thickness about 200 lm was formed on the surface.
After plasma nitriding process, the surface can form a high-hardness layer
including aluminum nitride (AlN) with hardness of 1000HV0.2. The bench test of
wear-resistant performance shows that the life can be improved for more than 3 times.
6.2.5 Plasma Surface Mo Alloying
Molybdenum (Mo) has similar physical and chemical properties with tungsten, as is
seen from W–Fe and Mo–Fe binary phase diagrams. Microstructure, morphology
characteristics, and elements distribution of Mo-alloy layer are all similar to those
of W-alloy layer. Mo-alloy layer on steel surface can also improve the wear and
corrosion resistance of carbon steel.
Figure 6.9 shows the cross-sectional microstructure and the depth profiling
curve of molybdenum content in the alloyed layer. After 1000 °C 3 h

of aluminum element content
in three alloyed layers [7]
Fig. 6.7 Microstructure of an alloyed layer on Steel-1045 after aluminizing and nitriding [7]
Fig. 6.8 a Microstructure and b aluminum content of alloyed layer on Steel-HW3 after
1000 °C 3 h aluminizing [7]
molybdenumizing, the thickness of Mo-alloy layer on carbon steel surface can

reach 90 lm and the maximal Mo content is 15 wt%. Subsequent mechanical tests
show that the corrosion resistance has been greatly improved by molybdenumizing.
The alloyed layer with molybdenizing + carburizing + quenching + tempering
process can greatly improve the surface wear resistance as well.
Fig. 6.9 a Microstructure and b molybdenum distribution of alloyed layer after 1000 °C 3 h
molybdenizing on Steel-1045
6.2.6 Plasma Surface Ta Alloying
Tantalum can form a very stable compound with carbon, nitrogen, and oxygen.
Tantalum alloys can improve the strength, toughness, creep resistance, and corro-
sion resistance of steel. Using double glow plasma alloying technology, tantalum
alloy was formed on the surface of Steel-1020 to improve the corrosion resistance
[8].
Figure 6.10a shows the cross-sectional microstructure of Ta-alloy layer on the
steel surface. The white area is the alloyed layer and the black area is the substrate.
They are separated by a clear interface line, indicating that there is no much
inter-diffusion for Ta–C in the alloyed layer. Figure 6.10b shows a Ta content
profile along the depth of the alloyed layer. The thickness of the alloyed layer is
about 33 lm, including deposition layer of 30 lm and diffusion layer of 3 lm. The
deposition layer is pure Ta. Ta content in diffusion layer changes continuously,
forming a good composition transition between the alloyed layer and the substrate,
enhancing their bonding strength. The main phase of Ta-alloy layer is a-Ta. The
hardness of Ta-alloy layer is higher than that of the substrate. The polarization
curve in 3.5% NaCl solution shows that the corrosion resistance of Ta-alloy layer is
much better than that of the substrate.
6.3 Multiple-Element Plasma Surface Metallurgy
Based on the single-element plasma surface metallurgy, the binary- and

multiple-element alloying processes have been carried out. This section mainly
introduces the surface-alloyed layer formed with binary elements.
Fig. 6.10 a Microstructure and b Ta content of an alloyed layer after 950 °C 3 h tantalumizing
on Steel-1010 [8]
6.3.1 Plasma Surface W–Mo Alloying
The author has studied W–Mo alloying process for many years in order to form
high-speed steel with improved hardness, wear resistance, and red hardness on the
surface of carbon steel. Source materials with W–Mo ratios of 8:2, 5:5, and 2:8
were used [9, 10].
Figure 6.11 shows the microstructure and alloying element content of an alloyed
layer (W, Mo) on Steel-1020 after double glow plasma W–Mo alloying at 1050 °C
for 6 h. The thickness of W–Mo-alloyed layer is over 300 lm. The element content
on the surface is about 3 wt% for W and 10 wt% for Mo, respectively. W–Mo
content distribution follows the diffusion pattern and gradients decrease along the
depth of the alloyed layer. After carburizing, the amount of fine carbides dispers-
edly distributes in the alloyed layer.
Fig. 6.11 a Microstructure and b W and Mo distribution of an alloyed layer after

1050 °C 6 h W–Mo alloying on Steel-1020
6.3 Multiple-Element Plasma Surface Metallurgy 99
In industrial application, W–Mo alloying was first used on handsaw blade in

1986, to form Mo–W high-speed steel on the saw teeth by W–Mo alloying and
carburizing. It will be introduced in detail in Chap. 7 (plasma surface metallurgy
W–Mo high-speed steel) and Chap. 12 (plasma surface metallurgy high-speed steel
handsaw blade).
6.3.2 Plasma Surface Ni–Cr Alloying
High Ni–Cr-alloyed layer has been formed on carbon steel surface by using double
glow plasma Ni–Cr alloying with Ni80–Cr20 as source target. The thickness of Ni–
Cr-alloyed layer is 70 lm. The content ratio of Ni–Cr follows that of Ni80–Cr20
target. The total content of Ni and Cr of the surface alloy reaches 95 wt% at the
surface, with a diffusion gradient decreasing deeply into the matrix. Its corrosion
resistance has reached or preceded austenite stainless steel. Figure 6.12 shows Ni
and Cr composition distributions in the Ni–Cr-alloyed layer on Steel-1010 surface,
alloyed at 1000 °C for 3 h with Ni80-Cr20 alloy as a source material [11, 12].
6.3.3 Plasma Surface Cr–Mo Alloying
Cr–Mo alloying was conducted on Steel-1020, -4317, and -1045. Figure 6.13
shows the microstructure and Cr/Mo content of alloyed layer after Cr–Mo alloying
at 1050 °C for 4 h on Steel-1020. There is a clear dividing line between the Cr–Mo
diffusion layer and matrix because of the inconsistent solid-state phase transfor-
mation of the different parts during alloying process.
Microstructure of the diffusion layer is in columnar a-Fe solid solution, con-
necting with the matrix grain. Cr and Mo content drops slowly in the alloyed layer
Fig. 6.12 Ni–Cr distribution

in an alloyed layer after
1000 °C 3 h Ni–Cr
alloying on Steel-1010 [12]
Fig. 6.13 a Microstructure and b Cr, Mo content of alloyed layer after 1050 °C 4 h Cr–Mo
alloying on Steel-1020 [13]
and the maximal value is 10.0 wt% Cr and 8.0 wt% Mo at the surface. The carbide
of alloyed layer is mainly composed of Cr23C6, Cr7C3, Mo2C, Mo6C, etc. [13].
6.4 Plasma Surface Metallurgy Superalloys
6.4.1 Superalloy
Superalloys are those high-performance alloys based on nickel (Ni), iron–nickel

(Fe–Ni), or cobalt (Co) elements. They exhibit several key characteristics: excellent
mechanical strength, resistance to thermal creep deformation, good surface stability,
and resistance to corrosion or oxidation, unmatchable by other metallic alloys.
Nickel-based alloy is particularly suitable for some serious anticorrosion engi-
neering applications under harsh medium environment, while stainless steel and
other corrosion-resistant metal materials are normally unable to do so.
Superalloys are primarily used in gas turbine engines in both aerospace and
marine, coal conversion plants, chemical process industries, and other specialized
applications that require to withstanding up in a high thermal intensity and corro-
sion resistance. Superalloy development has relied heavily on both chemical and
process innovations. Superalloys develop high-temperature strength through solid
solution strengthening. An important strengthening mechanism is precipitation
strengthening which forms secondary phase precipitates such as gamma prime and
carbides. Oxidation or corrosion resistance is provided by elements such as nickel
and chromium.
6.4 Plasma Surface Metallurgy Superalloys 101
6.4.2 Plasma Surface Ni–Cr–Mo–Nb Superalloys
Inconel-625 developed by American is a more versatile nickel-based alloy with

main compositions of nickel, chromium, molybdenum, niobium, etc. (61Ni, 21.5Cr,
9Mo, 3.6Nb, wt%) [14].
Using Inconel-625 as the source material, plasma surface alloying processes
were conducted on surfaces of industrial pure iron, Steel-1010, and stainless steel
304 at 850–1000 °C. The results show that a surface-alloyed layer with element
composition similar to that of Inconel-625 can be formed on these three substrates.
Figure 6.14 and Fig. 6.15 show the microstructure and alloying element (Ni, Cr,
Mo, Nb) depth distribution of surface-alloyed layer on industrial pure iron and
Fig. 6.14 a Microstructure and b Ni, Cr, Mo, Nb distribution of alloyed layer on a pure iron
substrate [14]
Fig. 6.15 a Microstructure and b Ni, Cr, Mo, and Nb distribution of an alloyed layer on
Steel-1010 [5]
Steel-1010. Nickel-based alloy layer is uniform, continuous, dense, and no hollow.

A metallurgical bonding is strongly formed between the surface-alloyed layer and
the substrate. The thickness of the alloyed layer is about 40 lm. Ni, Cr, Mo, and Nb
content gradient decreases in subsurface layers.
The corrosion resistance of plasma surface metallurgy Ni–Cr–Mo–Nb alloy has
been investigated by electrochemical method in 3.5%NaCl, 5%HCl, and 5%H2SO4
solution. The surface alloy on pure iron has similar corrosion resistance to
Inconel-625. The corrosion resistance of surface alloy on Steel-1010 is lower than
that of Inconel-625, but much better than that of stainless steel 304.
6.4.3 Plasma Surface Ni–Cr–Mo–Cu Superalloys
Hastelloy C-2000 nickel base corrosion-resistant alloy is the latest products of

HAYNES Company in 1995 and possesses excellent corrosion resistance for a
variety of media. The alloy is added to a small amount of copper in Ni–Cr–Mo
alloy. Its chemical compositions are 59Ni, 23Cr, 16Mo, 1.6Cu, and C < 0.01 wt%.
Using the Hastelloy C-2000 alloy as the source material, Ni–Cr–Mo–Cu alloying
was conducted on the surfaces of Steel-1020 and stainless steel 304 at 900–1000 °C
[15].
Figures 6.16 and 6.17 present the microstructures and Ni, Cr, Mo, and Cu
distribution curves of alloyed layers on Steel-1020 and stainless steel-304. Surface
composition of an alloyed layer is similar to Hastelloy C-2000, and the total content
of alloy elements surpasses 90 wt%. The average thickness of alloyed layer is
35 lm after 3 h alloying. Content of alloy elements in the alloyed layer of
Steel-1020 and 304 continuously drops from the surface to the substrate matrix.
A good metallurgical bonding is formed between the alloyed layer and the
substrate.
Fig. 6.16 a Microstructure and b Ni, Cr, Mo, and Cu distribution of Hastelloy C-2000 alloy layer
on Steel-1020 [15]
6.4 Plasma Surface Metallurgy Superalloys 103
Fig. 6.17 a Microstructure and b Ni, Cr, Mo, and Cu distribution of Hastelloy C-2000 alloy layer
on SS-304 [15]
The corrosion resistance of plasma surface metallurgy Ni–Cr–Mo–Cu alloy has

been investigated by electrochemical method in 3.5%NaCl, 5%HCl, and 5%H2SO4
solution. The test results indicated that the corrosion resistance of surface alloy on
Steel-1020 is lower than that of Hastelloy C-2000, and higher than that of stainless
steel 304.
6.5 Plasma Surface Metallurgy Precipitation Hardening

Stainless Steels
The precipitation hardening stainless steel (PHSS) was invented in the United States
in 1934 and was applied in industry in 1940s. The PHSS possesses high strength,
toughness, and corrosion resistance. It is commonly used in some important
components of sophisticated industry and civilian industry, such as aircraft struc-
tures, and rocket shells, etc. This type of steel includes high-precious metal ele-
ments, such as Cr, Ni, Mo, and Co.
In order to reduce the cost of materials, plasma surface metallurgy PHSS
alloying has been applied on the surface of the ordinary steel, to replace the pure
PHSS bulk material.
6.5.1 Plasma Surface Alloying Process
A 13Cr–25Co–5Mo (wt%) martensitic PHSS was used as the target composition.

Considering the atomic percentage, sputtering rate, and mutual influence of each
element, a source material of 25Cr–5Ni–15Mo–55Co (wt%) was defined. The
source plate was made by the powder metallurgy method. Industrial pure iron was
used as the substrate [16].
Fig. 6.18 a Microstructure and b the distribution of Cr, Ni, Mo, and Co elements of plasma
surface metallurgy PHSS [16]
The optimizing process parameters of plasma surface alloying are as follows: the
source voltage is −1100 V, cathode voltage ranges from −500 to −530 V, tem-
perature is 1050 °C, and processing time is 5.5 h.
Figure 6.18 shows the microstructure and composition distribution of the
alloyed layer. The alloyed layer is very dense and the thickness is about 80 lm. The
surface layer within 30 lm of the alloyed layer contains 12–17 Cr, 2–5 Ni,
3–6 Mo, 18–30 Co (wt%), very similar to that of 13Cr–25Co–5Mo PHSS.
6.5.2 Age Hardening Process
After plasma alloying process, solid solution and aging treatment were conducted.
After 1050–1220 °C solid solution treatment, hardness of the alloyed layer is
280–350 HV, which is far higher than that of pure iron substrate (140–170HV). At
540 °C aging treatment, hardness of the alloyed layer can reach 500 HV. X-ray
diffraction analysis (XRD) shows that the strengthening phase in the alloyed layer is
Fe2Mo and Ni3Mo. These intermetallic compound alloys have very small grain
sizes and can only be observed using transmission electron microscopy (TEM).
6.5.3 Corrosion and Wear Tests
The polarization curve in 5% HCl solution shows that corrosion potential of the
surface PHSS is more negative than other two kinds of steels. Its critical passivation
current density is at a minimum and the passivation ability is at the largest. High
corrosion resistance of surface PHSS is due to Mo addition.
6.5 Plasma Surface Metallurgy Precipitation Hardening Stainless Steels 105
The pin plate wear test results show that the wear resistance of the surface PHSS
is 3 times higher than stainless steel 304 and 6 times higher than pure iron.
6.6 Plasma Surface Metallurgy Antibacterial Stainless

Steels
In Japan, a new series of antibacterial stainless steels with Cu or Ag has been

developed since 1996. The steels are mainly formed by adding appropriate Cu
element or Ag element in the common stainless steels. Cu and Ag possess excellent
antibacterial properties because it can release a large amount of Cu ions and Ag ions
to penetrate bacteria cell walls and kill cells. Generally, ferrite antibacterial stainless
steel contains 1.5 wt% Cu, martensitic stainless steel contains 3 wt% Cu, and
austenitic stainless steel contains 3.8 wt% Cu, while Ag antibacterial stainless steel
contains roughly 0.05 wt% Ag. The cost of bulk antibacterial stainless steel is very
high due to a high content of copper or silver.
Since the antibacterial effect is only needed at the surface for most of the
application occasions, it is a smart choice to have a surface antibacterial alloy layer
formed on the common stainless steel surface by plasma copperizing or silverizing
with the Xu-Tec process.
6.6.1 Cu-Antibacterial Stainless Steel
Using a pure Cu plate as a source material, a Cu antibacterial alloy layer can be

formed on the surface of stainless steel 304 by the Xu-Tec process. Figure 6.19
shows the microstructure and Cu content of the antibacterial alloy layer after
Fig. 6.19 a Microstructure and b Cu content of antibacterial alloy layer after 950°C 3 h
copperizing [17]
950 °C 3 h Cu alloying. The maximal Cu content is about 3.0 wt% in the

alloyed layer. The thickness of the alloyed layer reaches roughly 30 lm. The
antibacterial rates against Escherichia coli and Staphylococcus aureus surpass 95%
[17, 18].
When putting Cu–Ce alloy on the stainless steel surface, rare earth element Ce
can promote the Cu atom diffusion and increase the thickness of Cu-alloy layer. The
maximal Cu content in an alloyed layer can reach 3.7 wt%. Because the solubility
limit of Cu in Fe is only at 5 wt%, Cu can infinitely dissolve into Ni. Cu–Ni
alloying on stainless steel surface can increase the Cu content maximal to 7.1 wt%
[19].
6.6.2 Ag-Antibacterial Stainless Steel
Using a hybrid steel–silver plate (nominal composition stainless steel SS-316L:

Ag = 5:1) as the source electrode for the double glow plasma Ag alloying, an Ag
antibacterial alloy layer was formed on the surface of SS-316L with a thickness
about 5 lm and the maximal Ag content of 14 at%. The XRD shows that Ag exists
in alloyed layer in the form of Ag and Ag2O3. Antibacterial rates of Ag-alloy layer
against both Escherichia coli and Staphylococcus aureus are over 97 and 90%,
respectively, within 6 h [20].
6.6.3 Ag–Cu Antibacterial Stainless Steel
Using Ag–Cu-alloy plate with the mass ratio of 7:3 as a source electrode, an Ag–
Cu-alloy layer was formed on the surface of SS-304 with a thickness about 20 lm
and the maximal Ag content at 3.0 wt% and Cu content at 4.9 wt%. The
antibacterial rate against Escherichia coli and Staphylococcus aureus are 100% [21].
6.7 Plasma Composite Treatment
After plasma surface alloying, in order to further improve hardness and abrasion
resistance of the alloyed layer, more alloying processes, e.g., carburizing or
nitriding, are often needed. Sometimes subsequent heat treatment is also needed. As
was stated earlier, to make the aluminized layer with a high hardness, nitriding
process must be conducted. To form a surface of high-speed steel, carburizing and
subsequent quenching and tempering treatment must be conducted after W–Mo
alloying. Furthermore, sometimes it is needed to combine two or more processes of
plasma alloying technology to prepare an alloy layer with more excellent
performance.
6.7 Plasma Composite Treatment 107
6.7.1 Plasma Titanium and Titanium–Nitrogen Alloying
Alloying coatings of titanium nitride and/or titanium carbide prepared by physical

vapor deposition (PVD) or chemical vapor deposition (CVD) possess ultra-high
hardness and excellent wear resistance. They are widely used in the engineering
surface coating process. However, the bonding between the coating and the sub-
strate is normally rather poor.
The author formed a 15-lm-thickness golden titanium nitride layer by titanizing
and the subsequent titanium–nitrogen alloying on Steel-1020 surface at 1020 °C
using Xu-Tec technology [22]. The thickness and the surface hardness of a TiN
layer increase with the rise of the temperature. The surface hardness is 1600–
3400HV0.2. Metallurgical bonding is formed between the titanium nitride layer and
the substrate. No flaking or chipping occurs.
6.7.2 Brush Plating and Plasma Surface Alloying
A nickel transition layer was formed on the surface of Steel-1020 using the brush
plating, and then a multielement alloy layer was formed by Ni–Cr–Mo–Cu alloy-
ing. The result of anticorrosion performance test of the alloy layer in 5% HCl
solution is obviously better than that of the single Ni–Cr–Mo–Cu alloying. The
better corrosion resistance of the composite treatment layer can be attributed to the
fact that the carbon diffusion from the substrate toward the surface-alloyed layer
was inhibited by Ni plating layer at the high temperature [15].
6.8 Summary
The double glow plasma surface alloying technology is an advanced surface met-
allurgy method. The technique can be easily used for single-element alloying,
multiple-element alloying, or various composite treatments. So far, single-element
alloying (such as tungstenizing, molybdenumizing, chromizing, aluminizing,
titanizing, tantalumizing, copperizing) and multiple-element alloying (such as W–
Mo alloying, Ni–Cr alloying, Cr–Mo alloying, Ag–Cu alloying, Ni–Cr–Mo–Nb
alloying, Ni–Cr–Mo–Cu alloying, Cr–Ni–Mo–Co alloying) have been conducted
on steels to form various surface alloy layers for wear-resistant, corrosion-resistant,
surface antibacterial stainless steels, and so on. This has demonstrated that the
Xu-Tec process possesses the huge potential for preparing various alloy layers on
the ordinary material surface.
References
1. Xu Z, Wang ZM, Gu FY (1982) Double glow plasma surface alloying process. Trans Mater.
Heat Treat 3(1):71–82
2. Gu FY, Wang ZM, Fan BH (1985) Double glow plasma surface tungstenizing and subsequent
heat treatment process. Heat Treat Met 3:59–64
3. Zhang H, Su YA, Gu FY, Xu Z (2000) Characteristics of tungsten alloy layer formed at
different temperature by double glow plasma surface alloying. J Chin Soc Corros Prot 20
(1):59–64
4. Xu Z, Gu FY, Fan BH (1986) Double glow plasma surface aluminizing and titanizing. Trans
Mater Heat Treat 7(2):95–99
6. Fan BH, Xu Z, Zheng WN (1987) Double glow plasma surface chromizing. Trans Mater Heat
Treat 2:3–8
7. Gu FY, Wang CZ, Gao Y, Xu Z (1989) Application research of double glow ion aluminizing
on exhaust valve. Heat Treat Met 7:27
8. Qiang B (2012) Research on processing and corrosion resistance of Ta alloyed layers on
Q235 steel formed by double glow plasma surface alloying. Nanjing University of
Aeronautics and Astronautics, Nanjing
9. Wang CZ, Su YA, Tang B, Xu Z (1990) The microstructure of alloyed layer treated by double
layer ionized W, Mo metalizing and its formation mechanism. Heat Treat Met 2:22–28
10. Gao Y, Liu XP, He ZY, Xu Z (2000) An analysis on microstructures of alloyed layer by
double glow plasma W-Mo alloying process after carburizing. Chin J Nonferrous Met 10
(1):55–58
11. Fan BH, Xu Z, Pan JD (1988) Double glow plasma Nickel-chromium alloying. J Taiyuan
Univ Technol 19(3):10–15
12. Fan BH, Xu Z, Pan JD (1988) Double glow plasma Nickel-chromium alloying. J Taiyuan
Univ Technol 19(3):10–15
13. Xu JY, Liu YP, Wang JZ (2005) Study on Mo–Cr plasma surface alloying high speed steel
and its performance. Mater Rev 19(1):114–116
14. Zhang X, Xie XS, Yang ZM (2003) A study of nickel-based corrosion resisting alloy layer
obtained by double glow plasma surface alloying technique. Surf Coat Technol 131:378–382
15. Xu J, He AJ, Shan XS, Xu Z (2003) The multi-element Ni–Cr–Mo–Cu surface alloying layer
on the steel using a double glow plasma. Surf Coat Technol 168(2–3):142–147
16. Liu XP, Gao Y, Li ZH (2006) Cr-Ni-Mo-Co surface alloyed layer formed by plasma surface
alloying in pure iron. Appl Surf Sci 252:3894–3902
17. Zhang JC (2011) Study on process and properties of antibacterial stainless steel by plasma
permeating technique. Guilin University of Electronic Technology, Guilin
18. Zhang XY (2012) Study on preparation and properties of surface antibacterial alloyed layers
of stainless steel. Taiyuan University of Technology, Taiyuan
19. Wang Y (2011) Preparation infiltration layer containing Cerium and Copper in surface of
stainless steel and properties of infiltration layer. Guilin University of Electronic Technology,
Guilin
20. Dong Y, Li X, Tian L (2011) Towards long-lasting antibacterial stainless steel surfaces by
combining double glow plasma silvering with active screen plasma nitriding. Acta Biomater
7:447–457
21. Ni HW, Zhan WT, Chen RS (2011) Microstructure and antibacterial properties of AISI304
stainless steel doped by Ag/Cu. Mater Rev B 25(4):27–29
22. Liu YP, Xu JY, Kui XY (2005) Study on structure and property of TiN multi-permeating
coatings prepared by plasma discharge technique. Trans Mater Heat Treat 26(6):109–112
Chapter 7
Plasma Surface Metallurgy High-Speed
Steel
Abstract This chapter introduces the plasma surface metallurgy high-speed steels
(HSS) formed on the ordinary carbon steel surface by double glow plasma surface
alloying technology (Xu-Tec process). The cases include W–Mo HSS, W–Mo–
C HSS, W–Mo–Ti HSS, and Mo–Cr low alloy HSS, as well as plasma surface
metallurgy aging hardening HSS. The process parameters, microstructures, com-
position distribution, and properties of above high-speed steels are presented in
detail. Plasma surface metallurgy high-speed steels on the ordinary steel not only
possess excellent performances by comparing to the bulk HSS materials, but also
save the precious alloy elements (tungsten and molybdenum) in producing a surface
layer and greatly reduce the overall material cost.
7.1 High-Speed Steels (HSS)
High-speed steels (HSS) were invented by Taylor and White in USA in 1898 and
successfully applied in fabricating high-speed cutting tools and molds. They exhibit
several key characteristics: high hardness (63–67 HRC), red hardness (>60 HRC at
550–600 °C), and excellent wear resistance. HSS has occupied an important
position in iron and steel materials, especially in special steels. The world annual
output of HSS has reached 250,000 tons and China’s annual output has reached
40,000 tons. In recent years, the applications have extended to some important
structure components requiring high hardness and high wear resistance, such as
gear, roller, and so on.
7.1.1 Conventional Metallurgy HSS
Conventional metallurgy HSS would inevitably generate coarse eutectic ledeburite

during solidification due to high alloy content, complex chemical composition,
large ingot size, and slow cooling rate. The coarse eutectic carbide grains distribute
DOI 10.1007/978-981-10-5724-3_7
110 7 Plasma Surface Metallurgy High-Speed Steel
unevenly in the matrix and cannot dissolve in austenite even heated to 1300 °C.
Though they may be eliminated by forging repeatedly, it is hard to eliminate them
completely. Carbide segregation can greatly reduce the hardness, red hardness,
wear resistance, and toughness of the steels. The segregation degree of the eutectic
carbide has become one of the important technical indexes for identifying HSS
quality.
7.1.2 Powder Metallurgy HSS
In 1965, America Crucible Steels Company invented the powder metallurgy HSS.
In 1970, powder metallurgy HSS began to put into production. Powder metallurgy
HSS is produced by sintering the mixed powders of tungsten carbide, molybdenum
carbide, and Fe. Comparing with the conventional metallurgy HSS, the powder
metallurgy HSS has no carbide segregation. Therefore, the bending strength and
toughness of powder metallurgy HSS are usually 20–50% higher than that of
conventional metallurgy HSS. It is suitable for manufacturing cutting tools used
under an impact load, such as milling cutters, gear shaper cutter, planer cutter, and
some thin blade cutter. Compared with conventional metallurgy HSS of the same
chemical composition, the room temperature hardness of powder metallurgy HSS
can increase 1–1.5 HRC or more. The high temperature hardness (at 550–600 °C)
can be also significantly improved, with the high durability.
7.1.3 Plasma Surface Metallurgy HSS
Plasma surface metallurgy HSS is formed by adding alloy element W, Mo, Cr, V,
Ti, Co, and C into the surface of low-carbon steel or low-carbon alloy steel, to
acquire the composition close to that of HSS. The surface HSS has no coarse
eutectic carbide segregation. The carbides are fine and dispersed as granular sec-
ondary carbides (<2 lm) precipitating from the solid solution. Fine carbides are
easier to dissolve in austenite during subsequent quenching and the potential of
alloy elements can be fully released. After tempering treatment, the surface prop-
erties of plasma surface metallurgy HSS are much better than that of conventional
metallurgy HSS.
Plasma surface metallurgy HSS can be used just like a bulk HSS. Since the
alloying elements are only added into the surface layer of the steels, the con-
sumption of alloying elements (e.g., W, Mo, etc.) tremendously drops compared to
the bulk HSS material. Surface HSS can greatly save the valuable alloying elements
and cut the material cost, compared with the conventional metallurgy HSS and
powder metallurgy HSS.
7.1 High-Speed Steels (HSS) 111
Plasma surface metallurgy HSS can be regarded as the third generation of

high-speed steel, where the conventional HSS is the first generation and the powder
metallurgy HSS is the second generation.
7.2 Plasma Surface Metallurgy W–Mo HSS
In 1985, based on plasma surface W–Mo alloying, a W–Mo HSS-alloyed layer has
been successfully produced on the surface of low-carbon steel by the Xu-Tec
process.
7.2.1 Plasma Surface W–Mo Alloying
High W–Mo-alloyed layer has been formed on the surface of low-carbon steel or
low-carbon alloy steel by Xu-Tec which has been described in Chap. 6. The
alloying layer is ɑ-Fe solid solution with W and Mo gradually distributed. Because
the composition smoothly changes from the surface to the matrix, the interface
binding issue between the alloyed layer and the matrix is eliminated, and also no
peeling or cracking occurs [1–5].
The typical plasma surface alloying parameters range as the following:
• Source material: powder metallurgy W–Mo alloy plate,
• Working gas: Argon,
• Working gas pressure: 20–60 Pa,
• Source voltage: 600–1100 V,
• Workpiece voltage: 200–600 V,
• Alloying temperature: 950–1200 °C,
• Alloying time: 1–6 h.
Figure 7.1 shows the cross-sectional microstructure and the composition depth
distribution of a W–Mo-alloyed layer on Steel-1020. The thickness of the alloyed
layer is about 200 lm. W–Mo content drops slowly in the alloyed layer with the
maximal value of 5.0 wt% W and 14.0 wt% Mo at the surface.
It is generally required that W and Mo contents of W–Mo HSS surface formed
by Xu-Tec process are falling in a range as W at 2–5 wt%, Mo at 8–14 wt%.
According to the calculation formula of tungsten equivalent of conventional HSS,
1.0 wt% Mo is equivalent to 1.6–2 wt% W. Tungsten equivalent of all alloy ele-
ments in conventional HSS generally exceeds 12 wt%. To meet the composition
requirements of HSS, the alloyed layer needs at least 2 wt% W and 7 wt% Mo.
Fig. 7.1 a Microstructure and b W–Mo distribution of an alloyed layer on Steel-1020 [1]
7.2.2 Carburizing, Quenching and Tempering
After plasma W–Mo alloying, carburizing must be conducted to make the

surface-alloyed layer acquire the necessary carbon content. Gas carburizing or
plasma carburizing can be used.
For the surface W–Mo HSS with 5 wt% W and 14 wt% Mo, the required carbon
content wC can be calculated by the balance carbon calculation principle as follows
[1, 6]:
wC = 0:033 5 + 0:063 14 ¼ 1:047 wt% ð7:1Þ
Carburizing process parameters are as follows: carbon potential 1.2–1.4%,

temperature 860–920 °C, holding time 4–5 h. After carburizing, it is normally
followed by 860 °C isothermal treatment and 20# hot oil quenching. Quenching
temperature range of plasma surface W–Mo HSS is generally 1180–1230 °C.
Tempering temperature range in the secondary hardening is generally 540–560 °C.
Tempering is usually conducted for two times.
Figure 7.2 shows the carbide morphologies of plasma surface W–Mo HSS and
conventional W–Mo HSS. It is very obvious that the plasma surface W–Mo HSS
possesses fine and uniformly and dispersedly distributed granular carbide particle in
less than 2 lm in diameter, much smaller than that in the conventional HSS.
After all of the above-mentioned quenching and tempering processes, surface
hardness can reach 800–1200 HV0.1. Tempering stability is stable and the red
hardness can maintain at 720HV0.1 (60HRC) after 4 h tempering at 620 °C.
7.3 Plasma Surface Metallurgy Aging Hardening HSS 113
Fig. 7.2 a Carbide morphologies of plasma W–Mo HSS and b conventional W–Mo HSS [6]
7.3 Plasma Surface Metallurgy Aging Hardening HSS
7.3.1 Aging Hardening HSS and Its Excellent Cutting

Performance
Aging hardening HSS first appeared in 1926. Aging hardening HSS contains a large
number of W–Mo–Co precious metal elements and strengthened by (Fe, Co)7(W,
Mo)6 intermetallic compounds, with very low-carbon content or no carbon. Its
hardness is at 67–68 HRC. The temper resistance is around 100 °C more than
conventional HSS. Its red hardness is between super-hard HSS and cemented
carbide. The steel also possesses good thermal conductivity. The durability of
W11Mo7Co23 type aging hardening HSS is 30–40 times longer than T1 HSS, 8–10
times longer than BK8 cemented carbide when cutting titanium alloy, 10–20 times
longer than cobalt HSS when cutting austenitic steel and refractory metal. It is one
of the best tooling materials to cut the hard cutting materials, such as titanium alloy
and nickel alloy [7, 8].
Plasma surface metallurgy aging hardening HSS is prepared by Xu-Tec process
with W–Mo–Co alloying and subsequent solid solution and aging treatments. In
order to meet the requirements of different matrix strength, base materials with
different carbon content such as industrial pure iron, Steel-1020, Steel-1045, and
Steel-1080 were used. The source materials are designed with the composition as
W35Mo15Co50 and prepared by the powder metallurgy method [9, 10].
7.3.2 Plasma Surface W–Mo–Co Alloying
The typical plasma surface alloying parameter ranges are as the following:
• Source material: W35Mo15Co50 powder metallurgy plate,
• Argon gas pressure: 30–50 Pa,

• Working-piece voltage: 400–700 V,
• Distance between the workpiece and the source: 15 mm,
• Alloying temperature: 950–1200 °C,
• Alloying time: 2–8 h.
Figure 7.3 gives the cross-sectional microstructure and alloy composition depth
element distribution in the alloyed layer on an iron substrate after Xu-Tec W–Mo–
Co alloying at 1100 °C for 6 h. The alloyed layer possesses a multilayer structure,
including the deposition layer, diffusion layer, and matrix.
The deposition layer possesses very high W–Mo–Co element content, with the
total content of 90 wt% near the surface and 50 wt% near the interface of the
deposition/diffusion layers. The distribution of Fe content is in opposite, 10 wt%
near the surface and 50 wt% near the interface of the deposition/diffusion layers.
The existent of Fe in the deposition layer will be beneficial to reduce the brittleness
of the deposition layer. W–Mo–Co content in the diffusion layer is much lower than
that in the deposition layer, but the distribution is very flat. The maximal content of
W, Mo, and Co in the diffusion layer is about 11, 7, 20 wt%, respectively, similar
with the aging hardening HSS.
XRD spectra, shown in Fig. 7.4, indicate that the diffusion layer is a solid
solution of W, Mo, Co in ɑ-Fe. The fine dispersive precipitates are (Fe, Co)7(W,
Mo)6 type intermetallic compounds (µ-phase). The deposition layer is the ɑ + µ
double phase structure, but the content of µ-phase is much higher than that in the
diffusion layer.
Due to a large amount of µ-phase precipitates (with the hardness of
1295 kg/mm2) in the deposition layer, its hardness reaches 1200–1300 HV0.025,
while the hardness of the diffusion layer is 200–450 HV0.025 because of less µ-
phase precipitates than in the deposition layer. The hardness gradually declines in
Fig. 7.3 a Microstructure and b Fe, W, Mo, and Co distribution of an alloyed layer on a pure iron
after 1100 °C 6 h W–Mo–Co alloying [9]
Fig. 7.4 XRD spectrum of a a diffusion layer; b a deposition layer [10]
an alloyed layer, but the minimum hardness is still higher than the matrix hardness
of 170–180 HV0.025.
7.3.3 Decarburization and Its Effect on Microstructure
When the carbide forming elements (such as W, Mo, V, and Ta) are used for plasma
surface alloying of medium and high-carbon steels by the Xu-Tec process, surface
decarburization sometimes may occur. During the process, the ion bombardment
decomposes carbides and makes the carbon atoms escape from the working-piece
surface. If this process is repeated, the carbon content in the working-piece surface
will decrease to form a gradient distribution in the substrate, thus the internal carbon
atoms will keep diffusing towards the surface. After a period of time, due to the
carbon content loss at the carbon steel surface, a decarburized layer will form in the
surface layer.
A different degree of decarburization can occur when W–Mo–Co alloying on
Steel-1045 and Steel-1080. Upon the influence of the carbon content in a carbon
steel and different alloying elements, the following three different types of
microstructures can be formed in the plasma-alloyed layer.
1. If decarburization seriously takes place in the substrate surface during alloying,
an a-Fe solid solution alloy layer that is similar to that on low-carbon steel and
industrial pure iron will be formed as is shown in Fig. 7.5. Besides the µ-phase,
it also contains a small amount of M6C carbides.
2. If a partial decarburization occurs in the substrate surface during alloying, a
pearlite alloy layer will be formed, as shown in Fig. 7.6. The pearlite alloy layer
is composed of dark pearlites and a small amount of white pro-eutectoid ferrites,
strengthened by the precipitates of M6C and µ-phase, is shown in Fig. 7.7. Its
hardness is 350–500 HV0.025, similar to a half aging hardening HSS.
Fig. 7.5 a Microstructure and b Fe, W, Mo, and Co distribution of a solid solution alloy layer on
Steel-1045 [10]
Fig. 7.6 a Microstructure, b depth distribution of Fe, W, Mo, and Co content, and c C distribution
of the carbide layer and the pearlite layer on Steel-1080 [10]
Fig. 7.7 XRD spectrum of a pearlite layer on Steel-1080 [10]
Fig. 7.8 a Microstructure, b depth distribution of Fe, W, Mo, and Co content, and c C distribution
of carbide layer on Steel-1080 [11]
3. If decarburization of substrate surface is strictly controlled during alloying, a

carbide layer will be formed. The carbide layer possesses excellent corrosion
resistance, shown in Fig. 7.8 as a bright white layer. After alloyed at 1100 °C
for 4 h, the thickness of the alloy layer is 21.5 µm. When Steel-1080 is alloyed
Fig. 7.9 XRD spectrum of a

carbide layer on T8 steel [11]
at 1100 °C for 6 h, the thickness of the alloy layer is 47.67 µm. Contents of
W, Mo, Co, and C are very high in the carbide layer. The main phases are
M6C + MC type carbides. Its hardness is about 1300–1400HV0.025. Figure 7.9
is an XRD spectrum of the carbide layer on T8 steel.
High degree of decarburization will cause poor carbon in matrix and affect
matrix properties. Low degree of decarburization will cause carbide layer or pearlite
alloy layer formed on the surface of the steel.
7.3.4 Solid Solution and Aging Treatment
As is mentioned above, the solid solution alloy layer belongs to aging hardening
HSS and the pearlite alloy layer belongs to half aging hardening HSS.
Figure 7.10a shows a solid solution alloy layer on Steel-1045, processed at
1240 °C for 5 min and isothermal aging treated at different temperature of 550,
600, 650 °C, respectively. Figure 7.10b shows the isothermal aging hardening
curves. It can be seen that the solid solution alloy layer possesses a strong age
hardening ability; the best aging process is 600 °C 80 min. Figure 7.10c gives
the hardness distribution curves of the alloyed surface layer after the solid solution
process at 1240 °C and aging at 600 °C for a different time. The hardness after
alloying is 300–400HV0.025. After solid solution, the hardness has no obvious
change. After aging at 600 °C for 20 min, the surface hardness increases to
980HV0.025. Then the hardness slowly rises with the aging time and reaches the
maximum of 1150 HV0.025 at the aging time of 80 min. It enters over-aging state
and the hardness begins to drop. The hardness gradiently declines. At the optimized
aging state, the hardness is 1150 HV0.025 at the surface, 900 HV0.025 at 50 lm depth
and 600 HV0.025 at 100 lm depth.
Figure 7.11a shows a pearlite alloy layer on Steel-1080 which is solid solution
treated at 1240 °C for 5 min and isothermal aging treated at 550, 600, 650 °C,
Fig. 7.10 a Solid solution alloy layer on Steel-1045, b isothermal aging hardening curve and
c hardness distribution curves [12]
respectively. Figure 7.11b shows the isothermal aging hardening curves. The
pearlite alloy layer also possesses a strong age hardening ability, the best aging
process is 600 °C 60 min. Figure 7.11c gives the hardness distribution curves of
alloy layer after alloying, 1240 °C solid solution, 600 °C aging for 60 min. The
hardness of alloy layer is 350–500 HV0.025 after alloying and increases to 580
HV0.025 after solid solution treatment. After the aging treatment, the surface
hardness sharply rises to 1000HV0.025. The hardness gradiently declines in alloyed
layer and, at the optimized aging state, the hardness is 1000 HV0.025 at the surface,
890 HV0.025 at 20 lm depth and 750 HV0.025 at 45 lm depth.
The temper softening resistances of the above samples with the best aging
treatment were tested. The solid solution alloy layers were tempered at 600, 700 °C
for 1, 2, and 4 h, respectively. The hardness declines to 800 HV0.025 after
600 °C 4 h tempering, and to 700 HV0.025 after 700 °C 4 h tempering. The
pearlite alloy layers were tempered at 550, 600, 650, and 700 °C for 4 h, respec-
tively. The hardness decreases to 850HV0.025 after 600 °C 4 h tempering, and to
650HV0.025 after 700 °C 4 h tempering. The temper softening resistance of the
pearlite alloy layer is stronger than that of solid solution alloy layer at lower temper
temperature of 600 °C, but weaker than that of the solid solution alloy layer at
Fig. 7.11 a Pearlite alloy layer on Steel-1080, b isothermal aging hardening curve and c hardness
distribution curves [10]
higher temper temperature of 700 °C. This is because more carbide precipitates
improve dispersion hardening effect through the higher resistance aggregation at
low temperature. The weaker resistance aggregation ability of carbides at high
temperature decreases dispersion hardening effect in the pearlite alloy layer.
Using the double glow plasma surface alloying technology, we have success-
fully prepared surface alloy layers with composition and microstructure similar to
aging hardening HSS and half aging hardening HSS on the surface of industrial
pure iron, Steel-1020, Steel-1045, and Steel-1080. These two kinds of plasma
surface aging hardening HSS have strong age hardening ability and temper soft-
ening resistance.
7.4 Plasma Surface Metallurgy W–Mo–C HSS
Based on plasma surface metallurgy W–Mo HSS, W–Mo–C HSS was directly
formed on low-carbon steel surface by plasma W–Mo–C alloying. During W–Mo–
C alloying, in addition to Argon gas, carbon–hydrogen mixture gas, such as
methane, is also added to generate carbon and hydrogen plasma. Thus, W–Mo
7.4 Plasma Surface Metallurgy W–Mo–C HSS 121
atoms sputtered from the source and carbon atoms generated in the plasma can
interact and simultaneously diffuse into the steel surface to form W–Mo–C HSS.
The optimal process parameters are as follows [13]:
• Source material: powder metallurgy W–Mo plate,
• Substrate material: low-carbon steel,
• Working gas: Ar: CH4 = 1:1,
• Gas pressure: 45 Pa,
• Workpiece voltage: 450–550 V,
• Alloying temperature: 1100 °C,
• Alloying time: 3 h,
• Ratio of time of different stages: 2/1(W–Mo alloying/W–Mo–C alloying)
The depth distributions of W, Mo, C content in such an alloyed layer are shown
in Fig. 7.12. The tungsten equivalent of W + Mo surpasses 12 wt%, the carbon
content exceeds the requirement of carbon balance principle, at 1.2–1.3 wt%.
Plasma surface metallurgy W–Mo–C HSS can be directly quenched in situ after
alloying treatment, followed by tempering treatment, as is shown in Fig. 7.13.
Plasma surface metallurgy W–Mo–C HSS possesses obviously secondary
hardening during 550 °C tempering. The hardness after 620 °C 4 h tempering
surpasses 700 HV, equal to that of W–Mo HSS.
It should be noted that the HSS formed by W–Mo alloying and carburizing is
called plasma surface metallurgy W–Mo HSS, the HSS formed by W–Mo–C
alloying is called plasma surface metallurgy W–Mo–C HSS. The former is more
mature and has been successfully applied to saw blade treatment, colloid mill, and
other industrial products.
Fig. 7.12 Depth distribution of a W and Mo contents and b C content in the alloyed layer [13]
W-Mo-C alloying Quenching Tempering
Fig. 7.13 Preparation process of plasma surface metallurgy of W–Mo–C HSS [13]
7.5 Plasma Surface Metallurgy W–Mo–Ti HSS
Titanium can form the stable compound of TiC with carbon in the steel substrate.
TiC possesses very high hardness and high wear resistance among all carbides. If
TiC dissolves into c-phase during quenching and dispersed precipitate in the form
of carbides during tempering, secondary hardening will occur and can greatly
increase hardness, red hardness, and wear resistance of HSS. Recent studies have
shown that hardness of M7 casting HSS surpasses 66 HRC, while the bending
strength and impact toughness also significantly increase when replacing 1/3 W and
Mo with 0.8 wt% Ti.
Based on W-Mo alloying process, plasma surface metallurgy W–Mo–Ti HSS
was formed on carbon steel surface by W–Mo–Ti plasma surface alloying.
7.5.1 Plasma W–Mo–Ti Alloying
The source structure is a multiple hollow cathode sputtering target made of

30 wt% Ti, 30 wt% W, 40 wt% Mo. The optimized process parameters are listed
as following [14]:
• Argon gas pressure: 60 Pa,
• Source voltage: 1000 V,
• Workpiece voltage: 500 V,
• Distance between the workpiece and the source: 20 mm,
• Alloying temperature: 1000 °C,
• Alloying time: 2 h.
The microstructure of the alloyed layer formed by W–Mo–Ti alloying is related
to carbon content in the surface layer. A pearlite alloy layer is generally formed on
the surface with the C content of more than 0.2 wt%. At a low working-piece
voltage, a deposition layer is usually formed on the top of pearlite alloy layer or just
a ferrite alloy layer. Otherwise a ferrite alloy layer will be formed at a lower C
content.
Figure 7.14a gives the depth distribution of W–Mo–Ti content in the alloyed
layer. The total content of W–Mo–Ti is about 80 wt%, including 17 wt% W, 30 wt
% Mo, and 32 wt% Ti. The content ratio of three elements is very similar to that of
the source target. Figure 7.14b indicates the distribution of Mo–W–Ti of ferrite
alloy layer formed in a low-carbon steel. In the diffusion layer, Mo content is about
7.5 Plasma Surface Metallurgy W–Mo–Ti HSS 123
Fig. 7.14 a W, Mo, and Ti distribution curves in the deposition layer + pearlite layer and b in a
ferrite layer [14]
Fig. 7.15 X-ray diffraction spectrum of alloy layer after W–Mo–Ti co-diffusion + carburizing
[15]
15 wt%, W is 12 wt%, and Ti content is low at only 1.8 wt%. In order to obtain
high Ti content, the content ratio of Ti in the source material must be increased.
7.5.2 Carburizing
In order to obtain the required carbon content of HSS, carburizing is needed after
W–Mo–Ti alloying. The conventional atmosphere carburizing furnace was used for
carburizing. The process parameters are as follows: heating temperature 920 °C,
carbon potential 0.9%, holding time 4 h, cooling in the furnace.
The XRD spectrum is shown in Fig. 7.15, illustrating that the carbides formed in
the alloyed layer after carburizing are M3C (Fe3C), M6C (Fe3W3C) and MC (TiC,
c-MoC, WC) type.
7.5.3 Quenching and Tempering
W–Mo–Ti HSS is generally quenched at 1180–1260 °C and tempered at 540–560 °C

for two times with air cooling. The alloyed layer after quenching and tempering is
composed of tempered martensite and uniformly distributed fine granular carbides
with diameter less than 2 lm. XRD spectrum in Fig. 7.16 shows that carbides are in
the forms of M6C(Fe3W3C), M7C3[(FeWMo)7C3] and MC(TiC, c-MoC).
The hardness of the alloyed layer is 800 HV0.1 after 1240 °C quenching, slightly
higher than the conventional HSS. The 560 °C tempering hardness is 900 HV0.1
(about 67HRC), showing secondary hardening. Surface hardness can maintain at
760 HV0.1 after 600 °C 4 h tempering, also showing a high red hardness.
7.6 Plasma Surface Metallurgy Mo–Cr Low Alloy HSS
Mo–Cr low alloy HSS possesses less alloy content, lower quenching temperature,
higher carbide dissolution, but its properties are similar to HSS.
Plasma surface Mo–Cr low alloy HSS is studied in order to reduce quenching
temperature. Plasma surface metallurgy Mo–Cr low alloy HSS is formed first by
Mo–Cr alloying, then plasma super saturated carburizing to acquire the needed
composition [15, 16].
Microstructure and Mo–Cr distributions in an alloyed layer formed on
low-carbon steel are shown in Fig. 7.17. Mo–Cr-alloyed layer is composed of an
Fig. 7.16 X-ray diffraction spectrum of alloying layer after quenching and tempering [15]
7.6 Plasma Surface Metallurgy Mo–Cr Low Alloy HSS 125
Fig. 7.17 a Microstructure and b Mo–Cr content distributions in Mo–Cr alloyed layer [16]
a-Fe solid solution with the columnar structure. Some columnar crystals connect
directly with the matrix crystals and grow through reaction diffusion by maintaining
the crystallographic orientation of the substrate. The depth of alloyed layer is about
90 lm with 12 wt% Mo and 4 wt% Cr at the surface, then slowly decline in depth.
Super-saturated plasma carburizing process was conducted at temperature much
lower than the solid phase line. Argon was used as the carrier gas in carburizing and
the flow rate was fixed. Carbon partial pressure in furnace atmosphere was con-
trolled by changing the methane flow rate. Carbon content of Mo–Cr-alloyed layer
after carburizing treatment is 1.42–2.26 wt%. Carbides in the alloyed layer are
uniformly distributed in tiny short rods or granular particles. XRD spectrum in
Fig. 7.18 shows that the carbides are Cr23C6, Cr7C3, Mo2C, and Mo6C types.
After Mo–Cr alloying and carburizing, quenching at low temperature 980–
1050 °C and tempering at low temperature 180 °C are usually required. When the
Fig. 7.18 XRD spectrum of the alloying layer after Mo–Cr co-diffusion + carburizing
red hardness is needed, high temperature quenching and high temperature tem-
pering should be conducted to increase the amount of carbide precipitation. After
1050 °C quenching and 180 °C tempering, surface hardness reaches 1300 HV0.025;
surface hardness can maintain at 750 HV0.025 when tempering at 600 °C, exhibiting
excellent temper resistance.
7.7 Conclusion and Prospects
Among three generation HSS processes introduced in this chapter, we have

demonstrated that the plasma surface metallurgy HSS by Xu-Tec process has many
advantages over other two generation processes.
1. By the double glow plasma surface alloying technology (Xu-Tec) and carbur-
izing, various types of conventional HSS can be formed on the surface of the
low-carbon steel.
2. In order to avoid the diffusion hindrance of carbide forming elements and
increase the surface alloy layer thickness, we usually adopt low-carbon steel as
the substrate material. However, after the alloying treatment, carburizing must
be carried out in order to transfer it into a HSS phase.
3. Aging hardening HSS has excellent cutting performance, but its mechanical
performance is poor. In a bulk form, it contains a lot of expensive alloy ele-
ments, so that the application of such bulk HSS materials is limited. When the
surface metallurgy aging hardening HSS is produced by the Xu-Tec process,
these problems could be easily solved, where the surface HSS layer gives high
cutting performance and the matrix steel maintains good mechanical
performance.
4. All plasma surface metallurgy HSS show many unique advantages including
high quality by very fine carbide (<2 lm) with no segregation, low consumption
of precious metal elements, low cost and high surface performances. In this
respect, the Xu-Tec HSS has very good development prospect in the future.
References
1. Xu Z, Wang CZ, Su YA (1988) Application research of plasma tungsten-molybdenum

alloying technology on the saw blade. Heat Treat Met 3:13–19
2. Wang CZ, Su YA, Tang B (1990) The microstructure of alloyed layer treated by double layer
ionized W, Mo metalizing and its formation mechanism. Heat Treat Met 2:22–28
3. Gao Y, Liu XP, He ZY (1998) Alloying elements in W–Mo ionized alloy hacksaw blades and
their cutting performance. Acta Armamentarii 19(4):331–334
4. Gao Y, Liu XP, He ZY (2000) An analysis on microstructures of alloyed layer by double
glow plasma W–Mo alloying process after carburizing. TNMSC 10(1):55–58
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5. Xu Z, Wang CZ, Su YA (1999) Xu-Tec hacksaw blades versus bimetal hacksaw blades.
J Adv Mater 31(1):3–6
6. Gao Y, Liu XP, He ZY (2000) An analysis on microstructures of alloyed layer by double
glow plasma w-mo alloying process after carburizing. Chin J Nonferrous Met 10(1):55–58
7. Li ZH, Liu XP, Gao Y (1999) Surface metallurgical technique of Fe–W–Mo–Co age hardened
alloy(I). TNMSC 9(4):790–793
8. Li ZH, Liu XP, Gao Y (2000) Characteristics of surface age-hardening of Fe–Co–W–Mo
surface age-hardening alloy(II). TNMSC 10(1):50–54
9. Zhang YM, Jie XH, Li ZH, Xu Z (2010) Formation mechanism of alloyed layer with W, Mo,
Co Co-diffusion in pure iron. Adv Mater Res 154–155:1817–1821
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Co alloying. Taiyuan University of Technology, Taiyuan
11. Zhang YM, Jie XH, Li ZH, Xu Z (2011) Friction and wear properties of W, Mo, Co alloyed
layer on T8 steel by double-glow technique. Adv Mater Res 189–193:1071–1074
12. Zhang YM, Liu YP, Li ZH, Xu Z (2005) Surface age-hardened high speed steel with high Co
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13. Gao Y (2003) Research on surface low alloy HSS by plasma surface metallurgy W, Mo, C
alloying process. Taiyuan University of Technology, Taiyuan
14. Wang CZ, Su XK, Ma J (2004) Characteristics of double glow plasma W–Mo–Ti alloying on
steel surface. Heat Treat Met 29(3):16–20
15. Liu Q (2002) The research on metallurgical HSS on surface containing Ti obtained by Xu-Tec
and wear behavior of the MHSSST. Beijing University of Technology, Beijing
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and its performance. Hot Work Technol 2:27–29
Chapter 8
Plasma Surface Metallurgy of Titanium
and Titanium Alloys
Abstract Titanium, known as the “aerospace material” or “marine material,” is an

indispensable material in the modern industry. Due to its low hardness and poor
thermal conductivity, the surface of titanium is prone to adhesion under a friction
condition. In some special media, the passivation film on the titanium surface loses
its protective ability and shows the strong chemical activity. As a consequence,
proper surface modification for its physical, chemical, or mechanical property
change is required for some specific applications. This chapter is to introduce
Plasma Surface Metallurgy on Titanium matrix and Titanium Alloys by the double
glow plasma surface alloying technology to enhance wear-, corrosion- and flame
resistance.
8.1 Introduction to Titanium and Titanium Alloys
Titanium is the fourth most abundant structural metal in the crust of the earth after
aluminum, iron, and magnesium. The development of its alloys and processing
technology started only in the late 1940s.
Titanium element was discovered in 1791. In 1908, Norway and USA started
producing titanium dioxide by the Sulfate Process. In 1910, sponge titanium was
first prepared by Sodium Method in the laboratory. In 1948, mass production of
sponge titanium was achieved by US DuPont Company with using the Magnesium
method. Afterward, titanium had begun to be wildly used as an important metallic
structural material. With further studies, people realized that titanium is a major
functional material as well.
8.1.1 Classification and Properties
There are two allotrope forms of titanium: a- Ti at 882.5 °C or lower, with a

close-packed hexagonal (hcp) lattice structure and b-Ti at 882.5 °C or higher with a
DOI 10.1007/978-981-10-5724-3_8
130 8 Plasma Surface Metallurgy of Titanium and Titanium Alloys
body-centered cubic (bbc) lattice structure. Upon the phase structure and the con-
tent of b stable element, Titanium alloy is classified into three categories: a, a+b,
and b. Upon the mechanical characteristics of titanium alloy, it can be further
divided into: corrosion-resistant titanium alloy, heat-resistant titanium alloy, low
temperature titanium alloy, structural titanium alloy, bio titanium alloy,
flame-resistant titanium alloy, etc.
Titanium and titanium alloy exhibit several unique properties and have been
widely used in the field of chemical industry, aviation, aerospace, marine, and
medical devices as regular supplies since 1950’s.
Main physical properties of titanium and titanium alloys include:
(1) Low density and high specific strength: The density of Ti is 4.51 g/cm3 with
tensile strength up to 1300 MPa. The specific strength is much higher than that
of aluminum and alloying steel, the highest among metal materials;
(2) Good heat resistance: Some new types of titanium alloys can be used for a long
time at 600 °C or higher, and is suitable for the aviation and aerospace
heat-resistance components;
(3) Good low temperature resistance: At temperature of −196 to −253 °C, titanium
maintains relatively good ductility and toughness. These make Ti to be an ideal
material for cryogenic vessels, and tank equipments;
(4) Good corrosion resistance: Ti is very stable among many media. For example,
Ti is corrosion resistant in the medium of oxidation, neutral, and weak
reduction.
However, as is listed below, Titanium also has some drawbacks along with its
aforementioned advantages.
(1) Low wear resistance: The low surface hardness of titanium makes the adhesive
wear easy to occur;
(2) Low oxidation resistance at high temperature: Titanium shows a strong ten-
dency of oxidation at a temperature of 350 °C or higher. The higher the tem-
perature is at, the higher degree of oxidation would occur;
(3) High cost: the price of titanium is about 5–10 times higher than that of the
stainless steel.
8.1.2 Effect of Alloying Elements
As discussed above, the intrinsic characteristics of titanium alloy determine its low
hardness, poor thermal conductivity, and prone to adhesion in friction. Therefore, in
many practical applications, the surface modification must be carried out to improve
their tribological property, when titanium parts are working under the condition of
friction and wear.
8.1 Introduction to Titanium and Titanium Alloys 131
Pure titanium metal has good corrosion resistance and biocompatibility, but its
mechanical strength is low. In order to meet the requirements for the structure
application, some other elements need to be added into titanium to form titanium
alloys with improved properties. Aluminum is the typical a-phase stable element
and most widely used in titanium alloy. In addition, carbon, nitrogen and oxygen
are also typical a-phase stable elements. In plasma surface metallurgy technology,
Al, C, N, and O are often used for plasma alloying treatment to improve the
strength, heat resistance, corrosion resistance, and wear resistance of titanium
surface.
According to the characteristics of the phase diagram, b-phase stable elements
can be divided into b-eutectoid elements and b-amorphous elements. b-eutectoid
elements, including Mn, Fe, Cr, Si, Cu, Co, Ni, W, and Ag, etc., have the limited
solid solubility in a- and b- phase. The positions of b- amorphous elements
including Mo, V, Nb, and Ta, etc. in the periodic table, are close to titanium, and
the lattice type of these elements is similar to that of titanium. They have the
unlimited solid solubility in b-titanium. In the plasma surface metallurgy process,
these elements can be used to improve the strength of the alloy while maintaining
high plasticity. There is no brittle phase generated by eutectoid or peritectoid
reaction in the alloyed layer. The structural stability is outstanding.
Hydrogen is rather a special element, falling into the gap element in the b-phase
stable element group. It can reduce the allotropic transition temperature, generate
eutectoid reaction, and form hydrogen composition gap solid solution. The solu-
bility of hydrogen in b-titanium is higher than that in a-titanium. The dissolved
hydrogen precipitates at room temperature and forms brittle TiH2, which makes
titanium brittle. This is so-called “hydrogen embrittlement.” In plasma surface
metallurgy technology, carbon vaporization is generated by solid graphite as the
target material. The existence of pure carbon overcomes the reaction of hydrogen in
traditional carburizing technology.
8.1.3 Optimal Alloying Parameters
In last 20 years, the double glow plasma surface alloying technique has been used
to prepare high-performance titanium surface-alloyed layer with high corrosion
resistant, wear resistant, flame resistant, and antioxidant and gives new properties to
titanium besides the original high specific strength. The superiority of the double
glow discharge technology in preparation of surface-alloyed layer has been
demonstrated.
The substrate materials are often selected among fully annealed and solid strengthen
Ti-alloy materials, such as TC4: (Ti6Al4 V), TC11: (Ti6.5Al3.5Mo1.5Zr0.3Si) and
industrial pure titanium TA1, TA2, and TA3.
The high purity metals or alloys are often selected as the source material, such as
high purity Pd, Nb, and Mo. High purity argon is often used as a gas source for
glow discharge plasma media. If the discharge gas is required to participate in the
reaction, high purity nitrogen is added. Both the working—pieces and the source
electrode are biased with negative potential by two DC power supplies. Typical
process parameters are set as:
• Background vacuity: better than 1 10−3 Pa,
• Gas pressure: 20–40 Pa,
• Discharge gas: Chemical pure argon or mixture of argon and nitrogen,
• Distance between workpiece and source electrode: 10–30 mm,
• Source electrode bias voltage: 800–1200 V,
• Workpiece electrode bias voltage: 600–1000 V.
The bias voltages on the working-piece and on the source electrode affect
directly the source sputtering yield for alloying element supply, as well as the
operation temperature on the working-piece for the diffusion rate control of alloying
elements. Therefore, in the whole process, the relationship between the voltage of
the workpiece and source electrode needs to be coordinated.
Through the aforementioned Xu-Tec process, the wear resistant of Ti–Mo, Ti–
Mo–N, and Ti–C-alloyed layers, flame resistant of Ti–Cu, Ti–Cr, and Ti–Cr–
V-alloyed layers, corrosion resistant of Ti–Pd and Ti–Nb-alloyed layers can be
formed on the surface of titanium and titanium alloy.
8.2 Plasma Surface Metallurgy Wear-Resistant Alloys
The research activities on plasma surface alloying of titanium alloys began in 1997.
Surface treatments on titanium alloys with molybdenizing, niobizing, chromizing,
nitriding, carburizing, oxidizing, and composite molybdenitriding, carbonitriding
have been adopted for experiments and applications for improving the surface
hardness and wear resistance.
8.2.1 Double Glow Plasma Molybdenizing
Molybdenum (Mo) has the same crystal lattice structure and similar atomic radius
with titanium. As a b-phase stable element, Mo is an unlimitedly solid-dissolved
element in b-phase with reduced b transition temperature, widely expanded b phase
region, and good stability. Using pure Mo material as a source electrode in the
Xu-Tec process, a Mo alloy layer can be formed on the surface of a titanium alloy
substrate [1, 2].
Figure 8.1 shows the microstructure of the Mo surface alloy on Ti6Al4V alloy
substrate by the molybdenizing process at 950 °C, together with the depth distri-
bution of Mo, Ti, V, and Al in the surface-alloyed layer. The alloyed layer on the
8.2 Plasma Surface Metallurgy Wear-Resistant Alloys 133
titanium surface is composed of a deposition layer and a diffusion layer, with the
total thickness of about 28 lm. From the depth profile analysis, it can be seen that
the top surface layer is mainly Mo, with a thickness of about 15 lm. In the fol-
lowing diffusion layer, the content of Mo is gradually decreased, and the thickness
is about 13 lm. It is also further found that, because the molybdenizing process is
carried out under high temperature, Al and V in the original surface layer of
titanium alloy have out-diffused slightly to the top Mo deposition layer and deep
into the titanium alloy substrate respectively, leading to impoverishment of Al and
enrichment of V.
Temperature of plasma molybdenizing has a significant influence on the for-
mation of a Mo–Ti-alloyed layer. Mo content in the alloyed layer has varied with
the layer depth at different substrate temperature, shown in Fig. 8.2. It is seen that,
with the increase of temperature, the thickness of diffuse layer increases. This is
Fig. 8.1 a Microstructure and b composition distribution of Mo-alloyed layer on surface of

Ti6Al4V [1]
Fig. 8.2 Distribution of Mo

element in alloyed layer at
different operation
temperatures [1]
caused by the increase of the diffusion coefficient of Mo in the matrix at the

elevated higher temperature.
The wear resistance of molybdenized Ti6Al4 V titanium alloys was studied. The
ball-disk wear tests were operated under the condition of dry friction with 30# oil
lubrication and GCr15 hardened steel ball of U4.75 mm for friction pair couple.
Shown in Fig. 8.3 is the correlation between the friction coefficient and the sliding
distance under oil lubrication. It can be seen that, under the test condition, 30# oil
lubrication has little anti-friction effect on Ti6Al4 V titanium alloy substrate. On the
contrary, the plasma Mo-alloyed sample showed excellent friction reduction per-
formance under oil lubrication. The friction coefficient of about 0.1 was very stable
in the whole sliding distance.
Figure 8.4 gives a SEM micrograph of wear surface topography of two samples
after a sliding test for 70 min. As is seen, the grinding marks of Mo alloy samples
Fig. 8.3 Relationship between friction coefficient of Ti6Al4V substrate and Mo-alloyed sample
and sliding distance in oil lubricated condition [2]
Fig. 8.4 SEM micrographs of surface morphology of a Ti6Al4V substrate and b Mo-alloyed
sample under a dry friction test [2]
are smaller than that of the substrate Ti6Al4 V. Its adhesion and abrasion perfor-
mance were effectively improved. The wear mark zone was full of the transfer
material of GCr15 and is caused by the high hardness and elastic modulus of
molybdenum-alloyed layer and the high bonding strength between the alloyed layer
and the substrate.
Under the condition of oil lubrication, the variation of friction coefficient is very
different from that of the above-mentioned materials. The fluctuation of friction
coefficient curve of Ti6Al4 V alloy is attributed to the constant formation and
rupture of boundary lubrication films in the process of friction. In contrast, the
hardness of the plasma Mo-alloyed layer is 8.6 times higher than that of the
Ti6Al4 V substrate. When the load capacity is enhanced, the boundary lubrication
has shown some improvement with a small and stable friction coefficient. Through
the above analysis, it is concluded that after going through a plasma molybdenzing
process, the friction state of titanium alloy to GCr15 is much improved, as well as
its wear resistance and anti-friction property.
8.2.2 Double Glow Plasma Molybdennitriding
In the plasma molybdenizing, the mixed plasma with argon, nitrogen and metal ions
can be generated through the gas mixture of argon and nitrogen in the vacuum.
Under this plasma condition, a Mo-N-alloyed layer can be produced on the surface
of a titanium alloy substrate. This alloyed layer has better tribological performance
and corrosion resistance than a pure molybdenum layer [3–6].
Normally, there are two processes to form a Mo-N-alloyed layer. The typical
processing is: first molybdenizing at 830 °C for 3 h, then cooling to 810 °C,
Fig. 8.5 Microstructure after

molybdenum nitriding of
Ti6Al4V [3]
followed with plasma nitriding for 3 h with Ar: N2 ratio about 2:1. Figure 8.5 is an
optical microstructure picture of a moly-nitriding alloy layer on the surface of
Ti6Al4 V substrate. Two uniform-alloyed layers (one in white bright and another in
black) at the surface are formed by double glow plasma surface alloying technology
in a thickness of about 10 lm.
The X-ray diffraction diagram of the sample, in Fig. 8.6, shows that both the
white alloy layer and black alloy layer have included three phases: Mo-N, Mo2N,
and Mo. The white alloy layer on the surface of Ti6Al4 V consists more Mo-N and
some Mo2N and Mo. The black alloy layer was mainly formed by Mo2N with a
small amount of Mo-N. Both the layers have no matrix elements, which means no
out-diffusion of Ti from matrix and all of the outmost-alloyed layers are molyb-
denum and Nitrogen.
The hardness of the Mo–N-alloyed layer by nitriding after molybdenizing is
1804 HV, the surface hardness of sample by molybdenizing is 1681 HV, com-
paring with the hardness of original sample at 360 HV. The hardness of both layers
is substantially increased.
Figure 8.7 shows the wear rate of two plasma treated samples and the original
Ti6Al4V sample (a), with the running-in distance of 200 m. It can be seen that the
wear rate (b) of modified sample by molybdenizing decreased by 405 times, and the
wear rate (c) of nitriding after molybdenizing modified sample decreased by 1081
times. Although the friction coefficient of TC4 sample with double glow plasma Mo
+N alloying is increased, the wear rate has decreased by 2–3 orders of magnitude,
showing excellent wear resistance. The test also shows that the width of the wear
Fig. 8.6 XRD spectra

of a a white alloy layer and
b a black alloy layer [4]
Fig. 8.7 Wear rate of a Ti6Al4V, b molybdenizing and c nitriding after molybdenizing [4]
Fig. 8.8 Wear surface morphology of a Nitriding after molybdenizing and b molybdenizing for
200 m and c Ti6Al4V for 100 m [4]
trace of Ti6Al4V sample for 100 m is much larger than that of the Mo-N modified
sample for 200 m, as shown in Fig. 8.8.
8.3 Plasma Surface Metallurgy Flame-Resistant Alloys
8.3.1 Method for Protecting Titanium Alloy

from “Titanium Fire”
“Titanium fire” is a kind of combustion on titanium or titanium alloy parts, caused

by some actions, such as severe impact and friction, resulting in a certain level of
damage or destruction to the part. In essence, titanium alloy combustion or “fire” is
caused by uncontrolled oxidation at elevated temperature. SEM micrograph in
Fig. 8.9 shows such damage on titanium alloy engine parts caused by
“titanium-fire.”
In the past, to prevent “titanium fire” from happening, a great effort of devel-
oping flame-resistant titanium alloy was carried out world-widely. Flame-resistant
Fig. 8.9 Titanium alloy

parts destroyed by “titanium
fire” [1]
titanium alloy mainly consists of Ti–Cr–V series, Ti–Cu–Al series, Ti–Nb series,
and TiAl intermetallic compounds. These four kinds of titanium alloys have certain
flame-resistant properties, but they also have the following limitations [7, 8]:
(1) The increase of the density of the titanium caused by adding large amount of
heavy alloy elements makes the titanium alloy no longer has the advantage of
high specific strength.
(2) The addition of alloying elements increases the difficulty of smelting and
processing, as well as the processing cost.
(3) The high content of valuable elements, such as Nb, Cr, and V, increases the
cost of flame-resistant Ti alloys.
Facing the above problems, it was proposed to prepare the surface-alloyed layer
with flame-resistant properties by using the double glow plasma surface alloying
technology. At present, a series of surface flame-resistant alloyed layers including
Ti–Cu, Ti–Mo, Ti–Cr, Ti–Nb, etc., have been prepared on the surface of titanium
alloys by the Xu-Tec process. Compared with the flame-resistant titanium alloy,
these surface-alloyed layers have the following characteristics:
(1) The flame-resistant performance is assumed by the surface flame-resistant
alloyed layer, while its mechanical properties are assumed by the substrate
material. Hence the advantage of high specific strength of titanium alloy is
maintained.
(2) Surface alloying is carried out on the common titanium alloy parts. This
overcomes the complicity and poor performance of the integral manufacturing
process for flame-resistant titanium alloy.
(3) The thickness of the surface flame-resistant titanium alloy can be in the range of
50–300 lm, with a small consumption of alloy element materials, leading to a
significant cost saving of the flame-resistant titanium alloy.
8.3 Plasma Surface Metallurgy Flame-Resistant Alloys 139
8.3.2 Plasma Surface Metallurgy Ti–Cu

Flame-Resistant Alloy
In the view of the good flame-resistant performance of the Russian Ti-Cu alloy
series, such as TTB-1 (Ti-13Cu-4Al-4Mo-2Z) and TTB-3 (Ti-18Cu-2Al-2Mo), Cu
content in Ti–Cu surface flame-resistant alloy on the titanium alloy to be prepared
by the Xu-Tec process is designed as 13–18% [9, 10]. It can be seen from the phase
diagram of Ti–Cu shown in Fig. 8.10, when the content of Cu is greater than
13.4%, the alloy enters in the b-phase. The liquid phase precipitation takes place
when the temperature reaches 990 °C due to friction heat. On one hand, Ti alloy in
the liquid phase acts as the role of lubrication that reduces friction coefficient and
prevents heating generation. On the other hand, the precipitation of liquid phase
absorbs a lot of heating energy, which reduces the temperature of the component.
As a result, the forming compound with a low melting point on the surface of
titanium alloy not only has the function of lubrication and heat absorption due to the
precipitation of a liquid phase, but also exhibits flame-resistant effect at a high
temperature due to friction.
In the double glow plasma surface alloying process, the concentration of
alloying elements in the alloying layer is mainly determined by the solubility of the
alloying elements in the substrate metal. The higher the solubility is, the higher the
concentration of alloying elements would be. The solubility of alloying element Cu
Fig. 8.10 Ti–Cu binary phase diagram [1]

in a-Ti is only 2.1%, which cannot meet the requirement of Cu content in the
flame-resistant titanium alloy. While the solubility of Cu in b-Ti is 17%, it matches
the concentration requirement.
Figure 8.11 shows the depth distribution of Cu element concentration in a Ti–
Cu-alloyed layer formed by the plasma-driven diffusion of Cu into the Ti6Al4V
substrate. The profiling test was done by glow discharge composition analyzer. It
can be seen that Cu element follows a gradient distribution along the depth of the
surface-alloyed layer. The weight percentage of Cu in the outer surface is 14%. At
the depth of 160 lm from the surface, Cu content remains at 12%. Element con-
centration of other components is similar to those of Russian BTT-1 alloy. The
content of Cu changes continuously from the surface to the substrate, which
gradually decreases along the depth with no mutation point of Cu content. When
the time of plasma diffusion reaches 3.5 h, the average thickness of the modified
layer is more than 200 lm. There is no clear mark of the interface boundary since
the top-alloyed layer formed through Cu diffusion into the Ti substrate. The
adhesion between the surface alloying layer and the substrate is excellent with
metallurgical bonding, so that there are no bonding and adhesion issues. Thus,
surface spalling is avoided during the application.
Shown in Fig. 8.12 is the microstructure image of such a surface alloy on
Ti6Al4V at 870 °C for 3.5 h by plasma Cu diffusion treatment. The X-ray
diffraction pattern of such an alloyed layer is shown in Fig. 8.13. The study found
that the substrate is in the a + b phase. The alloyed layer consists of a + b phase
with white precipitates distributed dispersively in the layer. According to Ti–Cu
phase diagram and XRD analysis result, white precipitates are of intermetallic
compound Ti2Cu.
The melting point of is 990 °C. At a high temperature condition, Ti2Cu will go
through softening or melting before combustion. This transition is useful for the
flame-resistant property. When the content of copper is high, the eutectoid reaction
temperature rises, which is good for the growth of Ti2Cu particles, but the substrate
structure will deteriorate.
Fig. 8.11 Concentration

depth distribution of Cu in
Cu-alloyed layer on Ti6Al4V
substrate [10]
Fig. 8.12 Microstructure of

Cu-alloyed layer on Ti6Al4V
substrate [10]
Fig. 8.13 XRD spectrum of 80

a Cu-alloyed layer on
Ti6Al4V after
Cu diffusion [10] 60
intensity (cps)
40 Ti
Ti2Cu
20
0
30 40 50 60 70 80
2theta (deg.)
8.3.3 Plasma Surface Metallurgy Ti–Cr

The main reason for making titanium flammable is due to a porous structure in
oxidation compounds produced under high temperature. This porous structure
makes oxygen continue to diffuse into the substrate. When such alloying elements
form a dense layer, the diffusion of oxygen into the substrate can be stopped,
preventing the flaming of titanium bulk. Experiments showed that the oxidation
products of Cr, Mo, V, and Nb have this property [11, 12].
Figure 8.14 is a microstructure image of Cr-alloy on TC4 by plasma surface
alloying of Cr at 900 °C for 3 h [13]. The thickness of the layer is more than
100 lm. By XRD analysis, it is identified that the layer structure is an intermetallic
compound, consisting of a-phase and b-phase of Ti. Most of Cr element is dis-
solved in the b-phase, with a small amount of Cr2Ti dispersively distributed.
Fig. 8.14 Sectional

microstructure of Cr-alloyed
layer on TC4 substrate [13]
Fig. 8.15 Sectional

microstructure of a Cr-alloyed
As shown in Fig. 8.15, the same microstructure is formed in the plasma-alloyed

layer with Cr at 900 °C for 2 h on TC11 substrate.
Figure 8.16 is the composition distribution of the alloyed layer formed by Cr
alloying on TC4 substrate at 900 °C for 3 h detected by GDS test. From this
diagram, the content of Cr is 75% on the outmost surface. At the depth of 70 lm
away from the surface, the content of Cr remains above 20%. This fully meets the
requirement of Ti–Cr two-element flame-resistant titanium alloy for Cr content. It is
worth noting that, the outward diffusion of Al and V in the substrate makes the
content of Al and V in an alloyed layer substantially lower than that of the substrate.
Cr element, which severely decreases the martensitic transition temperature of
titanium alloy, is an important element for the sub-stable b titanium alloy. Titanium
and chromium form a b-phase continuous solid solution. When the content of Cr
(atom) is about 50–70%, the temperature range for the existence of b-phase solid
solution is very small, about 1350–1400 °C.
100
90
80 Ti
Ti
Ti
Ti
70
Weight Conc. [%]
60
50
40
30 Cr2
Cr2
Cr2
Cr2
20
V V V V
Al2
10 Al2
Al2
Cr
Al2
Al Cr
Al Cr
Al Al
Cr
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
Depth [µm]
Fig. 8.16 Composition Distribution in a Cr-alloyed layer on TC4 substrate [13]
The composition distribution of surface-alloyed layer on TC11 by double glow

plasma Cr alloying at 900 °C for 2 h detected by GDS test is shown in Fig. 8.17. It
can be seen that the content of Cr is 100% on the outmost surface, indicating a pure
Cr layer deposited on the surface. The thickness of the layer is 45 lm.
8.3.4 Plasma Surface Metallurgy Ti–Mo

Molybdenum (Mo) is one of the most important alloying elements for Ti alloy. Mo,
in a body-centered cubic lattice structure, can form a continuous solid solution with
b-phase Ti, which has the same crystal lattice and a limited solid solution with a-
phase Ti in close-packing hexagonal lattice structure. The solubility of Mo in a-
phase Ti is very low, no more than 0.8%. The formation of Ti–Mo alloy is a
substitutional solid solution, with a small lattice distortion. The Ti–Mo substitu-
tional solid solution with high content of Mo not only has high mechanical strength,
but also maintains high plasticity [13, 14].
Figures 8.18 and 8.19 show the microstructure images of surface alloys on TC4
and TC11, formed by plasma surface alloying with Mo element. The composition
distribution of surface-alloyed layer on TC4 alloyed with Mo after 850 °C for 3 h
100 Ti
Ti
Mn
90
Mn
Ti
80 Ti
Mn Mn
70
Weight Conc. [%]
60
50
Zn Zn
40
Zn
Zn
30
Si Si Si
Si
Cr2
20 Cr2
Al2
Al2
Al2
10
Al2 Cr2 Cr
Cr
Al Cr
Al Cr
Al Cr2
Al
0
0 5 10 15 20 25 30 35 40 45
Depth [µm]
Fig. 8.17 Composition depth distribution of a Cr-alloyed layer on TC11 substrate [13]
Fig. 8.18 Sectional

microstructure of Mo-alloyed
detected by GDS test is shown in Fig. 8.20. The outmost surface is a 3 lm

deposition layer, with Mo content of 100%. In the layer 3–30 lm from surface, Mo
element content shows a gradient distribution. Outward diffused Al is concentrated
at a distance of 15 lm from the surface due to the blocking by the deposition layer.
There exists aluminum deficit at the depth of 10 lm from the surface and the
interface between the substrate and the alloyed layer.
Fig. 8.19 Sectional microstructure of Mo-alloyed layer on TC11 substrate [14]
Fig. 8.20 Distribution of Mo in alloyed layer on TC4 substrate [13]
Figure 8.21 shows the composition distribution of surface-alloyed layer on

TC11 after plasma surface alloying at 900 °C for 3 h measured by the GDS test.
The Mo content at the outmost surface is 15%, and remains above 7% at the
position 40 lm from the surface, with a low gradient concentration. The content of
Fig. 8.21 Distribution of Mo in alloyed layer on TC11 substrate [13]
other elements is basically constant, which indicates that a uniform-alloyed layer is

formed on the surface. Mo is a strong b stable element to Ti. It can drastically
decrease the a–b phase transition temperature of titanium. For titanium alloy with
Mo content less than 11–12%, the martensite transformation occurs during the
quenching of the b region. The thickness of the layer is over 40 lm. According to
XRD analysis, Mo element completely dissolved into b-phase, and formed a sub-
stitutional solid solution.
In addition to single element diffusion, the Xu-Tec process can also be used to
prepare Cr–Mo diffusion layer to forma surface flame-resistant alloy. The compo-
sition distribution of such an alloyed layer on TC11 after Cr + Mo diffusion
treatment at 900 °C for 3 h is shown in Fig. 8.22. The content of Cr and Mo
elements is a gradient distribution. The Mo content at the outmost surface is 3 and
13% for Cr. The concentration gradients of Cr and Mo are both small. Figure 8.23
shows the microstructure of Cr + Mo alloying on TC11.
Fig. 8.22 Component distribution of Cr–Mo-alloyed layer on TC11 substrate [13]
Fig. 8.23 Sectional

microstructure of
Cr–Mo-alloyed layer on
TC11 substrate [13]
8.3.5 Plasma Surface Metallurgy Ti–Nb

Ti-45Nb is a type of corrosion-resistant and flame-resistant titanium alloy, where

oxidation products of Nb alloying element can form a dense oxidation film with
good adhesion property, thus plays a protective role for the substrate and prevent
the flaming continues to carry out. Others believe that Nb has the minimum oxi-
dation heat among all metals. Adding Nb will decrease the heat released by Ti
oxidation, thus can further prevent the combustion of Ti alloy. When Nb is diffused
into the surface of titanium alloy, an alloyed layer with high resistance to high
temperature oxidation, flame resistance, and corrosion resistance is formed on the
surface. Nb has a body-centered cubic structure. The difference between the atomic
radius of Nb and Ti is small, so the substitutional solid solution is formed with the
unlimited mutual solution of Nb and Ti [15].
The concentration distribution of alloying elements along the depth of the
Nb-alloyed layer in TC4 and TA2 examined by glow discharge spectrometer is
shown in Fig. 8.24.
As it can be seen from the Fig. 8.24, Nb element exhibits a gradient distribution
in the alloyed layer, and the weight percentage of the Nb in the surface can reach
more than 45%. A steep drop zone of Nb content exists at the place several
micrometers from the surface, followed by a gentle gradient decrease, which can
improve the supporting effect of the substrate to the alloyed layer, and enhance the
bonding strength between the layer and substrate. It is worth noting that the outward
diffusion of Al and V elements in the substrate makes the content of Al and V in
alloy is substantially lower than that of the substrate.
Figure 8.25 shows sectional SEM photos of the alloyed layers on TC4 under
typical process conditions. It can be seen from SEM photo and the comparison of
the component distribution curve, a high alloyed layer (a white bright layer) exists
on the external surface of the layer. TC4 substrate presents a net-shape.
Fig. 8.24 Element depth 80

distribution curves of TC4 Ti
Nb-alloyed layers on TC4 70 Al2
substrate [15] Ti
60
content (wt.%)
V
50
Nb
40
30
20 Nb
10 Al
0 V
0 10 20 30 40 50 60
distance from surface (µm)
8.4 Plasma Surface Metallurgy Ti–Pd Corrosion-Resistant Alloy 149
Fig. 8.25 SEM photos of

Nb-alloyed layer on TC4
substrates [15]
8.4 Plasma Surface Metallurgy Ti–Pd

Corrosion-Resistant Alloy
8.4.1 Overview of Corrosion-Resistant Titanium Alloys
In order to improve the corrosion resistance of titanium in a reduction medium, it

was added alloy elements into titanium to form corrosion-resistant titanium alloy. In
1949, W. L. FiFlay found that the Ti–Mo alloy has excellent corrosion resistance to
strong reducing acid like sulfuric acid and hydrochloric acid. In 1956, US devel-
oped Ti–(20–25)Mo–20Nb, Ti–25Mo–15V, Ti–27Mo–17V and other acid-resistant
titanium alloy. In 1958, Ti15Mo5Zr alloy was developed in Japan. In 1962, the
Soviet Union developed Ti32Mo2.5Nb and used for mass production.
Together with the study of the Ti–Mo alloy, rapid progress has also been made
in the study of Ti–Pd alloy. Both Ti–0.2Nb and Ti–0.15Nb not only have good
corrosion resistance in oxidation acids, but also have certain corrosion resistance of
the reduction acid, especially with excellent resistance to crevice corrosion.
However, due to the high price of Pd, it makes the price of Ti–Pd alloy higher
than that of pure titanium, Ti–Ru–Ni, and Ti–Ru–W(Mo) and other cheaper tita-
nium alloys. At present, Ti–Pd and Ti–Mo–Ni are two major types of titanium
alloys that are largely used [16, 17].
Because of the high price of those two types of corrosion-resistant alloys when
adding with high price elements, like Pd, Ni, and Mo, it restricts the application
usage of titanium material. Therefore, preparing corrosion-resistant Ti–Pd alloy on
the surface of Ti substrate by the Xu-Tec process becomes significant in the cost
reduction of Ti alloy as it not only solves the problem of corrosion resistance, but
also can reduce the consumption of Pd through surface treatment.
8.4.2 Plasma Surface Metallurgy Ti–Pd Alloy
Shown in Fig. 8.26 is a typical microstructure of Ti–Pd-alloyed layer produced by

plasma surface alloying with Pd source on the titanium surface. The thickness of
Ti–Pd-alloyed layer is generally greater than 50 lm, and the layer is dense and
forms a “canine”-shaped interface with a Ti substrate [15, 18].
The Ti–Pd layer is made up of four sub-layers. The layer A is the outmost layer,
with a high content of Pd and uniform thickness; the layer B is continuous, in which
the Pd content is lower that of the layer A; the layer C is very thin, and not
continuous; the layer D forms “canine” shaped interface, connecting with the Ti
substrate. Scanning electron microscopy was used to analyze the energy spectrum
(relative content of alloy elements in the layer), which is shown in Fig. 8.27a. It can
Fig. 8.26 Back scattered electron microscopy of a section of the Ti–Pd layer [18]
Fig. 8.27 a Scanning photo of sectional energy line and the scanning position of energy line [18];
b Linear scanning energy spectrum [1]
8.4 Plasma Surface Metallurgy Ti–Pd Corrosion-Resistant Alloy 151
Fig. 8.28 Phase composition

of Ti–Pd-alloyed layers
created by plasma surface
alloying process [1]
be seen that, the content of Pd varies greatly in different layers. The curve of the
content of Pd in alloyed layers is shown in Fig. 8.27b. It can be seen that in each
layer the content of Pd is linearly decreasing, with a significant reduction jump at
the interface. According to the phase diagram, there will be several layers with
different intermediate phase structures. However, in each layer, there is only one
single phase structure. On the interface of the two phases, the element content has a
distinct mutation. It can be seen that the Ti–Pd-alloyed layer formed by the Xu-Tec
process is a typical reaction diffusion layer.
According to the phase structure analysis, the surface-alloyed layer formed by
diffusion of Pd concludes many different layers as shown in Fig. 8.28. From the
surface of the substrate there are followed layer as Pd, TiPd2, TiPd3, Ti2Pd, and
substrate a-Ti.
8.4.3 Corrosion Resistance of Plasma Surface Ti–Pd Alloy
The corrosion resistance of surface Ti–Pd alloy, the crevice corrosion resistance and
erosion corrosion resistance of industrial pure titanium and Ti–0.2Pd alloy were
studied. According to the analysis, the immersion test in the 100 °C NaCl saturated
and HCl solution shows that the crevice corrosion resistance of Ti–Pd alloy is not
only superior to that of TA1 industrial pure titanium, but also better than that of Ti–
0.2Pd alloy. In another analysis, at room temperature of 25 °C, industrial pure
titanium, Ti–0.2Pd alloy and titanium surface Ti–Pd alloy are immersed in 80%
H2SO4 solution and 30% HCl solution. After the immersion test for 145 h, the
calculated corrosion rates are listed in Table 8.1. The corrosion rate of
Ti–Pd-alloyed layer on the titanium surface is only 0.682 mm/a in the 25 °C water
solution of 80% H2SO4, 1/6 of that of Ti–0.2Pd alloy and 1/20 of that of industrial
pure titanium. In the 25 °C water solution of 30% HCl, the corrosion rate of the
Table 8.1 Acid corrosion resistance of materials

Sample 80% H2SO4, 145h 30% HCl, 145h
TA1 pure titanium 13.005 mm/a 0.863 mm/a
Ti–0.2Pd 3.754 mm/a 0.032 mm/a
Ti-Pd alloyed surface Titanium 0.682 mm/a 0.004 mm/a
Ti–Pd-alloyed layer is only 0.004 mm/a, equivalent to 1/8 of that of Ti–0.2Pd alloy,
and 1/215 of that of industrial pure titanium. The corrosion resistance of titanium
alloy was greatly improved after the double glow Pd treatment.
8.5 Plasma Surface Metallurgy Ti–Nb

Corrosion-Resistant Alloy
The Ti–Nb-alloyed layer on titanium surface, prepared by the Xu-Tec process, not
only improves the flame resistant and tribological properties, but also improves its
corrosion resistance. The Ti–Nb alloy is especially favor to the service performance
of titanium under corrosion and friction situation. Figure 8.29a shows the weight
losing versus time curve of the Ti–Nb alloy on TC4 surface in 10% H2SO4 solu-
tion. It can be seen that passivation of Ti–Nb-alloyed layer occurred after 144 h of
immersion. The passive film can effectively protect the substrate, and improve the
corrosion resistance in 10% H2SO4 solution. This phenomenon also occurs in 10%
HCl solution, as shown in Fig. 8.29b [15, 19].
Electrochemical test indicates that, since a Ti–Nb-alloyed layer is formed
through the diffusion of Nb into TC4 substrate, the self corrosion potential of TC4
is increased. Ti–Nb layer is more prone to passivation than TC4. Therefore, the Ti–
Nb-alloyed layer prepared by plasma surface metallurgy on the surface of titanium
has excellent corrosion resistance.
Fig. 8.29 Weight losing curves of Nb-alloyed sample and TC4 sample in a 10% H2SO4 and
b 10% HCl [19]
8.6 Plasma Surface Carburizing Without Hydrogen 153
8.6 Plasma Surface Carburizing Without Hydrogen
Hydrogen impurities are normally involved in all of the traditional carburizing

technologies. Titanium is an active metal with strong affinity to hydrogen. It can
easily absorb hydrogen and forms hydrides. When the accumulation of hydrides
reaches a certain level, the impact toughness and extensibility of titanium reduce
rapidly. Titanium will go through hydrogen embrittlement transition.
Double glow plasma surface metallurgy uses solid graphite as a carbon source.
Active carbon atoms produced by ion sputtering deposit and diffuse in the surface
of titanium sample, thus plasma carburizing under non-hydrogen environment is
realized. When the mixture atmosphere of argon and nitrogen is used as discharging
gas, the non-hydrogen carbon-nitriding can be realized [20, 21].
8.6.1 Plasma Carburizing with no Hydrogen
In plasma carburizing process, the sample temperature has a great influence on the
thickness of the carburizing layer [21, 22]. The higher the temperature is, the thicker
the carburizing layer would be. However, they are not linearly correspondent. As
shown in Fig. 8.30, there is a critical temperature, that is, when the temperature is
lower than this critical temperature, no matter how long the time of carburizing is, it
will not produce an obvious carburizing layer, but leaves a deposition layer of
graphite on the surface of titanium. However, the excessive high temperature would
make the titanium substrate course and hinder the mechanical properties of the
substrate. Taking all of those into account, a suitable temperature for non-hydrogen
carburizing and carbon-nitriding on titanium and titanium alloy is between 850–
1000 °C.
Fig. 8.30 Relationship

between the thickness of
carburizing layer and the
treatment temperature [21]
Fig. 8.31 Relationship

between the thickness of
carburizing layer and the
heat-retaining time [21]
Figure 8.31 shows the relationship between the thickness of the carburizing
layer and the heat-retaining time at the working-piece temperature of 1000 and
950 °C. It can be seen that the thickness of the carburizing layer is increasing with
the prolonging of the heat-retaining time. Even in a very short heat-retaining time, a
certain level of carburizing layer can be formed. With a sample temperature as high
as possible, in order to get a thicker carburizing layer, the carburizing time needs to
be prolonged, but no more than 5 h. The mixture gas of argon and nitrogen needs to
be charged during the titanium non-hydrogen carburizing. The differences in
composition and hardness of surface-alloyed layer will inevitably lead to different
mechanical and tribological properties. It is found that the hardness of carburizing
layer reaches a maximum with the volume ratio of argon to nitrogen for 16/28.
8.6.2 Microstructure and Composition of Carburized Layer
Figure 8.32 shows the sectional morphology of non-hydrogen carburizing layer of

industrial pure titanium under different carburizing temperatures, time and gas
partial pressures, respectively. As the carburizing temperature exceeds the trans-
formation temperature of titanium, the phase structure has transformed from a to b.
When the temperature is higher than 1000 °C, the structure turns into
Widmanstatten structure [23].
The surface X-ray diffraction indicated that high hardness phase TiC is formed in
the diffusion layer. The TiC phase increases the hardness of the material, reduce
friction coefficient, and improve the wear resistance of the material.
Figure 8.33 shows composition distribution of carburized layer on pure titanium
after 960 °C 3 h non-hydrogen carburizing. Figure 8.34 shows a hardness curve
of pure titanium after non-hydrogen carburizing. It can be seen that the hardness is a
Fig. 8.32 Sectional microstructure of pure titanium after carburizing a 1000 °C, 3 h, 100x;
b 980 °C, 2 h, 200x; c 960 °C, 3 h, 200x; d 980 °C, 2.4 h, 200x
Fig. 8.33 Composition

distribution of non-hydrogen
carburizing layer on pure
titanium [24]
Fig. 8.34 Hardness curve of

pure titanium after
non-hydrogen carburizing
[24]
Fig. 8.35 Element depth

distribution curves of
Ti6Al4V after non-hydrogen
nitro-carbonitriding [25]
parabolic-shaped curve, with the maximum value at the surface. Besides the for-
mation of high hardness TiC, the mechanism of surface hardening consists of
dislocation hardening, solid solution hardening [24].
Figure 8.35 gives the distribution of elements in the alloyed layer on the surface
of Ti6Al4 at 950 °C for 4 h with Ar/N2 gas of a ratio of 16/28 by double glow
plasma non-hydrogen carbon-nitriding. Overall, the results are very much similar
with aforementioned analysis [25]. Carbon and nitrogen showed a gradient descent,
while titanium showed a gradient ascent. It is same with the results of non-hydrogen
carburizing on pure titanium. There are high hardness phases TiC and TiN, as well
as not yet diffused carbon in the diffusion layer.
8.6.3 Tribological Properties
The friction coefficient of a non-hydrogen carburizing layer on titanium surface was

studied by a ball-disk wear test, and the wear resistance of the material was char-
acterized by specific wear rate test [26].
Figure 8.36 shows the relationship curve of friction distance and friction coef-
ficient of the TC4 substrate and carburized TC4 grinding with GCr15 under the dry
friction condition. Due to the existence of a large amount of high hardness phase
TiC and other carbides, the friction coefficient with an average value of 0.23 and
30% is lower than that of the untreated sample. The test results indicate that
carburizing can greatly improve the wear resistance of titanium.
To determine the weight loss rate, it is required to weight the sample before and
after the friction test. The wear rates of three samples are shown in Fig. 8.37. It can
be seen that, the wear rate of original TC4 samples is 0.0934 g/h; after carburizing,
the wear rates are 0.0032, 0.0064, 0.0026 and 0.0019 g/h. The wear rates of
Fig. 8.36 Curves of friction coefficient of a TC4 and b carburized TC4 [26]
Fig. 8.37 Wear rate of

different carburized
samples [26]
Fig. 8.38 SEM images of a TC4 alloys wear friction surface and b carburized TC4 alloys wear
friction surface [26]
carburized samples are about 2–7% of that of the original one, which shows that
wear rate can be reduced by carburizing. Due to the TiC wear-resistant phase
formed and solid solution strengthen effect, the wear resistance of TC4 can be much
improved, and the wear rate is much reduced.
The wear surface morphology after 30 min (1838 m) of friction test on the raw
substrate and carburized sample are compared. Figure 8.38a shows the SEM
morphology of wear surface of untreated TC4 after friction. Figure 8.38b gives the
SEM morphology of wear surface of carburized TC4 after friction. It can be seen
that, with the same friction distance, there were wide wear scars, furrows, grinding
particles and adhesion zone appeared on the untreated TC4 sample, and the
adhesion zone went beyond the wear scars at some locations; the wear scars on the
carburized sample were mild. No furrow or tear trace is observed, except for some
slight traces.
The wear rate and friction coefficient of the carburized sample is 2–7% while
50–60%, for a sample without carburizing. The wear rate is reduced, and the wear
resistance is improved. After the high-speed ball-disk wear test, the wear of TC4
titanium alloy was serious. On the surface, it was mainly adhesion wear; no wear or
tear on the surface of carburized samples, except for some scratches.
8.7 Applications
With the development of aviation, aerospace, marine, petroleum chemical industry

and field of daily use, titanium and titanium alloys will have a good opportunity for
a wide range of applications. However, the inherent performance defects of titanium
alloys will impede the study of applications and products development of titanium
alloys. By surface engineering treatment, especially the double glow plasma surface
metallurgy, the performance can be improved in the area of the flame-resistant
property under the environment of high temperature friction, the crevice corrosion
8.7 Applications 159
resistance and corrosion resistance in reducing acid, and the wear resistance and
erosion resistance under the friction of titanium alloy. The application of titanium
alloy mainly includes the following aspects:
(1) Plasma surface wears-resistant titanium alloy: Using the Xu-Tec process,
the corrosion and wear-resistant TiC-alloyed layers are formed on the surface of
titanium alloy. This process has been successfully applied in many engineering
fields, such as titanium alloy valves, fasteners, hydraulic cylinders, gears, and
bearings. These components play a key role in improving the performance of
devices. From the current application results, the application of titanium alloy
formed by the Xu-Tec process has just begun, with a very bright future.
(2) Plasma surface corrosion-resistant titanium alloy: surface Ti–Pd alloy in the
future will mainly be used to prevent crevice corrosion on the calcium chloride
reaction kettle in the chemical industry and seawater desalination equipment.
Surface Ti–Mo-based alloy is mainly used on the reaction equipment with
sulfuric and hydrochloric acid in chemical industry.
(3) Plasma surface flame-resistant titanium alloy: the main application will be
on the titanium alloy compressor blade and casing of the airplane turbine with a
high bypass ration and high thrust weight ratio.
8.8 Prospect
Specific gravity of titanium is only 1/2 of iron. Titanium and titanium alloys have a
high specific strength and good corrosion resistance in seawater, so it has a very
important and broad application prospects in the field of aerospace and marine
engineering.
For example, titanium has a strong corrosion resistance and the test shows no
corrosion after immersion in seawater for 5 years. Using a titanium alloy for
manufacturing ships and marine engineering would greatly extend its service life. In
the aerospace industry, using titanium in aircraft, spacecraft and space station will
greatly reduce the weight.
The development work introduced in this chapter has demonstrated that a great
number of high hardness, wear-resisting, anti-corrosion and flame retardant alloys
can be formed by the Xu-Tec process on the surface of titanium and titanium alloy.
This provides a new method for titanium and titanium alloy broader industrial
applications.
The Xu-Tec process has given a huge improvement and innovation to the tra-
ditional surface alloying technology and opens up a new door for plasma surface
alloying technology. We found that in the future, the following studies need to be
carried out:
Based on the successful preparation of Ti–Pd surface-alloyed layer, the further
study of the Xu-Tec process for reducing the Pd content in Ti–Pd-alloyed layer
should continue to carry out, together with the application engineering development
of corrosion-resistant equipment materials for chemical industry.
The flame-resistant performance evaluation method and test for the prepared
surface flame-resistant titanium alloy need to be explored and developed. In order to
meet the high precision requirement of titanium alloy casing for aero-engine, the
process coordination of surface metallurgy process and structure of titanium alloy
casing for the aero-engine need to be studied. The study of the manufacturing
technique of titanium alloy compressor casing with surface flame-resistant
titanium-alloyed layer need to be performed to provide the technical support for
the manufacturing of titanium alloy compressor casing with flame-resistant
property.
The Xu-Tec process may also be used to form functional alloys of electric,
magnetic, acoustic, wave and other aspects on the surface of titanium alloy, and
develop new types of titanium alloy.
References

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Chapter 9
of Intermetallic Compounds
Abstract TiAl and Ti2AlNb as typical intermetallic compounds have better

specific strength and high temperature strength than the nickel based alloys. They
are the ideal high temperature structural materials in the aerospace industry. But the
practical applications of intermetallic compounds are limited due to their poor wear
and high temperature oxidation resistance. In this chapter, it is presented that the
double glow discharge plasma surface alloying treatment with Nb, Mo, Cr and Ni–
Cr–Mo–Nb has been applied to TiAl and Ti2AlNb alloys for improving their
properties. The results show that after surface alloying treatments, the wear resis-
tance of the two materials increases, and the high temperature oxidation resistance
of TiAl alloy is also greatly improved as well.
9.1 Background
9.1.1 Intermetallic Compound and Its Classification
Intermetallic compound was developed by British metallurgical scientists in 1914.

Unlike the traditional metal materials, intermetallic materials contain two or more
metal elements with a long-range ordered crystal structure. The super lattice
structure coexists with covalent bonds, and such a compound can be hold up to its
melting point, leading to an excellent thermal property at high temperature.
Potential intermetallic materials mainly include the series of Ti–Al, Ni–Al,
Fe–Al, etc. [1, 2]. Ti–Al intermetallic compound is a typical high-temperature
structural material for aerospace vehicles due to the low density, light weight and
high strength. It also has a broad application in the automobile industry. TiAl
intermetallic is very attractive by its good mechanical and thermal properties, such as
high specific strength/modulus and excellent high temperature strength, etc. [3, 4].
Figure 9.1 is the Ti–Al binary phase diagram. The diagram indicates that the Ti–Al
series consists of a2-Ti3Al (D019), c-TiAl (L10) and d-TiAl3 (D022). c-TiAl has a
wide Al content of 48–69.5 at% and is stable below the melting point (1465 °C) [5].
The development of TiAl intermetallics could be traced back to the early 1950s.
DOI 10.1007/978-981-10-5724-3_9
164 9 Plasma Surface Metallurgy of Intermetallic Compounds
Fig. 9.1 Ti–Al binary phase diagram [5]
American researchers first studied the property of Ti-50Al alloy, but abandoned
their work for its poor plasticity. Actually single-phase c-TiAl has little use value.
The usable TiAl based alloys are made by doping elements such as W, Cr, Nb, Mn,
Si, B, etc. in c-TiAl intermetallics. It usually contains Ti–(45–48)–Al–(1–10)–M
(at.%), where M is an adding element [6, 7]. The low density of c-TiAl with the
properties similar to Ni alloy is very important for aerospace applications. Typical
casting alloys like Ti–47/48Al–2Nb–2Cr, Ti–47Al–2W–0.5Si and Ti–45/47Al–
2Nb–2Mn–0.8 vol.% TiB2 have been applied practically [8].
In exploring the effect of Nb on Ti3Al based alloys, Banerjee et al. found the
ternary intermetallics based on the stoichiometry Ti2AlNb, designated as an
O-phase [9, 10]. The strength (especially yield strength), fracture toughness and
creep resistance of the O-phase alloy increase with increasing Nb content. At the
present, the O-phase alloy has become a focus of intermetallics as a high temper-
ature structural material. The matured Ti2AlNb based materials in America include
Ti–22Al–23Nb and Ti–22Al–27Nb (at%). In China, a unique composition of
Ti2AlNb based alloy containing O and B2 phases was generated by advance melting
and heating processing. It has been used for turbo rotors in rocket engines.
9.1 Background 165
9.1.2 Conventional Surface Treatment
1. Improved Oxidation Resistance

When a TiAl based alloy is exposed in air at high temperature, a thin layer of
TiO2 − TiO2 + Al2O3 − Al2O3 oxides is formed on the surface. TiAl alloy
becomes stable in pure oxygen atmosphere above 1000 °C due to the formation of
continuous Al2O3 film on the surface as a barrier layer. Traditional aluminizing is
effective to the improvement of oxidation, but thick TiAl3 or TiAl2 + TiAl3 layers
are too brittle to be applicable. Gas nitriding of TiAl will lead to the lower oxidation
resistance [11].
According to the effect on oxidation, elements can be divided into three kinds:
(a) beneficial elements such as Nb, W, Si, Al, Cl, and P; (b) neutral elements of Cr,
Y, Er, Mo, Mn, Pt, and Ti; and (c) harmful elements like V [12, 13]. Those
beneficial elements can be added in the surface of TiAl alloy by ion implantation,
plasma spray, cementation or duplex treatment, to improve oxidation resistance
[14–16].
2. Improved Wear Resistance
For many parts that are used at high temperature and subjected to compressive
stress, their wear resistance is one of the key properties to determine their usability
and extended life.
Early, Hawk and Alman [17] found that minor additions of a third or fourth
element in intermetallic alloys are not sufficient to reduce the specific wear rate of
the base binary compound. Only more alloying element additions, such as Ti, Ni,
Zr, Cr, Nb or Mo, may be able to produce precipitation hardening, resulting in a
significant improvement in ductility and toughness. In the recent years, there are
many methods to improve the wear behavior of TiAl based alloys, including laser
surface alloying, laser surface deposition, chemical heat treatment, and ion
implantation [18, 19], as well as other coatings prepared by PVD and CVD
processes.
9.2 Plasma Surface Metallurgy of TiAl
9.2.1 Plasma Surface Metallurgy Nb-Alloy
The TiAl substrates have been alloyed by the Xu-Tec process with a source alloying
element Nb [20]. Figure 9.2 shows a cross sectional morphology and chemical
composition depth profile of the Nb-alloyed (TiAl–Nb) layer formed on the TiAl
alloy surface at 1100 °C. The TiAl–Nb layer consists of four diffusion sub-layers
with different microstructures. The white top layer (A) has a higher Nb content and
a lower concentration of Al and Ti. The layer (B) is Al-rich, where the Nb
Fig. 9.2 a Cross-sectional SEM image and b composition depth profile of the alloyed layers
formed on TiAl surface at 1100 °C [20]
concentration decreases rapidly, while the Ti content increases from 3 to 35 at%.

Ti–Nb precipitates are found in the Ti-rich region (C). The Nb-deficient layer (D) is
contiguous to the matrix and a few c + a2 lamellar structure retained in the layer.
The result of XRD shows that the Nb-alloyed surface is composed of c-TiAl, Nb3Al
and Ti2AlNb.
Figure 9.3 shows the interrupted-oxidation kinetics of untreated TiAl and
TiAl-Nb specimen. At 950 °C and 1050 °C, untreated TiAl reveals a linear increase
in the mass gain with the oxidation time. However, the rate of mass gain for
untreated TiAl at 1050 °C is much greater than that at 950 °C. The oxidation
kinetics of the TiAl–Nb specimen follows approximately the logarithmic law for
both samples. During the initial stage of oxidation, the mass gains of Nb-alloyed
specimens are higher than those of untreated TiAl, as Nb oxide is formed and some
of them spall at initial oxidation stage due to the high Nb content in Nb-alloyed
surface. After the initial oxidation, Al-oxide forms at the surface and slows down
further oxidation. Oxidation behavior at two process temperature conditions looks
very much the same [21, 22]
Figure 9.4 shows the cross-sectional morphology of oxide scales of untreated
and Nb-alloyed TiAl after oxidation for 360 ks at 950 °C. It is shown in Fig. 9.4a
that the scale of TiAl exhibits a typical layered structure which is basically com-
posed of four layers from the surface: from the outer, (1) TiO2, (2) TiO2 + Al2O3,
(3) Al2O3-rich, and (4) Al-depleted layer. The Al2O3-rich layer is very thin and
unstable. Ti nitrides may exist and break the continuousness of layers. A gap
composed of numerous pores starts from the scale/substrate interface and propa-
gates into the inner of the scale, resulting in the scale spalling. Compared with
untreated TiAl, the oxide of Nb-alloyed TiAl is dense, adherent and no pores appear
at the scale/substrate interface. Figure 9.4b shows that it also exhibits a typical
structure: (1) the outer Al2O3, then (2) Nb3Al + Nb2Al rich layer and
(3) Al-depleted layer. A uniform and adherent Al2O3 layer formed on Nb-alloyed
9.2 Plasma Surface Metallurgy of TiAl 167
Fig. 9.3 Oxidation kinetics curves of untreated and Nb-alloyed TiAl at a 950 °C and b 1050 °C
[21]
Fig. 9.4 Cross-sectional morphology of oxide scales after 360 ks oxidation at 950 °C: a TiAl and
b Nb-alloyed TiAl [21]
TiAl can be an obstacle prohibiting oxygen from diffusing inwards, providing an

excellent protection for the substrate.
Figure 9.5 shows the coefficient of friction by a wear test and Fig. 9.6 gives two
micrographs of wear tracks of Nb-alloyed TiAl and TiAl substrates, respectively.
The improved tribological performance after Nb-alloying treatments is clearly seen,
as the coefficient of friction changes from 0.6 to 0.15, illustrating the formation of
hard intermetallic compound and strong bonding to the substrate.
Nb alone is too soft to increase hardness of TiAl, but it is used to strengthen the
wear resistance indirectly through the lattice distortion by Nb atoms substitution for
Ti atoms. The hardened surface increases the yield strength of the contact surface in
the coating system. It reduces the tangential stresses and the interfacial stresses, thus
enhancing the wear resistance of TiAl based alloy.
Fig. 9.5 Coefficient of friction of untreated and Nb-alloyed TiAl [20]
Fig. 9.6 Worn surfaces of a TiAl and b Nb alloyed TiAl [20]
The combination of plasma Nb-alloying and plasma carburization, i.e. Nb–C

duplex treatment, can also be used to improve the properties of TiAl based alloy.
The XRD spectrum of the TiAl–Nb–C layer formed in the Nb–C duplex treated
surface is shown in Fig. 9.7. As is seen, the carbide of NbC and Nb2C are the main
constitution phases in the surface layer. These hard carbides result in a higher
surface hardness of 913HV and a low and stable coefficient of friction, as well as an
excellent wear resistance.
It is worth to mention that the subsequent carburization does not make oxidation
worse, but getting better than that of the surface treated TiAl–Nb alloy.
Fig. 9.7 XRD spectrum of Nb–C duplex-treated TiAl
9.2.2 Plasma Surface Metallurgy Mo-Alloy
Figure 9.8 shows a cross-sectional SEM micrograph and corresponding composi-

tion profile of the Mo-alloyed layer formed on a TiAl substrate. A surface layer
fabricated on the TiAl substrate exhibits a fine lamellar structure inherited from
TiAl substrate, as is shown in Fig. 9.8a. Figure 9.8b reveals that the surface layer of
about 10 lm thick is an inter-diffusion layer by as-deposited Mo with diffused Al
elements, followed by a Mo–TiAl mixed layer. Since the solubility of Mo is 5 at.%
in a phase and 4 at.% in c phase, the excess Mo atoms could pile up on the surface
to form compounds or mono-phases. In the Mo-alloyed layer, there is Ti2MoAl as
the major phase and the minor phase of c-TiAl [23, 24].
The oxidation kinetic curves for untreated TiAl and TiAl-Mo specimens are
shown in Fig. 9.9. The Mo-alloyed TiAl possesses a better oxidation resistance
after exposed at 850 °C for 100 h, as the mass gain is much lower than that of
untreated TiAl. The oxide scale formed on the TiAl was spalled repeatedly and the
Fig. 9.8 a Cross-sectional SEM image and b concentration depth profile of Mo-alloyed TiAl
surface layer [24]
16
Mass gain (mgcm )

12
-2
8
TiAl
4
TiAl-Mo
0 100 200 300 400

Time (ks)
Fig. 9.9 Cyclic oxidation curves of TiAl and Mo-alloyed TiAl [24]
Fig. 9.10 Cross-sectional image and composition of oxidized at 850 °C for 100 h for a, b
untreated TiAl, c, d Mo-alloyed TiAl [24]
mass gain versus the exposure time is almost linear during the oxidation period. The
mass gain of the Mo-alloyed TiAl reduces during the initial exposure of 60 h. It is
believed to be derived by the evaporation of MoO3 formed in the early stage of
oxidation. Afterwards, the mass gain starts increasing slowly in nearly parabolic
kinetics and no spall of the oxide scale takes place, indicating a protective oxide
scale formed on the treated TiAl.
Figure 9.10 shows SEM cross section images and corresponding EDS concen-
tration of untreated and Mo-alloyed TiAl samples oxidized at 850 °C for 100 h.
The dashed line in the EDS plot stands for the location of an oxide/substrate
interface. As shown in Fig. 9.10a, b, the oxide scale formed on TiAl is thick, with a
typical layer structure, an outer TiO2 layer and an inner mixture of Al2O3 + TiO2.
Almost all the oxide scales were spalled off when untreated TiAl samples were
cooled to the room temperature. In contrast, from Fig. 9.10c, d, for the Mo-alloyed
TiAl, a continuous mixed oxide scale of Al2O3 + TiO2 is formed at the surface,
with a strong bonding to the alloyed substrate. The EDS concentration profile also
shows the presence of a Mo-containing layer below the alumina scale, but no Mo
enrichment is detected in the outer layer although a Mo-rich layer is initially
accumulated in the alloyed TiAl surface. Furthermore, the mixed oxide layer is
composed predominantly of Al2O3 with a minor amount of TiO2. An Al-rich oxide
scale becomes a diffusion barrier and, in turn, significantly lowers the oxidation rate
[25].
The addition of Mo improves the oxidation resistance, but the formation of an
Al2O3 scale or an Al2O3-rich scale is prerequisite for obtaining the sufficient oxi-
dation resistance for TiAl-based alloys. The data on cyclic oxidation kinetics and
the oxide structures indicate two distinct oxidation states. One stage is a transient
state, in which the oxidation is most likely controlled by the formation and
volatilization of primary MoO3. The other is a steady state, marked by the for-
mation of a continuous Al2O3-rich mixed scale with a good protective function.
As is shown in Fig. 9.11, the micro-hardness profile of the Mo-alloyed TiAl is
similar to the composition distribution, tapering from the surface to the matrix.
Figure 9.12 presents the friction coefficient of untreated TiAl and the TiAl–Mo with
respect to the sliding time. The low friction coefficient results from Ti2MoAl pre-
cipitating in the Mo-alloyed surface. The result of measuring worn scars (Table 9.1)
shows that the wear resistance of TiAl is improved after Mo alloying.
After the further carburization, the Mo–C alloyed layer, including MoC and
Mo2C, can be formed on the Mo-alloyed surface. During carburization, the acti-
vated carbon is adsorbed to the surface and diffused inwards to from carbides.
Similar to the result after Nb–C duplex treatment, both wear and oxidation resis-
tances are greatly enhanced after plasma Mo–C treatment, compared with
Mo-alloyed TiAl.
Fig. 9.11 Micro-hardness 700

distribution cross a TiAl–Mo
surface
Microhardness (HV)
600
500
400
0 5 10 15 20 25 30 35 4
Distance from surface (µm)
0.7
0.6 TiAl
Coefficient of friction
0.5
0.4
0.3
TiAl-Mo
0.2
0.1
0 5 10 15 20
Sliding time (min)
Fig. 9.12 Coefficient of friction for hard surfaces obtained by Mo-alloying treatment
Table 9.1 Measuring results of worn scars after different treatments

Treatment Wear width Wear depth Wear volume Wear rate
(mm) (mm) (mm3) (mm3/N m)
Untreated TiAl 0.617 0.04879 5.06496 2.026 10−2
TiAl–Mo 0.385 0.018725 1.20943 4.8377 10−3
9.2.3 Plasma Surface Metallurgy Cr-Alloy
The oxidation resistance of TiAl is also improved significantly after treated with
plasma Cr-alloying process. Figure 9.13 is the typical chemical concentration depth
profile in the surface TiAl–Cr alloy layer. The outer portion of the alloyed layer is
an as-deposited high Cr concentration zone with a thickness of about 10 lm.
Further inward, it is a diffusion layer with a thickness of about 50 lm. The
oxidation kinetics of the TiAl–Cr surface alloy and untreated TiAl are shown
in Fig. 9.14. After oxidized for 100 h, the weight gain of the TiAl–Cr sample is
about a quarter of untreated TiAl. The curve of the TiAl–Cr layer is parabolic,
100
Concentration / at %
80
60 Ti
40 Al
20
Cr
V
0
0 10 20 30 40 50 60 70 80 90 100
Distance from surface /µm
Fig. 9.13 Concentration depth profile of a TiAl–Cr surface alloy [25]

25
Mass gain (mgcm2)

20
TiAl
15
10
TiAl-Cr
5
0
0 100 200 300 400
Time (ks)
Fig. 9.14 Oxidation kinetics of TiAl and TiAl–Cr, oxidized at 900 °C for 100 h [25]
Fig. 9.15 SEM image of Ni–

Cr–Mo–Nb alloy formed on
the TiAl surface [26]
revealing that protective scale has been formed. On the contrary, the weight gain in
TiAl is linearly increasing as it is lack of oxidation resistance. The short period of a
drop in the curve of TiAl at around 20 h is probably the result of evaporation during
the oxidation.
Surface treatment with Cr on a TiAl alloy can induce the formation oxide scales
at the surface and therefore changes the oxidation mechanism. As is mentioned
above, the oxidation scale of TiAl is a mixture of Al2O3 and TiO2, which is entirely
loose and porous, suffering from delamination and spalling throughout the oxida-
tion process. For the TiAl–Cr surface alloy, the scale is composed of mainly by a
mixture of Cr2O3, Al2O3 and TiO2, through Cr inwards diffusion. The scale remains
dense and compact all the time, no cracking and spalling are observed. Cr2O3 acts
with many functions, initially as the protective scale owing to the high Cr content of
the alloyed layer, then as the ‘binding agent’ to enhance the adhesion of the oxide
mixture due to its solubility with Al2O3 and compatibility with TiO2, and finally as
a solute doping element to promote the growth of protective Al2O3.
9.2.4 Plasma Surface Metallurgy Ni–Cr–Mo–Nb Alloy
A multi-component Ni–Cr–Mo–Nb alloy has been prepared on TiAl surface by

using the source cathode made of Ni–21Cr–9Mo–3.65Nb. As is shown in Fig. 9.15,
the multilayer structure with the columnar crystal is composed of Ni3(Ti,Al),
Ni2TiAl, Ni(Al,Ti) and Ni2(Al,Ti), as is confirmed by XRD analysis.
Figure 9.16 shows the oxidation kinetic curves of untreated and alloyed c-TiAl
(Ti-50Al, at%) exposed in air at 950 °C for 396 ks. Over the first 120 ks, the mass
of untreated TiAl increases due to the formation of oxides, and decreases rapidly
after 200 ks owing to the oxide scale spalling off. The mechanism of c-TiAl oxi-
dation as above mentioned is related to the unstable TiO2/TiO2 + Al2O3/Al2O3
scale formation in TiAl surface. The oxidation curve of Ni–Cr–Mo–Nb alloyed
samples is basically parabolic to reveal a good oxidation behavior. Alloying ele-
ments of Ni, Cr, Mo and Nb are concentrated in the oxide scale and the alloyed
layer, as a diffusion barrier during oxidation [26].
9.3 Plasma Surface Metallurgy of Ti2AlNb
9.3.1 Plasma Surface Metallurgy Cr-Alloy
As is shown in Fig. 9.17a, after Cr-alloying treatment at 1000 °C for 3 h, a 30 lm

thick Ti2AlNb-Cr layer has been built at the surface. The concentration depth
profile measured by GDOES (Fig. 9.17b) shows that Cr element has completely
diffused into the substrate for more than 10 lm. The Cr content distribution follows
the diffusion function with 38 wt% at the outmost surface. Limited by the Cr solid
Fig. 9.16 Discontinuous 8

oxidation kinetic curves of TiAl-NiCrMoNb
6
TiAl treated by complex
Mass change (mgcm )
-2
alloying [26] 4
2 TiAl
0
-2
-4
0 100 200 300 400

Time (ks)
9.3 Plasma Surface Metallurgy of Ti2AlNb 175
Fig. 9.17 a SEM morphology and b GDOES composition of Ti2AlNb–Cr layer obtained at
1000 °C for 3 h [5]
solubility in Ti, the redundant Cr exists in intermediate phases of Al8Cr5, Cr2Ti and
Cr2Nb. These hard intermetallic compounds cause a high surface hardness of
HV950 and high wear resistance.
9.3.2 Plasma Surface Metallurgy Mo-Alloy
From the SEM image shown in Fig. 9.18a, the Ti2AlNb–Mo layer treated by Mo
alloying is in a shape of lath and most precipitate phases could be Al5Mo or a little
AlNb2 and other Ti–Al intermetallics. Figure 9.18b is GDOES composition dis-
tribution of Mo treated Ti2AlNb. There is a Mo-deposit layer with a depth of 5 lm
and a fraction of Mo content reaches 95 wt%, followed by a Mo diffusion tail deep
Fig. 9.18 a SEM image and b chemical composition of Mo-alloyed Ti2AlNb surface [5]
900
Hardness (HV)
600
300
0 300 600 900

Distance from surface (µm)
Fig. 9.19 Depth distribution of micro hardness in a Mo-alloyed Ti2AlNb surface [5]
to 12 lm. A small amount of Al element exists in the Mo-deposition layer, caused

by Al out-diffusion with a little solid solubility of Al–Mo at high temperature.
Figure 9.19 shows surface micro-hardness distribution in the Ti2AlNb–Mo layer,
from the top hardness of HV800 at the surface to HV360 in the substance matrix.
A high hardness value on the top surface is contributed to that microcrystalline
Mo-deposit layer, as well as hard Al5Mo crystals precipitated in the Mo-alloyed
diffusion surface, overall leading to a hardness increase in the TiAl–Mo surface
layer.
The wear resistance of Ti2AlNb alloy has been significantly improved by Mo
alloying treatment, as is tested at a dry friction at room temperature. The wear rate
of the Mo alloying layer is only 7.5% of untreated Ti2AlNb. As is shown in
Fig. 9.20, the corresponding wear scar of untreated Ti2AlNb is a very deep furrow,
accompanying with tearing. In contrast, the wear surface produced by the
Ti2AlNb–Mo layer is very shallow, with no complete groove formed, showing a
Fig. 9.20 Wear scar of a Ti2AlNb-Mo and b untreated Ti2AlNb [5]

9.3 Plasma Surface Metallurgy of Ti2AlNb 177
significant improved wear resistance. The average friction coefficient for Ti2AlNb–
Mo surface is 0.085, while it is up to 0.7 for untreated Ti2AlNb [27].
Apparently the low friction coefficient of plasma alloyed samples is attributed to
the increase of the surface hardness and selective wear. For Ti2AlNb–Mo and
Ti2AlNb–Cr layers, the distribution of hard inter-metallic containing Mo or Cr with
other soft phases in Ti2AlNb substrate causes a selective wear and anti-friction
effect.
9.4 Prospect
The intermetallic compound represented by TiAl series has many excellent prop-
erties. As a new generation of high temperature structural material, it has a very
important application prospect in the field of aeronautics and astronautics. For
example, c-TiAl became one of the most important intermetallic materials after it
was successfully applied in the key components of aircraft engines.
As is introduced in this Chapter, it has been demonstrated that the Xu-Tec
process can be a new method for surface treatment to make better performance of
intermetallic compound materials. Experimental results presented in this chapter
have shown that the Nb, Cr, Mo, and Ni–Cr–Mo–Nb multicomponent surface
alloys formed in the TiAl and Ti2AlNb by the Xu-Tec process can significantly
improve their wear resistance and high temperature oxidation resistance. It will be
helpful to widening the application spectra of intermetallic materials.
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of TiAl intermetallics. Mater Rev 16(11):14–16
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Mater Sci Eng A239–240:899–906
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19. Liu XB, Yu LG, Wang HM (2000) Microstructure and wear resistance of laser surface alloyed
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Chapter 10
Plasma Surface Metallurgy of Other
Materials
Abstract With many unique advantages, the double glow plasma surface metal-
lurgy technology, or Xu-Tec, has been continuously developing into many appli-
cations with the deeper and wider coverage. This chapter introduces the research
achievements in the surface alloying by the Xu-Tec process on other materials, such
as copper and its alloys, niobium, molybdenum, tungsten, and C/C.
With the advancement of our modern industry, high demands for surface engi-
neering technology have been put forward. These are mainly embodied in three
aspects: the first is the universality of the substrate material; the second is the more
excellent surface performance; the third is to diversify the function of the substrate
and surface. The research and application of the Xu-Tec process of modern surface
metallurgy technology in many metallic and conductive materials have opened very
broad development space in the future. In addition to many applications introduced
in previous Chapters, this chapter introduces the research achievements in the
surface alloying by the Xu-Tec process on other materials, such as copper and its
alloys, niobium, molybdenum, tungsten, and C/C.
10.1 Plasma Surface Metallurgy of Copper

and Copper Alloys
Copper has been extensively applied in electronic and electrical industry due to its
excellent electrical and thermal properties, such as low electrical resistivity (1.7
lX cm) and high electron mobility. It is the preferred material for electrode clamp,
blast furnace, welding equipment of conductive nozzle, conductive wheel, etc.
However, there are some disadvantages for copper, which give the limitation on its
application in many engineering areas, such as low strength, low wear resistance
and bad oxidation and corrosion resistance. On the other hand, the electric con-
ductivity of copper is sensitive to the content of alloying elements. The solute
elements will increase resistivity of copper [1, 2] which severely lowers the
DOI 10.1007/978-981-10-5724-3_10
180 10 Plasma Surface Metallurgy of Other Materials
excellent electrical conductivity. In the recent years, surface modification to

improve the oxidation and corrosion resistance on the surface of pure copper has
been extensive researched. The oxidation resistance of copper can be improved by
the formation of a special coating or an alloyed layer, which should not significantly
influence the electric conductivity of the whole copper. Considerable progress has
been made in improving the surface strength of copper. For example, a silicon layer
on the surface of copper, producing Cu–Si solutions and Cu–Si compounds, can
improve the corrosion resistance [3, 4]. In addition, several other processes, like
aluminizing on the surface of pure copper, chromium plating or cobalt plating
followed by boronizing on the surface of copper, can also form a high-hardness and
wear resistant layer to improve the corrosion resistance [5]. Sobolev [6, 7] has made
good studies on the preparation and properties of thermal sprayed WC–Co com-
posite coating on copper surface. The study on the preparation and properties of
electric deposited titanium di-boride on copper has been also conducted by Agarwal
et al. [8, 9].
We have experimented with Cu–Ti, Cu–Ni and other alloyed layers on the
surface of copper by the double glow plasma surface metallurgy processing to gain
excellent oxidation and corrosion resistance.
10.1.1 Plasma Surface Metallurgy Ti Alloy
Cu–Ti alloy has excellent conductivity and mechanical properties [10]. Surface
titanizing on copper can strengthen the surface and also maintain the excellent
conductivity. We have demonstrated an effective surface modification with Cu–Ti
alloyed layer on Copper by plasma surface metallurgy technology.
The cross-section morphology and Ti composition depth profile of Ti alloyed
layer on Copper are shown in Fig. 10.1. The total thickness of the alloyed layer is
Fig. 10.1 a Cross-section morphology and b Ti depth distribution curve in Ti alloyed layer on
copper [10]
10.1 Plasma Surface Metallurgy of Copper and Copper Alloys 181
Table 10.1 Friction and wear properties of copper and Ti alloyed layer
Load (N) Copper Ti alloyed layer
Weight loss (mg) Friction coefficient Weight loss (mg) Friction coefficient
300 9.20 0.125 1.80 0.30
750 9.89 0.650 5.70 0.31
Fig. 10.2 a Cross-section morphology and b Ni content depth distribution curve in Ni alloyed
layer on copper [11]
about 80 lm. Ti content is concentrated in the top 10 lm thick layer, followed by a

Ti diffusion layer and Cu substrate, indicating the inter diffusion of Cu–Ti alloy
with the reaction and diffusion of titanium on the surface under the conditions of
alloying temperature. The layer is filled with eutectic microstructure formed by
dendritic a solid solution and the second phase Cu4Ti.
The friction wear performance tests of copper and Ti alloyed layer are listed in
Table 10.1, which respectively glided against GCr15 steel ball for 2 h. The results
show that the weight loss of Ti alloyed layer greatly increases with load increase,
but still much less than that for pure copper. The friction coefficient of pure copper
under 300 N load changes rapidly, while the friction coefficients of Ti alloyed layer
maintains at a constant, reflecting that Ti alloyed layer on the surface of pure copper
can improve the abrasion resistance and bearing capacity significantly.
The formation of Ti alloyed layer on the surface also improves the oxidation
resistance of copper. Ti alloyed layer exhibits excellent oxidation resistance at high
temperature. The XRD analysis of oxidized samples shows that there exist much
Cu2O and little CuO on the surface of pure copper, while TiO2 has formed in the
surface of Cu–Ti alloyed layer, with no Cu oxide compound. By the thermody-
namic analysis, the stability of TiO2 is much higher than that of Cu oxide
compound.
Fig. 10.3 AC impedance of

pure copper and Ni alloyed
layer at different frequency
[12]
10.1.2 Plasma Surface Metallurgy Ni Alloy
Copper and nickel can form continuous solid solution. Nickel–copper alloy has
excellent performance such as excellent corrosion resistance, medium strength, and
widely used as conductive materials in the corrosive medium. Traditional nickel
plating method only forms a pure Ni layer on the surface of pure copper, which has
poorer properties than that of white brass. Therefore, the development of Cu–Ni
alloyed layer on the surface of copper can improve corrosion resistance, but not loss
its good conductivity.
Figure 10.2 is the cross-sectional morphology and Ni content depth profile of a
Ni alloyed layer on the surface of pure copper. There is no clear boundary between
Ni alloyed layer and the substrate with smooth diffusion transition. The content of
Ni on the surface exceeds 80% and declines from the surface to the substrate [11].
AC impedance of pure copper and Ni alloyed layer are tested. The results are
shown in Fig. 10.3. The surface AC impedance of the Ni alloyed layer increased
slightly compared with pure copper, but with a small range [12].
10.2 Plasma Surface Metallurgy of Niobium Alloy
Niobium is a refractory metal in the VB family with a high melting point and low
density, and has excellent mechanical and thermal properties both in room tem-
perature and high temperature. For example, Nb can keep high ductility strength
and thermal conductivity at 1000 °C, and high strength up to 1650 °C. It is a
favorable high-temperature structural material [13], widely used in the manufacture
of aerospace engines, weapons pusher, rocket missile liquid two-component engi-
nes, gas turbines, etc. [14]. However, one main problem which restricts the
application is its low oxidation resistance at high temperatures. In order to relieve
the oxidation in some extent, surface alloying treatment is applied [15, 16].
To improve the high temperature oxidation resistance of niobium, several sur-
face treatment methods can be used, such as chemical vapor deposition, metal
organic chemical vapor deposition, magnetron sputtering, pulsed laser deposition,
electroplated deposition, etc.
10.2 Plasma Surface Metallurgy of Niobium Alloy 183
10.2.1 Plasma Surface Metallurgy Ir Alloy
Iridium (Ir) with a series of excellent performance is very popular as an

anti-oxidation alloyed layer [17]. Ir is currently the only refractory metal that has
the high strength, high melting point and good oxidation resistance. In addition, Ir is
more inerter than other metals and has the ability of resisting oxidation and car-
bonization at high temperature. Therefore, the Ir alloyed layer is regard as the
preferred oxidation resistance alloyed layer for servicing at ultra high temperature.
By using the Xu-Tec process, Ir alloyed layers have been prepared on the surface
of Nb. Figure 10.4 shows the cross-sectional morphology of an Ir alloyed layer on
niobium. The thickness of the Ir alloyed layer is about 17 lm. There is a sharp
interface transition from Ir to Nb substrate, but they are closely tight with no
shedding, delamination, voids and other defects. There exists a blending area where
Ir and Nb elements are inter-diffused in gradient distribution in the interface
between the alloy layer and the substrate.
The nano-indentation tests show that the hardness of Ir alloyed layer is
14.085 GPa and elastic modulus is 2470.6 GPa, much higher than those of Nb
metal.
10.2.2 Plasma Surface Metallurgy Mo Alloy
High temperature oxidation resistant Mo alloyed layer is prepared on the surface of

Nb521 (Nb–5W–2Mo–1Zr). The cross-section morphology and Mo distribution
curves are shown in Fig. 10.5. Combining the results from two tests, it is seen there
exist two layers: the deposition layer at the exterior in 8 lm thick and the diffusion
layer of 4.5 lm thick close to the substrate.
Fig. 10.4 Sectional

morphology of an Ir alloyed
layer on niobium
Fig. 10.5 a Cross-section morphology and b Mo distribution curve of Mo alloyed layer on Nb–
5W–2Mo–1Zr alloy
10.2.3 Plasma Surface Metallurgy Fe–Cr–Mo–Si Alloy
Ti–Cr–Si and Fe–Cr–Si alloyed layer system developed by the Versailles Company
have been successfully used in many space niobium alloy parts as anti-oxidation
materials. To further improve their oxidation resistance performance, some alloyed
elements such as Ge, W, Ti, Zr, V, B, and rare earth elements have been added to
Ti–Cr–Si and Fe–Cr–Si alloyed layer system.
A Fe–Cr–Mo–Si alloyed layer has been prepared on niobium surface by plasma
surface metallurgy method at 1200 °C. As shown in Fig. 10.6, the thickness of the
alloyed layer is about 28 lm, with a columnar crystal grown along the perpen-
dicular direction. There is no visible perfoliate crack. The columnar crystal structure
can make the interface to withstand for thermal cycle and the change of stress. XRD
analysis shows the structural phases of the alloyed layer consist of FeMoSi, CrSi2
and FeSi2.
Fig. 10.6 a Cross-section morphology and b composition distribution of Fe–Cr–Mo–Si alloyed

layer on niobium
10.2 Plasma Surface Metallurgy of Niobium Alloy 185
Fig. 10.7 XRD analysis of

Fe–Cr–Mo–Si alloyed layer
on niobium
Results of oxidation test indicate that Fe–Cr–Mo–Si alloyed layer has an

excellent oxidation resistance at 1200 °C. The XRD spectrum of the oxidation
tested sample is shown in Fig. 10.7. There are volatile complex oxides composed
by NbO2, SiO2 and Cr2(FeO2)6. One can find green oxides in the crucible at the
same time. A thermal shock test has also proved that the alloyed layer is very
reliable.
10.3 Plasma Surface Metallurgy of Molybdenum
Molybdenum is one of important refractory structure materials used in high tem-

perature environment. However, the oxidation resistance of Molybdenum is poor.
When reaching 725 °C, molybdenum (Mo) can produce oxide volatilization and
liquid oxide. In order to solve this problem, there are two processing choices: one is
the preparation of anti-oxidant alloy; the other is the addition of anti-oxidant pro-
tection alloyed layer. As was mentioned early, Iridium (Ir) has good high tem-
perature oxidation resistance. Ir alloyed layer is regard as the preferred oxidation
resistance alloyed layer for servicing at ultra high temperature.
The Ir alloyed layer on the pure Mo was prepared by the Xu-Tec technology at
900 °C. Figure 10.8 shows the cross sectional morphology of the Ir alloyed layer of
about 11 lm thick. The Ir alloyed layer and the substrate have formed metallurgical
bonding without obvious delamination and holes. The bending area in the interface
between the Ir alloyed layer and the substrate reflects the good combination of the
alloyed layer and the substrate.
Fig. 10.8 Line scanning at

cross-section morphology of
Ir alloyed layer
10.4 Plasma Surface Metallurgy of Tungsten
Tungsten and its alloy, as classical high temperature resistant materials, have prop-
erties of high melting point, excellent high temperature strength, excellent thermal
conductivity, small thermal expansion coefficient, high ray absorption, high corrosion
resistance and excellent ray shielding function. They are widely used in the fields of
high temperature and high vacuum, such as nuclear industry, aviation, aerospace,
military and electronic industry. However, the specific gravity of tungsten is large, the
processing is difficult and it can be easily oxidized at high temperature [18].
In order to improve oxidation resistance of Tungsten, plasma surface alloying with
Ni was carried out by the Xu-Tec process. The cross-section morphology of Ni alloyed
layer is shown in Fig. 10.9. The deposited layer is composed of pure Ni and the average
thickness is 19 lm. The diffusion layer, a silver gray part, is 2–3 lm thick. The interface
between deposition layer and diffusion layer is distinct, where no cracks and holes
appear. No apparent interface can be found between the permeability layer and the
matrix, which represents metallurgical bonding and dense alloyed layer structure.
The XRD spectrum of Ni alloyed layer on Tungsten is shown in Fig. 10.10,
which indicates that Ni, W and intermetallic NiW and Ni4W are the main phases in
Fig. 10.9 The cross-section

morphology of Ni alloyed
layer on tungsten
10.4 Plasma Surface Metallurgy of Tungsten 187
Fig. 10.10 XRD analysis of

Ni alloyed layer on tungsten
Fig. 10.11 Line scan

component EDAX spectrum
from B to C parts in Fig. 10.9
the alloyed layer. The existence of interphases suggests there is the interface
reaction between Ni and W.
In Fig. 10.11, the line scan EDAX spectrum from B to C parts shows that the
deposition layer has sole Ni element. Ni and W appear in gradient distribution in the
diffusion layer in a range of about 2–3 lm, suggesting the diffusion of Ni and W in
a very limited range.
The formation of the Ni layer on the W surface has a close relationship with the
plasma characteristic. The ion bombardment on the working-piece generates the
vacancy concentration of the surface of W, promoted the diffusion of Ni into the W
substrate. So it improves the bonding force between the alloyed layer and the
substrate significantly.
10.5 Plasma Surface Metallurgy of C/C Composite
Carbon/Carbon (C/C) composite material is a suitable high temperature structural

material in the field of aeronautics and astronautics, due to its properties in low
density, high strength, high modulus, low thermal expansion coefficient, durable to
thermal shock, good creep resistance, resistance to erosion and abrasion resistance,
et al. However, when the temperature reaches 370 °C, C/C composite material will
begin to be oxidized in the air. This will cause serious damage to the material itself,
which greatly limits the application of C/C composite material as the high tem-
perature structural material. Applying a high temperature oxidation resistance layer
on the surface of C/C composite is an effective way to built anti-oxidation layer for
using in high temperature and aerobic environment. There are four type sub-layers
for C/C composite anti-oxidation layer system: the glass layer, metal layer, ceramic
layer and composite layer. Silicon carbide, silicon nitride, and various oxygen
barrier layers can protect the C/C composite for a long time below 1650 °C, but a
lot of the spacecraft needs to run at higher temperature. Platinum group metals,
rhodium (Rh), iridium (Ir), ruthenium (Ru) and intermetallic compounds can be
used as candidate materials of high temperature C/C composite oxidation resistant
layer [19, 20].
An Ir layer was formed on the surface of C/C composite material by double glow
plasma surface alloying. Figure 10.12 are the microstructure graphs of the surface
and interior of C/C composite matrix, and the surface of Ir alloyed layer. The
surface of the carbon fiber of the C/C composite material has holes of certain depth
after annealed at 2000 °C, which can be seen from Fig. 10.12a. There are some
pores between the transverse carbon fiber and the matrix carbon due to the
volatilization of impurities. Phenomenon of stratification also observed in the
pyrolysis carbon. It can be attributed to the mismatch of thermal expansion coef-
ficient between the matrix carbon and fiber. Figure 10.12b is the structure of carbon
fiber in the matrix inside of C/C composite. The quality of carbon fiber remained
good, and no damage was found. After high temperature heat treatment, the
impurities were removed, and the crystal tended to be perfect. The holes in the
interface of a single fiber bundle were covered by the Ir layer preferably, as shown
in Fig. 10.12c, d.
10.6 Plasma Surface Metallurgy Ta Alloy
Tantalum (Ta) has a strong affinity with carbon and nitrogen. Those stable com-
pounds can improve the strength, toughness, creep resistance of steel. On the other
hand, Ta alloy can also contribute an excellent performance of corrosion resistance
of steel.
Based on the excellent corrosion resistance of Ta, a Ta alloyed layer was pre-
pared on the surface of Q235 Steel by the Xu-Tec process [21].
The optimum process parameter are as below: source voltage: 900–950 V,
cathode voltage: 300–450 V, temperature: 950 °C, holding time: 3 h, working air
pressure: 30 Pa, space between the electrodes: 15 mm.
Figure 10.13 gives a SEM picture and EDS spectrum for cross-section mor-
phology of Ta alloyed layer. The thickness of alloyed layer is about 33 lm. There is
a clear dividing line between alloyed layer and the matrix. Figure 10.13b is EDS
10.6 Plasma Surface Metallurgy Ta Alloy 189
Fig. 10.12 Microstructure of C/C composite matrix and Ir alloyed layer a C/C composite,
b interior of C/C, c Ir alloyed layer; and d local amplification
Fig. 10.13 a SEM morphology and b EDS analysis for cross-section of Ta alloyed layer on
Steel-1020 [21]
analysis of Ta alloyed layer section. It can be seen that there are a deposition layer
of 30 lm and a diffusion layer of 3 lm.
Figure 10.14 gives the polarization test curves of Ta alloyed layer and substrate
in 3.5% NaCl solution. It can be seen that polarization potential of Ta alloyed layer
Fig. 10.14 Polarization curves of E235 steel and Ta alloyed layer [21]
Table 10.2 The electrochemical kinetics parameters of E235 and Ta alloyed layer
Ecorr (V) icorr (A/cm2) Rp (Ω/cm2)
Steel-1020 −0.539 1.533E−5 2.553E+3
Ta layer −0.122 7.935E−9 4.209E+6
is greater than the matrix. The higher of polarization potential, the more difficult for
the electro-chemical reaction is. When polarization potential is higher than the
corrosion potential, the bare Steel-1020 surface is dissolved with a fast speed. The
curve becomes the linear relationship and the matrix is always in active dissolution
area without passivation. But the polarization curve of the alloyed layer has a
passivation range. The surface Ta alloyed layer can effectively improve the cor-
rosion resistance of the matrix.
From the polarization curves of the Ta alloyed layer and the matrix in 3.5%
NaCl solution data shown in Table 10.2, it can be seen that the Ecorr and polar-
ization resistance (Rp) of Ta alloyed layer are −0.122 V and 4.209 106 Ω/cm2,
which are higher than Steel-1020 of −0.539 V and 2.553 103 Ω/cm2, and the
corrosion current density (icorr) of Ta alloyed layer, which is 7.935 10−9 A/cm2,
is less than the Steel-10 of 1.533 10−5 A/cm2. According to the principle of
electrochemical corrosion, icorr and corrosion rate are proportional relation, while Rp
on the contrary. So that Ta alloyed layer prevents the invading of Cl−, weakens the
galvanic corrosion.
10.7 Plasma Surface Metallurgy Fe–Al–Cr Alloy 191
10.7 Plasma Surface Metallurgy Fe–Al–Cr Alloy
Fe–Al alloy has super high temperature oxidation resistance, anti-wear property and
corrosion resistance.
Fe–Cr–Al alloys have been prepared on a carbon steel surface by the Xu-Tec
process [22]. Figure 10.15 shows the cross-sectional morphology of Fe–Al–Cr
alloyed layer on the surface of Steel-1020 in a thickness of 25–30 lm. This layer
can be divided into three parts: the deposition layer has a thickness of about 10 lm;
the compound layer is about 15–20 lm; and the diffusion layer. However, the
specific element Al presents the impoverishment phenomenon at the surface area.
Yet the ultimate concentration can up to 27% at 10–15 lm away from the surface
and then gradually decreases along with the depth.
The XRD diffraction pattern of Fe–Al–Cr alloyed layer is shown in Fig. 10.16.
The intermetallic compound of Fe2AlCr develops at the deposition layer while
Fe3Al and FeAl appear at the compound layer. Furthermore, due to their higher
strength, hardness, toughness, resistance to oxidation and sulfide at high tempera-
tures, the compounds referred above are the basis of excellent comprehensive
properties of the layer.
The sectional micro-hardness presents parabolic change alone with the increase
of the depth, as shown in Fig. 10.17. The lower hardness at the diffusion layer can
be explained by the impoverishment of Al. And then, hardness is maintained at a
high range at 5–15 lm away from the surface. All figures are above 500HV0.1 and
the maximum can reach 587.7HV0.1.
The polarization curves of Steel-1020, Steel-304 and Fe–Al–Cr alloyed layers in
a 3.5% NaCl solution are shown in Fig. 10.18. The natural corrosion potential Ecorr
of Fe–Al–Cr alloy layer is higher than Steel-1020 and Steel-304. It can be con-
cluded that the occurrence of the electrochemical reaction is harder in the alloy
layers, which demonstrates that more effective corrosion resistance can be provided.
Fig. 10.15 a Cross-sectional morphology and b element distribution of Fe–Al–Cr alloyed layer
on Steel-1020 [22]
Fig. 10.16 XRD diffraction

patterns of Fe–Al–Cr alloyed
layer [22]
Fig. 10.17 Distribution of

micro-hardness of Fe–Al–Cr
alloyed layer
Figure 10.19 shows the comparison between friction curve and average friction
coefficient of Steel-1020 and the alloyed layer under 200, 300 and 400 °C. Due to
the softening at higher temperature, the strength and hardness of Steel-1020 decline
sharply with temperature increase, resulting in the continued increase of the friction
coefficient. Moreover, the oxidation product formed in the friction process exac-
erbates the abrasive wear and adhesive wear. Consequently, the friction coefficient
has a tendency to increase with the increase of temperature, and the friction curve of
substrate has large amplitude as well. However, when the temperature increases
from 200 to 300°C, the friction coefficient of Fe–Al–Cr alloy layer just raises from
0.39 to 0.58 resulting from the adhesive wear with the temperature increase. When
the temperature reaches 400 °C, oxidation is accelerated to form an oxide alloyed
layer. And the friction coefficient of this alloyed layer decreases by playing its solid
lubrication function, which reduces the direct contact and adhesion tendency in the
interface of friction pair. Comparing with the two friction curves, the friction
10.7 Plasma Surface Metallurgy Fe–Al–Cr Alloy 193
Fig. 10.18 Polarization curves of three samples in 3.5% NaCl solution
Fig. 10.19 Friction curve of 1020 and Fe–Al–Cr alloyed layer at different temperature a 1020
steel and b Fe–Al–Cr alloyed layer
coefficient of Fe–Cr–Al alloy is lower and stable without violent fluctuation, which
indicates that the layer has a better wear resistance at high temperature.
10.8 Prospect
Chapter 9 introduces the double glow plasma surface alloying of iron and steel
materials, titanium and titanium alloys, intermetallic compounds,while this chapter
presents more of the plasma surface alloying of copper and copper alloys, niobium,
tungsten and molybdenum rare and precious metal materials. It is showed that the
double glow plasma surface alloying/metallurgy technology may apply any
chemical composition as alloying elements for surface alloying on any conductive

materials. It is possible to adopt the Xu-Tec process for a broad range of metallic
materials and industrial applications.
However, up to now, both the funding and personnel for this study and tech-
nology development are subject to very large limitations. There is still a large space
for development in the aspect of both depth and width, even in the study of the
surface alloying of steel materials. It is hopeful that this book would promote a
worldwide attention and effort for its research and development.
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22. Luo XX, Yao ZJ, Zhang PZ (2014) A study on high temperature oxidation behavior of double
glowplasma surface metallurgy Fe–Al–Cr alloyed layer on Q235 steel. Appl Surf Sci
305:259–266
Chapter 11
Gradient Ceramization of Metal Surface
and Metallization of Ceramic Surface
Abstract Gradient ceramic on metal surface and metal film on ceramic surface
have very important application prospects in the material engineering development.
This chapter introduces some engineering research achievements of the Xu-Tec
process for forming gradient ceramic layers on the surface of carbon steels, as well
as metallization of titanium alloys on the surface of a variety of ceramics such as
TiSi30, Si3N4, ZrO2, Al2O3, and diamond. As a special example, forming a gradient
luminescent functional ceramic Er–ZrO2 layer on the surface of titanium alloy by
the Xu-Tec process is presented. In addition, this chapter describes the experimental
device, processing procedure, and technological parameters of ceramization and
metallization. Their mechanical properties of the formed surface ceramic and metal
layer, such as surface hardness, wear and abrasive resistances, and adhesion
enhancement, are presented.
11.1 Ceramization of Carbon Steels
A series of failures of metal materials, due to fatigue fracture, poor wear resistance
and poor oxidation resistance, have caused significant economic loss. It is reported
that almost a half of steel usages are consumed in producing spare parts every year,
and a large quantity of these steels can hardly meet the engineering requirements
due to the limited wear life [1].
The ceramic coatings on the surface of carbon steel substrates, with excellent
resistance to wear, corrosion, and oxidation, can prolong service life and increase
usage efficiency [2]. In addition, the application of ceramic coatings for the surface
modification of metallic materials is introduced to the production of
high-performance composite materials, which can remedy the limitation of ceramic
coatings due to the high toughness, ductility, and conductivity [3, 4]. These com-
posite materials, as the substitutes of the buck ceramic materials, can significantly
reduce the broken risk and the processing cost.
Double glow plasma surface alloying technology has been used for producing a
surface-alloyed layer on the conductive material and a gradient ceramic on the
DOI 10.1007/978-981-10-5724-3_11
198 11 Gradient Ceramization of Metal Surface and Metallization …
surface of metals. In the Xu-Tec process, the sputtered alloying element atoms are
deposited and diffused in the surface of cathode working-piece under the influence
of plasma. By introducing non-metallic element (e.g., C, N, B or S) to the plasma
alloying process, ceramic (e.g., metal carbide and nitride) can be formed.
Recently, the Xu-Tec process has succeeded in producing gradient ceramics
such as WC, TiN, TiC, and Ti(CN) on the surface of steels. The formation of these
ceramic layers is similar to that of plasma-assisted reactive physical vapor depo-
sition (PVD) with nitrogen or carbon plasma. However, the high working tem-
perature process accelerates the diffusion behaviors of alloying elements and
improves the adhesion between the diffusion coatings and substrates [5].
11.1.1 Plasma Surface Metallurgy TiN Ceramic
TiN ceramic is popularly used in the tools and molds due to its excellent wear and
corrosion resistance, as well as its beautiful golden color appearance. It can be
prepared by chemical vapor deposition (CVD) and PVD. By CVD, it is to form the
TiN ceramic layer on the surface of substrates by the means of the chemical reaction
using metal halide gases containing Ti atoms in the chamber. However, some
disadvantages, such as corrosion, pollution, and process complication, have limited
its application. In contrast, TiN ceramic layers produced by nitrogen
plasma-assisted PVD are widely used in industry. The low working temperature
leads to the poor adhesion between the ceramic layer and substrates, thus the
deposition layer is likely to peel off during service. The problems outlined above
can be well solved by the Xu-Tec process [6].
The fabricating process for TiN gradient ceramic layers is involved two
sub-processes. First, a layer of Ti solid solution is formed on the surface of the
working-piece by the plasma surface titanizing, then, followed by titanium diffusion
process with plasma nitriding with nitrogen refilled into the vacuum chamber. The
overall alloyed surface was composed on TiN deposition layer, TiN precipitation
layer, and Ti solid solution diffusion layer.
The plasma surface titanizing was performed on low carbon Steel-1010 and
Steel-1020, medium carbon steel and high carbon steel 1080. In this study, a single
DC power supply is used for the plasma surface alloying, and the experimental
device set up is shown in Fig. 11.1.
An array of Ti wires of a diameter of 2–3 mm is inserted in a circular cover plate
to be a source target. A hollow cathode discharge formed among the cover plate, the
working-piece and the drum cathode. The combination of the hollow cathode
discharge and the tip discharge has greatly enhanced the sputtering rate of Ti
element. The working-piece (cathode) and the source material are sealed in a drum
cathode. This configuration can prevent the escape of sputtered titanium atoms and
also acts as a heat shield to reduce heat radiation loss and enhance the operation
temperature of the working-piece.
In our repeated experiments, the main process parameters are used as follows:
11.1 Ceramization of Carbon Steels 199
Fig. 11.1 Schematics of experimental device setup
• Sample material: Carbon steel 1045;

• Source material: Titanium wire with a diameter of 3 mm;
• Ultimate base vacuum: 7 10−3Pa;
• Working gas: high purity Ar and N2;
• Working pressure: 30 Pa;
• Working-piece and source voltage: 360–400 V;
• Working current: 2.8 A;
• Alloying temperature: 1000 °C;
• Alloying time: 3 h;
• Distance of Sample and titanium wire: 18 mm.
As an example, the microstructure and composition distribution of plasma
Ti-alloyed layer produced by the Xu-Tec process are shown in Fig. 11.2 [7].
Fig. 11.2 a Microstructure and b Ti–Fe distribution of Ti-alloyed layer

Fig. 11.3 a Microstructure and b Ti-N depth distribution of a Ti-N co-diffusion layer
The thickness of the Ti-alloyed layer is about 8 µm and the content of Ti decreases
with the increase of depth from the surface, which shows the gradient distribution.
On this basis, the second sub-process of Ti-N co-diffusion will carry out by
Xu-Tec process. The composite layer of TiN/Ti is formed [8]. The microstructure
and Ti-N content depth distribution of plasma surface TiN/Ti-alloyed layer are
shown in Fig. 11.3. The thickness of the Ti-alloyed layer is about 14 µm and the
content of Ti and N decreases gradient in depth as a diffusion behavior.
It is very obvious that the surface-alloyed layer is a typical gradient diffusion TiN
ceramic layer which ensures that metallurgical bonding with good bond strength is
produced in the interface between the gradient TiN ceramic layer and the substrate.
Figure 11.4 presents an XRD spectrum of a TiN ceramic layer. A few peaks of
TiN phase are correlated with crystal faces (111), (200), (220), and (222). The
results reflect that TiN ceramic layer is multi-crystal complex with an obvious
preferred orientation of (220).
Figure 11.5 shows the depth profile of hardness. The surface hardness of
deposition is as high as 2400HV0.1, and gradually decreases along with the depth. It
can be seen that the overall thickness of TiN/Ti layer is about 20 lm.
The wear behaves of Xu-Tec TiN/Ti is tested with PVD-TiN for comparison.
The wear test conditions are as follows:
• Steel ball friction pair: TGS15, i.e., ASTM grade;
• Relative humidity: RH 45 ± 5%;
• Motor speed: 500 r/min V;
• Test time: 20 min;
• Treatment temperature: 15°C;
• Load: 50 g;
• Processing time: 2 h;
• Diameter of grinding ball: 3 mm;
• Surface roughness Ra: less than 0.05 lm;
• Hardness: 61 HRC.
Fig. 11.4 XRD patterns of

TiN ceramic layer formed on
surface of Steel-1010
Fig. 11.5 Hardness curve of

TiN ceramic layer on steel
1010 along with depth
As is seen from the wear morphology of the plasma-alloyed TiN/Ti layer in

Fig. 11.6a, the wear crack is very shallow. In contrast, the wear morphology of
PVD-TiN layer indicates that the hardened layer ruptures, and a large number of
flakes appear around the wear crack. The adhesion wear and plough are seriously
poor [9]. The excellent corrosion resistance of TiN ceramic layer makes it a
promising surface modification on carbon steels [10]. The result of electrochemical
test in the 10% H2SO4 solution indicates that the corrosion resistance of TiN
ceramic layer is better than that of 1Cr18Ni9Ti (Fig. 11.7). The result of electro-
chemical test in the H2SO4 solution is illustrated in Table 11.1. Comparing the data
of Table 11.1 and Fig. 11.7, it is found that TiN ceramic layer prepared by Xu-Tec
process has a lower corrosion current and higher potential than the matrix and
PVD-TiN coating. The corrosion resistance of TiN ceramic layer prepared by
Xu-Tec process is better than that of TiN prepared by PVD.
Fig. 11.6 Wear morphology of a TiN/Ti and b PVD-TiN on Steel substrates
Fig. 11.7 Polarization curve of a TiN/Ti and b 1Cr18Ni9Ti exposed in 10% H2SO4 [10]
Table 11.1 Results of electrochemical test, TiN prepared by Xu-Tec and PVD exposed in 10%
H2SO42 solution [10]
Sample Passive current Icorr Ecorr Corrosion rate Relative
(mA cm−2) (mA/cm2) (mV) (g m−2 h) corrosion rate
TiN (Xu-Tec) 0.194 0.0794 −296.30 0.916 4.280
TiN(PVD) 0.355 0.818 −407.41 9.443 44.126
Gr.D matrix 2.243 12.589 −328.15 131.537 614.658
Process parameters for preparing TiN ceramic layer by PVD: final vacuum: 7 10−3 Pa; Ar:
N2 = 50:3; working pressure: 1 Pa; source voltage: 400 V; source current: 1 A; processing time:
10 min; distance between source and cathode: 40 mm
To investigate the adhesive strength between TiN coating and the substrate, a scratch
test was carried out. Figure 11.8 presents the results of scratch morphology and acoustic
emission signal, respectively. In the scratch trace, there is only very weak background
acoustic emission signal and no emission signal increases when the pressure head glide
on the surface of the gradient TiN/Ti layer at continuous load range 0–100 N. Combined
with the metallographic scratch morphology, the crack and peeling off on the surface of
Fig. 11.8 a Scratch morphology and b acoustic emission test
ceramic were not observed, indicating a good bonding strength between the gradient
TiN/Ti ceramic layer and the substrate. The result of the scratch test indicates that the
adhesion force between the deposition layer and the substrate is over 100 N, higher than
that of specimen produced by PVD [11].
11.1.2 Plasma Surface Metallurgy WC Ceramic
WC ceramic coatings have many advantages, such as high strength and hardness,
good chemical stability, excellent resistance to wear and corrosion. The WC coating
as a promising material is often applied on the surface of cutting tools, printer
heads, and precision molds. However, the coatings produced by conventional
surface treatment technologies such as low-temperature PVD and CVD is likely to
fail when applied in conditions such as high temperatures, heavy loading, and fast
sliding. It is mainly attributed to the low thickness and poor adhesion between
coatings and substrates. To solve these problems outlined above, WC ceramic
layers are fabricated on the surface of Steel-1020 by applying a special structure of
the source cathode during the double glow plasma surface alloying process [12].
The sputtering yield for pure tungsten plate and C graphite plate are different due
to their mass-related differential sputtering rates. To compensate this difference, a
new cathode structure is introduced to adjust the composition more precisely. In
addition, the distance between the source and the working-piece could also be
controlled respectively. The optimized process parameters are shown in Table 11.2.
Table 11.2 Optimized parameters for WC ceramic layer on surface of 1020 steel
Parameters Settings
Processing temperature (°C) 1150
Processing time (h) 4
Working pressure (Pa) 45
Distance between source and cathode (mm) 15
Source voltage (V) 1000
Workpiece voltage (V) 300–550
Fig. 11.9 Surface SEM micrographs, with different magnification, of a WC ceramic layer on
Steel-1020 [12]
Figure 11.9 presents the surface morphology of WC ceramic layer produced on

the surface of Steel-1020. It can be clearly seen in Fig. 11.9a that WC film is
compact and dense with fine and uniform-sized grains. Figure 11.9b shows that the
WC film is mainly composed by fine particles in a size 1–4 lm in diameter. The
growth of WC films seems to follow the Volmer–Weber (VW) mode. The crystal
cores are generated in the initial stage, then grow laterally during the deposition
process and finally come into contact to be a continuous layer. The mechanism of
Volmer–Weber mode is that the deposited atoms have the tendency to join together
instead of sticking with substrates, indicating the low wetting capability of the
source materials on the substrates. However, pinhole-like pores exist in the film.
The porosity is highly dependent on the deposition rates.
The depth distribution of W and C from such a deposition layer is displayed in
Fig. 11.10. The surface deposition layer of W–C is about 20 lm. An interface
diffusion layer is shown at the depth of 20 lm in approximately 4 lm thick with a
composition gradient distribution, giving a strong metallurgical interface bonding
between the diffusion layer and matrix.
Figure 11.11 presents the XRD patterns of a WC layer deposited on the clean
surface of 1020 steel. It can be observed that the deposition layer is dominated by
Fig. 11.10 Depth distribution of a C and b W elements of the WC-alloyed layer [12]

WC layer formed on surface
of 1020 steel for 4 h [12]
W2C and WC. A small amount of Fe3W3C and Fe is also detected with relatively
low diffraction intensity. The element distribution shown in Fig. 11.10 indicates
the process gives a pure WC deposition layer (20 lm) plus a gradient layer at the
interface to the substrate through inter-diffusion. More content of W in
the deposited layer may be attributed to preferential sputtering of W than C. The
formation of W2C is just the result of the combination of W-rich and C-poor in
some areas, while the existence of WC is formed in the areas with both W-rich and
C-rich. Besides, the combination of C and Fe in the W-rich areas is likely to form
the M6C phase (i.e., Fe3W3C). The existence of the M6C phase is beneficial for the
increase in the adhesion of deposition layer and substrates, which mainly appears in
the depth of 20–25 lm shown in the EDS results (Fig. 11.10).
Fig. 11.12 Comparison of hardness between the matrix and the WC ceramic layer [12]
(a) (b)
Sliding distance /m Sliding distance /m
Fig. 11.13 Friction coefficients of a matrix and b WC ceramic layer on 1020 steel at room
temperature [12]
It is generally believed that excellent wear resistance and high hardness have a
positive correlation. Micro Vickers hardness test shows an average value of
150HV0.1 for the substrate. In a deposited layer, the micro Vickers hardness value
varies with the element composition and phase distribution. The average hardness
value for the surface of a deposition layer is 1188HV0.1, 8 times higher than that
of Steel-1020 matrix. This change is attributed to the high hardness and mechanical
strength by WC and W2C phase, which is beneficial for improving wear resistance
of the substrates (Fig. 11.12).
Figure 11.13 presents typical coefficient of friction versus the sliding distance for
a WC ceramic layer and the substrate matrix, tested under dry friction condition.
Fig. 11.14 Wear morphology of a Steel-1020 substrate and b WC ceramic layer on steel [12]
The initial coefficient of friction of 1020 steel opposite to TGS15 reaches 0.65
quickly and then remains stable at 0.65 in a steady stage. As for the WC ceramic
layer, the coefficient of friction is below 0.25 at the early stage, then fluctuates after
10 min sliding. The change is caused by the hard material phase such as WC and
W2C, which diminishes the adhesive wear and thus increases the wear resistance.
Figure 11.14a, b presents the wear morphologies of Steel-1020 matrix and a WC
ceramic coated layer respectively. It can be clearly seen that the wear width of the
WC ceramic layer is smaller than that of 1020 steel. The wear test on the substrate
shows the characteristics of adhesive, abrasive, tear, and plastic flow with obvious
furrows and striation on the surface. In contrast, the main wear mechanism of WC
ceramic layer is abrasive wear with many shallow grooves on the wear surface. It is
a common agreement that the typical microstructure of wear resistance materials is
some hard particles dispersed evenly among the plastic substrate. The hard particles
are responsible for bearing the loads while the soft substrate bears the hard particles.
The increase in the wear resistance is attributed to the combination of a WC ceramic
layer and substrates.
A surface WC ceramic layer is also beneficial to improve the corrosion resis-
tance of Steel-1020. Figure 11.15 illustrates the polarization curve of Steel-1020
and WC ceramic coating samples in the 5% solution of sulfuric acid. The current
density of the matrix increases along with potential and falling into active region
quickly, indicating no passivation occurred. As for the WC ceramic layer, when the
potential is higher than self-corrosion potential, the anodic oxidation starts. The
current density of WC ceramic layer also increases with potential and falling into
active region, indicating that passivation does not occur on the deposition layer. It
can be seen that WC ceramic layer has a lower corrosion current and higher
self-corrosion potential than Steel-1020 matrix. Therefore, the corrosion resistance
of the matrix is greatly improved with a WC coating.
Table 11.3 describes the self-corrosion potential and the density of corrosion
current of Steel-1020 and WC ceramic layer. The minimum self-corrosion potential
of Steel-1020 is −556 mV, while that of WC ceramic layer is −261 mV. The result
indicates that the deposited sample possesses better electrochemical stability.
Fig. 11.15 Polarization

curve of an alloyed sample in
5% sulfuric acid solution [12]
Table 11.3 Electrochemical kinetic parameters of matrix and WC ceramic layer in 5% solution of
sulfuric acid
Sample matrix WC ceramic layer
Ecorr (mV) −556.2 −261.7
Icorr (µA/cm2) 84.28 36.02
In addition, the corrosion current of deposited samples is much lower than that of
the matrix, demonstrating that the corrosion resistance is improved greatly.
11.1.3 Plasma Surface Metallurgy TiC Ceramic
The process for TiC ceramic layer on the surface of carbon steel is similar to that for
WC diffusion coating. Carbon atoms are sputtered from the graphite target in a
shape of grille or mesh to increase the hollow cathode discharge effect, reinforce the
sputtering for C atoms.
The surface morphology of a TiC ceramic layer on Steel-1020 is shown in
Fig. 11.16. The size of uniformly distributed TiC grains is smaller than 1 µm. The
thickness of deposition layer is about 8 lm. In Fig. 11.17, the XRD pattern of a
TiC deposition layer displays the diffraction peaks of TiC phase and a-Fe phase as
the major composition in both the surface and subsurface.
Figure 11.18 presents the elements distribution of the TiC layer on the surface of
Steel-1020. The contents of both Ti and C gradually decrease in depth, and the ratio
of Ti: C is about 1:1. The ceramic alloy layer includes a TiC deposition sub-layer
and an inter-diffusion sub-layer.
Fig. 11.16 SEM images of a the surface and b the cross-section of a TiC layer [13]
Fig. 11.17 XRD pattern of 25000

TiC layer on Steel-1020 [13] TiC
20000 Fe
15000
cps
10000
5000
0
10 20 30 40 50 60 70 80 90 100
2θ /deg.
Fig. 11.18 Element 100

distributions in a TiC layer 90
C
Contents of Ti, C, Fe / at%
on Steel-1020. Unpublished
80 Ti
70
Fe
60
50
40
30
20
10
0
0 2 4 6 8 10 12 14
distance from the surface ( m)
Fig. 11.19 Hardness depth 2400

distribution of a TiC ceramic
layer. Unpublished
2000
Hardness / HV0.1
1600
1200
800
400
12 14 16 18 20 22 24
Distance between Ti source and substrate/ m
Figure 11.19 presents the distribution of hardness along depth for a TiC ceramic
layer on the surface of Steel-1020. The initial hardness at the surface is up to 2200
HV0.1, and decreases along with the depth.
11.1.4 Plasma Surface Metallurgy Ti(CN) Ceramics
Ti–C–N multi-component layers have been fabricated on the surface of carbon

steels by the Xu-Tec process in order to increase wear and corrosion resistance of
substrates [13]. The preparation process of Ti(CN) ceramic layer is as below:
plasma depositing Ti and C in Ar for 1.5 h first, then pumping into appropriate
amount of N2 for 2 h to produce a Ti(CN) ceramic layer [14].
Cross-section micrograph of Ti(CN) ceramic layer prepared on Steel-1020 by
the Xu-Tec is shown in Fig. 11.20. The thickness of is over 20 µm. The Ti(CN)
ceramic layer is tightly bonded with the substrate through a pre-deposited Ti layer
and inter-diffusion.
Fig. 11.20 Cross-sectional

SEM micrograph of a Ti(CN)
ceramic layer [13]
Fig. 11.21 XRD spectrum of

a (Ti, C, N) ceramic layer on
Steel-1020 [13]
Figure 11.21 presents the XRD pattern of Ti(CN) layer. Phases of Ti2C0.06, TiN,
TiC and TiC0.3N0.7 have been detected respectively.
11.2 Metallization of Ceramics
Ceramic materials are widely used in industry due to their excellent hardness, high
strength, and good insulation performance. In many cases, there are some needs for
ceramic and metal parts to be welded together, owing to the electric conduction of
metals and electrical insulation for ceramics. Thus, it is required to have a metal-
lization layer on ceramics.
The conventional welding process of ceramic and metal includes burning glaze
sealing, sintered metal powder method, welding, solid-phase pressure diffusion
bonding, active metal brazing, self-propagating high-temperature synthesis (SHS).
A common feature of these methods is the high working temperature. In order to
obtain the high weld strength, the solder should possess sufficient wettability with
ceramics, which accounts for the range of high welding temperature between 1100
and 1500 °C. However, such temperature exceeds the phase-transition temperature
of the solder, which limits the application of welding. The surface treatments play
an important role in improving the wettability of solder and ceramics, making it
possible for brazing at low temperatures.
11.2.1 Metallization of TiSi30 Ceramic
A Zirconium deposition layer was formed on the surface of the duplex ceramic by
double glow plasma surface alloying process. Figure 11.22 presents an SEM

SEM image of a Zr deposition
layer on the surface of TiSi30.
Unpublished
morphology and the composition distribution of a Zr deposition layer on the surface

of TiSi30 ceramics prepared at 1100 °C for 3 h. It can be clearly seen that the
alloyed layer is composed of a Zr deposition layer and a Zr–Si inter-diffusion layer.
11.2.2 Metallization of Si3N4 Ceramic
Si3N4 ceramics stays stable at high temperature and is capable of maintaining high
strength before decomposition due to the strong bonding force between N and Si.
Because of its low coefficient of thermal expansion, high hardness, good wear, and
corrosion resistance, Si3N4 ceramics is one of the promising materials for dielectric
engineering application.
In order to achieve the brazing connection between Si3N4 ceramic and Ag–Cu
materials, a Ti deposition layer on the surface of Si3N4 is prepared by the double
glow plasma surface alloying process. Figure 11.23 presents a cross-sectional
image of brazing connection between Si3N4 and Ag–Cu materials.
The differences in the coefficient of thermal expansion and elastic modulus of
ceramics and metallic materials would generate the residual stress near the con-
nection interface and thus weaken joint strength. In order to solve this problem,
introducing a buffer layer can effectively slow down the formation of the residual
stress. Cu is regarded as a good buffer layer material. Cu–Ti composite deposition
layer is applied on the surface of Si3N4 ceramics [15]. The processing parameters
for producing Cu–Ti alloy layer on the surface of Si3N4 are listed as following: the
background vacuum is 5 Pa; working Ar partial pressure is 15 Pa; the distance
between composite target and specimen is 15 cm; the glow voltage is 600 V; the
holding time is 50 min.
11.2 Metallization of Ceramics 213

SEM image of the brazing
connection between Si3N4
and Ag–Cu. Unpublished

SEM image of a Cu–Ti alloy
on surface of Si3N4
ceramics [15]
Figure 11.24 presents a cross-sectional SEM micrograph of an alloy layer. The

left side is Si3N4 ceramics, and the white-layer in the middle is the Cu–Ti alloy.
The overall thickness of the alloy is about 20 lm. The transition layer guarantees
the good adhesion between the coating and the ceramic substrate.
Figure 11.25 presents the XRD pattern of Cu–Ti alloy layer on the surface of
Si3N4 ceramics. It is seen that Cu, CuTi2, and TiSi2 are formed in the deposition
layer. Compared with Ti, the lower activity of Cu is the main reason for the
existence of single Cu phase. The presence of Si2Ti and CuTi2 is beneficial for
wetting and spreading of a liquid metal on the subsequent surface alloying for
ceramic and metal connection.
Acoustic emission scratch test is conducted to evaluate the adhesion between the
Cu–Ti alloy layer and Si3N4 ceramic. The results show that samples fabricated for
Fig. 11.25 XRD spectrum of

Cu-Ti alloy on surface of
Si3N4 ceramics [15]
30 and 50 min exhibits excellent adhesion with no spalling under the maximum
load of 100 N.
11.2.3 Plasma Surface Metallurgy Ta–C on Diamond

and Cemented Carbide
The CVD diamond coating possesses many unique properties including low
coefficient of friction, wear resistance, and high hardness, which can significantly
increase the life of cemented carbide (WC–Co) tools [16]. However, the interface
adhesion limits the application of these tools, caused by the deleterious catalytic
reaction of cobalt (Co) binder during the growth process of diamond. Therefore, it
is essential to improve the adhesion of diamond coatings by eliminating or reducing
the deleterious effect of Co [17]. The introduction of transition layers can restrain
the deleterious effects of Co without reducing the substrate’s mechanical properties
and toughness [18].
Among many interlayer materials, Ta-based interlayer has been studied for some
years. The research result shows that a Ta carbide layer could greatly enhance the
nucleation density of diamond. Ta interlayer could suppress the diffusion of Co
effectively. However, the adhesion between a Ta interlayer and the WC–Co sub-
strate is poor due to the existence of the thermal stress at the interface. Based on the
previous work, Ta carbides can be utilized as a good substitution due to their
additional high hardness, good resistance to thermal shock, and stable chemical
properties [19, 20]. Moreover, double glow plasma surface technique is an efficient
method for the modification of the substrates by forming TaxC gradient-alloyed
layer [21], which can release the thermal stresses by a diffusion layer [22, 23].
In the experiment, a WC–Co (6 wt%) sheet is used as the substrate. The TaC
interlayer is deposited on the WC–Co substrate via the Xu-Tec process. The source
target is composed Ta metal and graphite C. The main experimental parameters are
shown as follows: substrate temperature: 800 ± 5 °C; processing time: 1 h;
Fig. 11.26 XRD spectrum of a TaxC layer formed on the WC–Co substrate [24]
Fig. 11.27 SEM image of

the TaxC surface [24]
working pressure: 35–40 Pa; the distance between the two cathodes: 17 mm; the
source voltage: 600–750 V; the workpiece voltage: 350–500 V.
After the synthesis of TaxC interlayer, diamond coatings are deposited via a
self-designed system of microwave plasma chemical vapor deposition (MPCVD) [24].
In this work, the TaxC interlayer and the mixture of Ta2C and TaC (Fig. 11.26)
are produced by the Xu-Tec method for adhesion improvement of the diamond
coatings. The interlayer is a compact nanostructure with flower-shaped pits
(Fig. 11.27).
The interlayer consists of an inner diffusion layer and an outer deposition layer.
Due to the formation of the diffusion layer, the adhesion between the interlayer and
Fig. 11.28 Cross-section

morphology of diamond
alloyed with TaxC
interlayer [24]
Fig. 11.29 Rockwell

indentation with a load of
1470 N [24]
the WC–Co substrate is greatly improved. After the Xu-Tec treatment, the surface
micro-hardness of has been significantly improved from 1799 HV0.2 to 2595 HV0.2.
By the subsequently CVD process, a uniform and tense diamond coating is
deposited onto the interlayered substrate (Fig. 11.28). In Fig. 11.29, it is found that
a distinct circumferential contour with several tiny annular cracks appears around
the indentation mark and no obvious coating detachment is observed. Therefore, it
is concluded that the TaxC interlayer can provide significant improvement of the
adhesion of diamond coating for cutting tools.
11.2.4 Surface Metallization of Diamond Films
The adhesion strength between the diamond coatings and the bonding substrates
(e.g., metals or alloys) is low due to the chemical inertness of diamond and the poor
wettability of molten metal. This has become the main barrier for its application.
In general, the well-bonded metallic coatings by CVD on diamond have become an
effective approach to solve the adhesion problem. We have employed the Xu-Tec as
the metallization method of preparing W metallic coatings onto CVD diamond
films [25].
A tungsten (W) plate was used as the target for supplying W alloying element.
Free-standing diamond films deposited by a homemade microwave plasma-assisted
CVD system were used as substrates. During the alloying process, the distance
between the diamond substrate and the target was set at 18 mm, with Argon gas
flow rate of 70 sccm. The deposition pressure was maintained at 35–38 Pa. Other
surface alloying parameters were conducted under the following conditions: source
electrode voltage −550 to −700 V, substrate voltage −350 to −500 V, and the
alloying time 2 h.
During the alloying process, continuous and compact W coatings were prepared
and its SEM micrograph is shown in Fig. 11.30. WC and W2C were formed by the
inter-diffusion and reaction between W and C. The cross-section was smooth and
compact, which was made up of clusters and slender fibrous crystals. It is shown in
Fig. 11.31 that the thickness of the W-alloy is about 6 lm and no cracks could be
found at the W-diamond interface, indicating a well-bonded interface.
Fig. 11.30 Surface morphologies of W-alloy on CVD diamond film [25]


morphology of the
as-deposited W metallic
coating on a CVD
diamond [25]
11.3 Plasma Surface Metallurgy Gradient-Function

Luminescent Ceramics Er–ZrO2 on Ti6Al4V [26]
11.3.1 Zirconia Functional Ceramics
(ZrO2) is a very promising candidate for the future mechanical engineering and
functional materials fields due to its wide band gap, high refractivity, and high
hardness [27, 28]. Due to the low phonon energy, the intrinsic luminescence of
ZrO2 is relatively weak for practical luminescence applications [29]. The rare earth
(RE) ions-doped ZrO2 can frequently use an optical material to improve the
luminescent property. The luminescence characteristics of RE-ions in ZrO2 are
concentration-dependent. The correlation of the emission intensity with the doping
concentration can be used to determine the optimum Er ions concentration in the
samples [30].
The above-mentioned luminescence characteristics had been studied on the early
warning of material failure by real-time online monitoring without interrupting their
service [31]. Material failure is difficult to be observed under some extreme external
conditions (e.g., high and low temperature, tremendous speed). Once the parts
exceed the tolerance limitation and cannot obtain timely feedback, the entire system
will suffer the tremendous damage. In view of this, Gentleman and Clarke [32] first
proposed such concepts about the luminescence response of material failure. Due to
the fact that the optical signal is in a noncontact mode, the luminescence response
can be considered as an effective and convenient method to feedback the material
failure. The ideal had thus been widely used to develop some smart coatings. For
instance, it has been reported [33] that RE-doped ZrO2 coating had the potential
application in the luminescent response for the real-time monitoring material fail-
ure. Muratore et al. [34] developed multilayer coatings for tribological application,
which can monitor coating lifetime through the luminescent response. These
11.3 Plasma Surface Metallurgy Gradient-Function Luminescent Ceramics ... 219
coatings had been carried out using a hybrid filtered vacuum arc, magnetron
sputtering, and pulsed laser deposition system. The main obstacle is that the
thickness of the alloyed layer is no more than 3 lm and the adhesion strength is
poor.
Herein, we proposed the preparation of Er–ZrO2 layer by Zr–Er alloying under
the oxygen plasma conditions using the Xu-Tec. The luminescent properties of
Er-doped ZrO2 layer on Ti-based by the DGPA process were investigated.
11.3.2 Material Preparation and Processing Parameters
The pure Zr and Er lathes (100 mm 20 mm 5 mm, purity 99.9%) were used
as the source target, and Ti6Al4V substrate in 10 mm 10 mm 5 mm was used
as a cathode. A special source target structure was designed based on the hollow
cathode effects, shown in Fig. 11.32. The source target consisted of two pieces of
Er laths and three pieces of Zr lathes, which were placed at regular intervals in a
grid-like structure. The adjacent distance among metal plates was dt and the elec-
trode spacing was d between the bottom the target and the sample. The parameters
of ZrO2 and Er–ZrO2 layers were shown in Table 11.4.
11.3.3 Microstructure Analysis
Figure 11.33 shows that the cross-sectional morphology of a Zr–Er layer prepared
by the Xu-Tec process under the oxygen plasma conditions. As can be seen from
Fig. 11.33a, there was no distinct interface appearing between the layer and sub-
strate. The Zr and Er co-sputtering under oxygen plasma exposure is accompanied
Fig. 11.32 Working-piece-source structure for Er–ZrO2 formation [26]

Table 11.4 Process parameters of double glow plasma surface alloying treatment
Items Glow discharge sputtering
Processing temperature (°C) 850–900
Processing time (h) 3
Workpiece pressure (Pa) 40
Source voltage (V) 800–950
Cathode (workpiece) voltage (V) 400–550
Distance (dt) among Zr and Er laths (mm) 10
Spacing (d) between source and sample (mm) 15
Ratio of oxygen and argon 1:2
Fig. 11.33 a Cross-sectional morphology of an Er–ZrO2 layer and b concentration distribution of

different elements [26]
by the heat treatment, for successive nucleation and growth stages. The effective
thickness of the layer based on the atomic percent content (at.%) of alloying ele-
ments was about 50 lm and the Zr, Er, and O contents in the layers gradually
decrease along the depth direction, shown in Fig. 11.33b. In fact, under the hollow
cathode discharge plasma, the kinetic energy of the discharged ions affect the
formation of a large of vacancy defects on the surface of the layer [35]. A higher
vacant concentration leads to more atoms dissolution, forming a high concentration
gradient which accelerates the diffusion of Er, Zr and O elements into the substrate.
Figure 11.34 displays two XRD spectra from ZrO2 and Er–ZrO2 layers.
Substrate element (Ti) present in both alloyed layers can be detected. The spectrum
of the ZrO2 layer is dominated by the peaks centered at 30.17° (1 0 1)t characteristic
of the tetragonal structure, while another main peak centered at 28.18° (−1 1 1) m is
indentified as the characteristics of the monoclinic structure, indicating the presence
of a mixture of tetragonal and monoclinic phase. In contrast, the tetragonal phase in
Er–ZrO2 layer is absent, suggesting that the transition to the monoclinic phase is
completed with the addition of Er element.

ZrO2 and Er–ZrO2 layers [26]
11.3.4 Friction and Wear Properties
The friction coefficient of plasma ZrO2 layer is much lower than that of the substrate
at the room temperature as is shown in Fig. 11.35. The average friction coefficient of
the layer at the room temperature was about 0.15, while that of the substrate was
0.4, and the average friction coefficient of the substrate was about 4 times higher than
that of the ZrO2 layer at the room temperature. As shown in Table 11.5, the layer
showed has a lower specific wear rate (1.158 10−5 mm−3/N m) than that of the
substrate (2.195 10−4 mm−3/N m) at room temperature. The results indicated that
the surface treatment has improved the wear resistance. In view of the above friction
process, the surface worn morphologies of TC4 alloys with and without the alloyed
layer are shown in Fig. 11.35. It is apparent that the wear track of the substrate is
clearly wider and deeper (see Fig. 11.36a) than that of the ZrO2 layer
Fig. 11.35 Friction

coefficient of the Er–ZrO2
layer and substrate.
Unpublished
Table 11.5 Worn volume and specific wear rate of the ZrO2 layer and substrate
Samples Load P/N Sliding distance (S/mm) Specific wear rate K/(mm3 N−1 m−1)
TC4 2 10 2.195 10−4
ZrO2 layer 2 10 1.158 10−5
Fig. 11.36 Wear morphologies of a the Er–ZrO2 layer and b the substrate. Unpublished
(see Fig. 11.36b), indicating that the latter has better wear performance than the
former at room temperature. The enhancement of the friction and wear behavior of
the ZrO2 layer can be attributed to the high micro-hardness and excellent adhesive
strength between the surface layer and substrate.
11.3.5 Special Gradient Luminescent Properties
To study the gradient luminescent properties along the depth of the alloyed layer,
PL spectra (Labram HR800 Jobin Yvon) were recorded through micro-area analysis
at 350 nm excitations. Figure 11.37 shows the luminescence spectra of the Er–ZrO2
layer with 325 nm excitation. Three regions are identified to study the change in
luminescence intensity with the gradual distribution of the Er and Zr content.
Within the outermost layer (Region I), the luminescence intensity of the alloyed
layer is the strongest and evidently exhibits four emission bands at 435, 525, and
564 nm for the Er–ZrO2 layer, which are attributed to the electronic transitions of
2
H11/2 ! 4I15/2 and 4S13/2 ! 4I15/2 of Er3+ ions [36]. It is noted that the emission
peaks at 525 and 564 nm Er3+ ions in the ground state can be excited directly to the
excited level 4I11/2 by 325 nm laser and then these excited Er3+ ions will undergo a
process of strong green emission. The emission spectrum from the Er-doped sample
with a broad band, centered at around 435 nm, corresponds to the ZrO2 host
emission. Beneath the outermost layer (Region II), the luminescence intensity
becomes weak as the Zr and Er contents decrease, while there is a strong broadband
centered at 529 nm and a weak band at approximately 435 nm observed due to the
Fig. 11.37 Change in

luminescence spectra of the
Er–ZrO2 layer with gradual
distribution [26]
decrease in the fluorescent emission of the host (ZrO2). For Region III, the main
peak at 529 nm is clearly observed, but the full width at half maximum (FWHM)
becomes narrow. Herein, the content of Er and Zr elements reduces to the lowest,
thus the luminescence intensity of the alloyed layer is very weak, corresponding to
the green emission band of the 2H11/2 ! 4I15/2 of Er3+ transitions. The peak at
435 nm is similar to that of the region II. Similarly, in three regions, the emission
peaks at 650 nm are very weak, corresponding to the red emission band of the
4
F9/2 ! 4I15/2 of Er3+ transition. Therefore, the increase in the ion concentration
promotes the energy transfer process, thus increasing the fluorescent emission of the
erbium ions.
Er3+ ions in the ground state can be excited directly to the level 4I11/2 by 325 nm
laser. These excited Er3+ ions will undergo a process of green emission. The
presence of Ti in both alloyed layers play a crucial role in photoluminescence
properties and leads to a defect luminescence of ZrO2 layer. It is noted that the
luminescent center at 435 nm might be due to Zr4+ ions in an asymmetric site
surrounded by oxygen ions and the substitution of Ti for Zr. The possible emitting
mechanisms can be explained that the photoluminescence phenomena originates
from the combination of electrons trapped by oxygen vacancies and holes created in
the valence band [37].
11.4 Prospect
As is known to all, metal materials have high strength, high toughness, and are easy
to process, but the surface hardness is normally low, leading to poor wear resis-
tance, corrosion resistance, and oxidation resistance. In another aspect, ceramic
materials possess better properties than the metal material, but it is not easy to
process. Therefore, in order to meet the higher requirements of metal surface
treatment, the ceramic layers on the surface of the metal material are prepared by
the means of various surface technologies, such as thermal spraying, PVD, and
CVD methods.
However, combining the ceramic and metal materials formed by the above
methods is to have a physical mechanical bonding and non-metallurgical adhesion.
Under an external force and elevated temperature, this combination is easily
damaged and separated with the stripping and brittle fracture. Therefore, if a
composition gradient of ceramic-alloyed layer can form on the surface of metal
material, the presence of the transition layer will lead to the metallurgical bonding
between the ceramic layer and metal materials and greatly strengthen the adhesion
between ceramic and metal.
One of the main merits of the double glow plasma surface alloying process is the
occurrence of the thermally driven diffusion of deposited alloying elements, which
is benefit to the formation of the gradient ceramic layer. The experimental results in
this chapter have fully confirmed that the Xu-Tec process is an effective method for
fabricating gradient ceramic layers of a variety of materials on the surface of metal
substrates.
Forming the gradient ceramic layer on the surface of metal materials has
demonstrated important application prospects in the material surface engineering.
The formation of metallic materials on the surface of ceramic not only gives the
ceramics a beautiful appearance, but also is a new method to realize the welding
between metals and ceramics.
In view of the demanding requirement of the functional material for structural
and elements, we have demonstrated the development and application prospects of
the Xu-Tec process in fabricating gradient functional ceramic materials, as well as
using the luminescent response for the real-time monitoring material failure. This
research result has opened up a new direction in the research of the gradient
functional ceramic materials.
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Chapter 12
Industrial Applications and Equipment
Scaling-Ups of Xu-Tec Process
Abstract This chapter presents some industrial applications and associated

equipments of the Xu-Tec process. Some application examples in industrial prod-
ucts, such as high-speed steel (HSS) saw blade, HSS colloid mill, and Ni–Cr alloy
corrosion resistance steel plate, are introduced. Many possible applications in
carbon steel, titanium and its alloy, intermetallic compound and other metallic
materials are also discussed briefly in this chapter. The technical specifications and
design principles of the industrial processing equipment scaling-up are presented.
12.1 Xu-Tec High-Speed Steel (HSS) Handsaw Blade
12.1.1 Xu-Tec HSS Process
Since 1985, we have been engaging in the development of industrial applications of

Xu-Tec and aiming at the surface alloying of steel plate and cutting tools. An
industrial production scale processing lines has been successfully setup. Using the
Xu-Tec to fabricate High-Speed Steel (HSS) in carbon handsaw blade teeth is the
first example [1–4].
Xu-Tec HSS treatment on handsaw blades is directly processed by the double
glow plasma surface metallurgy technology in following three steps:
• First, by the Xu-Tec process, W, Mo, and other desired alloying elements were
deposited and diffused into the tooth of low-carbon steel or low-carbon alloy
steel handsaw blade.
• Then, the standard carburizing was applied on the tooth with subsequent heat
treatment.
• Finally, a pretreated handsaw blade with high-speed steel tooth was further
treated through quenching and tempering processes.
These as-formed HSS handsaw blades have an excellent cutting performance,
good plasticity, and toughness. As is shown in Fig. 12.1, this new type of handsaw
blades can be flexibly bent.
DOI 10.1007/978-981-10-5724-3_12
228 12 Industrial Applications and Equipment Scaling-Ups of Xu-Tec …
Fig. 12.1 Flexible Xu-Tec

HSS handsaw blades [6]
12.1.2 Working-piece-Source Structure for Xu-Tec

Handsaw Blade
Xu-Tec HSS handsaw blades are produced in a horizontal furnace, as shown in

Fig. 12.2. A frame is used for hanging the handsaw blades. There are ten rows of
handsaw blades that are placed in the furnace and each row consists of 1000 pieces
of the handsaw blades. Five rows of Mo80W20 alloy plates of 6 mm thickness are
hung in the upper part of the furnace as source targets. Every two handsaw blades
placed at both sides of each row Mo80W20 plate. The teeth of handsaw blade are
facing to the W–Mo alloy plate. The space between the teeth and the source plate is
about 20 mm. Each run can handle 10,000 pieces of handsaw blades in each
furnace. Figure 12.3 shows a picture of real working-piece-source structure setup
for handsaw blade treatment.
Fig. 12.2 Schematic diagram of the working-piece-source structure for handsaw blades. 1 Source
electrode; 2 W–Mo alloy plate; 3 handsaw blades; 4 cathode electrode; 5 source power
transmission device; 6 cathode power transmission device
12.1 Xu-Tec High-Speed Steel (HSS) Handsaw Blade 229
Fig. 12.3 Real working-piece-source structure for handsaw blades
12.1.3 Production Processes
The standard bi-metal HSS (M2-HSS) handsaw blade, as one of the most popular
cutting tools, was invented by L.A. Wikie of US Doall Company in 1933, which
was fabricated by vacuum electron beam welding technology. The production
processes of bi-metal HSS handsaw blade and Xu-Tec HSS handsaw blade are
showed in Figs. 12.4 and 12.5, respectively [5]. Bi-metal HSS handsaw blade is
made by vacuum electron beam welding of HSS thin strip on carbon steel base
strip, then go through teeth cutting, quenching, and tempering. While the Xu-Tec
HSS handsaw blades are made with a low-cost carbon steel material, with surface
alloying treatment on blade teeth. In comparison, the Xu-Tec HSS handsaw blade
offers many advantages, such as a simple production process, low consumption of
high-speed steel, materials, and cost saving.
The technological parameters for Xu-Tec HSS of each process are listed below
Process parameters of plasma surface W–Mo alloying
• The working-piece: handsaw base blade: Steel-1020
• The source target: W–Mo powder metallurgy plate with 20:80 wt%;
• Working gas: Industrial pure argon;
• Working pressure: 40–60 Pa;
• Voltage of source: 950–1100 V;
• Voltage of work piece: 350–450 V;
• Working temperature: 1100–1200 °C;
• Holding time: 6 h.
Strip steel of
Cutting
blade
Vacuum
electron beam Teeth-cutting
welding
Precision rolled
High speed steel
into thin strip
Tempering Quenching
Fig. 12.4 Production process of bi-metal HSS handsaw blade
Alloying
Strip steel of
Cutting Teeth-cutting elements
blade
diffusion
Tempering Quenching Carburizing
Fig. 12.5 Production process of Xu-Tec HSS handsaw blade
Process parameters of carburizing

• Gas carburizing;
• Carbon potential: 0.85–1.05% C;
• Temperature of carburizing: 920–940 °C;
• Holding time: 5 h;
• Cooling method: oil cooling.
Process parameters of quenching:
• Salt bath quenching;
• Heating temperature: 1170 °C;
• Holding time: 1.5–2 min;
• Cooling method: oil cooling.
Process parameters of tempering:

• Salt bath tempering;
• Temperature of tempering: 560 °C;
• Holding time: 1 h, two times.
12.1.4 Microstructure and Composition
The microstructure of Xu-Tec HSS handsaw blades after each processing step was
examined. In Fig. 12.6, the white and dense layer along with tooth profile is a W–
Mo co-diffusion alloy layer. Figure 12.7 shows the microstructure of such a layer
after carburizing, where a HSS-alloyed layer was formed. The microstructure of the
tooth after quenching and tempering was presented in Fig. 12.8. The white layer
was HSS tempered martensite after tempering treatment.
Fig. 12.6 Microstructure after the W–Mo diffusion alloying on a low-carbon steel [6]
Fig. 12.7 Microstructure of an alloyed handsaw blade after carburizing [6]


an alloyed handsaw blade
teeth after quenching and
tempering [6]

the prong [6]
Figure 12.9 gives the microstructure of prong, while the composition depth
distributions of W–Mo along with angle bisector of the tooth was illustrated in
Fig. 12.10. The contents of W–Mo on the surface of the prong are 3 and 10%,
respectively. The diffusion depth has reached above 300 lm [6].
The carbide grain structure of M2-HSS and Xu-Tec HSS are presented in
Fig. 12.11, respectively. As is seen in Fig. 12.11b, the carbides of Xu-Tec HSS are
10
Alloying elements content /wt.%

W
Mo
8
0
0 50 100 150 200 250 300 350
Distance from surface /µm
Fig. 12.10 Distribution of W and Mo along angle bisector of tooth [6]
Fig. 12.11 Morphology of the carbides: a M2 HSS; and b Xu-Tec HSS [6]
fine and disperse. The absence of coarse primary carbides in Xu-Tec gives the
biggest advantage over M2-HSS formed during the liquid solidification and after
much hot rolling (see Fig. 12.11a).
12.1.5 Cutting Performance
The cutting performance test of bi-metal HSS handsaw blade is performed in

British BS 1919-1983 standard. Nine cold-rolled 18-8 stainless steel strips, by
25 mm wide and 2.6 mm thick are used to compose cutting test bar with
25 23.4 mm cross section. The total cumulative time of cutting test bar for ten
times shall not exceed 124 min, and the wear rate must be less than 40.
Ten Xu-Tec HSS handsaw blades, chosen randomly, were used for cutting test.
The results were listed in Table 12.1. It is clear that the Xu-Tec HSS handsaw
blades fully pass the requirement of bi-metal HSS handsaw blade according to the
British BS 1919-1983 standard.
It should be emphasized that some Xu-Tec HSS handsaw blades with very
excellent cutting performance were found during the cutting test. They cut the test
bar off 100 times. The time consumed in the last 10 times reached 124 min and the
wear rate was less than 40. This result is probably due to the fine (smaller than
2 lm) and dispersed carbides in Xu-Tec HSS handsaw blade. This points to us that
the Xu-Tec HSS handsaw blade may have a great potential for future optimization
development.
12.1.6 Industrialization
Since the early 1990s, we have studied the plasma surface metallurgy HSS handsaw
blade and made an effort for promoting the industrialization and applications of
Xu-Tec HSS handsaw blade.
We successively established the Xu-Tec HSS handsaw blade production line in
Guangzhou through government sponsored technology transfer program and
enterprises cooperation. The production line had been built with an annual pro-
duction capacity of over 500,000 units of handsaw blades. This handsaw blade was
sold on the market with “South Eagle” trademark.
In 1994, with the support of China National 863 Program, a production line of
plasma surface metallurgy HSS handsaw blade with 800,000 annual output was
established at the Taiyuan University of Technology. The production line system
was composed of Xu-Tec furnace, controlled atmosphere carburizing furnace, and a
Table 12.1 Results of cutting test for Xu-Tec HSS handsaw blade
No. of blade 5 6 7 8 9
1 2 1 2 1 2 1 2 1 2
The cumulative 84 85 78 87 76 77 77 75 84 88
time in 10
times/min
Wear rate 14 21 20 25 26.3 19.7 19.8 16.4 19 15
Fig. 12.12 A pilot production line of double glow discharge plasma surface metallurgy
production line of salt bath quenching and tempering with robot operation and
control. The production line successfully put into the operation in 1996. Later on,
the original production line was reconstructed under the support of the Shanxi
Provincial Planning Commission to eliminate the air pollution of salt bath process.
The reconstructed pilot production line is showed in Fig. 12.12. The functions of
each component in the pilot production line are listed as following:
1. The Xu-Tec furnace: This furnace was composed of vacuum chamber, vacuum
pumping system, gas supply system, power supply, control system, and so on.
2. The HZQT-150 vacuum carburizing and high-pressure gas quenching furnace
can be applied for both vacuum carburizing and high-pressure quenching of the
handsaw blade in the same furnace. The high-pressure cooling gas used for
quenching is nitrogen.
3. The HZRD-50 furnace for high vacuum tempering and nitriding. The furnace
can be used for high quality tempering and vacuum gas nitriding.
12.2 Xu-Tec HSS Treatment of Colloid Mill
12.2.1 Introduction
In the recent decades, fuel ethanol as a clean renewable energy fuel is attracted
widely attention. The fuel ethanol can be obtained by fermentation of corn which
needs to be crushed into a paste by grinder. The colloid mill, usually made of 9Cr18
stainless steel, is the key component of the grinder. The colloid mill consists of the
rotor and stator. The heat treatment to a colloid mill includes quenching at a salt
bath and tempering in a chamber furnace. The main failure modes for the rotor and
stator are wear and crack. The service life of a rotor or stator is only 8–10 days
under a normal operation condition, but the production cycle of products is required
more than 10 days. Improving the service life of the colloid mill had been a key
issue in the fuel ethanol production.
12.2.2 Process of Xu-Tec HSS Colloid Mill
In order to improve the wear resistance and service life of a colloid mill, we
proposed a composite vacuum heat treatment process, as illustrated in Fig. 12.13,
including double glow discharge plasma surface alloying, ion super-saturation
carburizing, vacuum heating high pressure and high flow rate gas quenching, and
vacuum heating positive pressure tempering.
With the above-defined treatment process, the surface of 9Cr18, 3Cr13, 2Cr13
stainless colloid mill and other products can be modified. It is required that the total
content of W, Mo, and Cr alloying elements in the alloyed layer should be no less than
25 wt%, and the content of carbon should be more than 2.4 wt%. Moreover, the depth
of alloyed layer should be above 100 lm, and that of carburizing layer above 500 lm.
The surface hardness should be higher than HRC 60, and the substrate hardness HRC
50–55. The grade of carbide should be less than three levels.
12.2.3 Workpiece-Source Configuration Setup

for Colloid Mill
For such a big colloid mill with U500 mm 180 mm in size and 50 kg in weight,
it is hard to manufacture a special source structure. Thus, the glow and tip dis-
charges are used for surface alloying of the colloid mill. The W–Mo alloy rods as
Fig. 12.13 Schematic diagram of the process

12.2 Xu-Tec HSS Treatment of Colloid Mill 237
Fig. 12.14 Schematic diagram of working-piece-source structure for colloid mill. 1 Source
electrode; 2 W–Mo alloy rod; 3 colloid mill; 4 base of working-piece; 5 steel cylinder
source material are inserted in a steel cylinder. The working-piece-source structure

is shown in Fig. 12.14. The diameter of the steel cylinder is about 60 mm larger
than that of the colloid mill. On the steel cylinder wall, there are a lot of evenly
distributed processing holes in a diameter of 4 mm and a spacing of 30 mm. The
W–Mo alloy rods with 4 mm in diameter and 50 mm in length are evenly set in the
hole of the cylinder wall. Figure 12.15 shows the real workpiece-source structural
configuration.
After Xu-Tec alloying processing, followed by vacuum ion carburizing, plus
high-pressure gas quenching and tempering, the service life of the treated colloid
mill is 5–7 times longer than original colloid mill.
12.2.4 Surface Alloying, Carburizing, Quenching,

and Tempering
(1) Plasma Surface Alloying

The Xu-Tec plasma surface metallurgy treatment with W–Mo alloys is the first
step in colloid mill surface modification. The source structure is composed of
Fig. 12.15 Real working-piece-source structure for a colloid mill
Fig. 12.16 Elements

distribution of an alloyed
layer on a colloid mill [6]
W–Mo metal bar. In the mass production mode, four pieces of 200 kg was loaded
in one furnace.
The process parameters of plasma surface alloying are: source electrode voltage
800–900 V; source current 60–80 A; working gas Ar; working temperature
1100 °C; processing time 8 h; working pressure, 30–50 Pa.
The distribution of alloying elements in the coating is analyzed by glow dis-
charge spectroscopy (GDS), and the result is showed in Fig. 12.16. There is a
10 lm thin layer of as-deposited W–Mo elements at the surface with a composition
ratio 70% W and 15% Mo, followed by a diffusion layer with a composition ratio
decreased to 10 and 6%, respectively. Cr element from the base matrix went on
out-diffusion to the surface, with a concentration of about 5%, versus 17% in the
matrix. This diffusion layer is a good solid solution layer between the W–Mo alloy
and substrate and created a good metallurgical bonding.
(2) Ion Carburizing
After Xu-Tec surface alloying treatment, the second step for the colloid mill
surface treatment is of the plasma carburizing. A conductive, heat insulating, and
shielding cathode structure was designed. This cathode structure has merits of
longer usage time, less-carbon deposition, stability, and reliability.
The plasma carburizing parameters are: pulse power supply voltage, 600–800 V;
pulse power supply current, 10–20 A; auxiliary heating voltage, 30 V; auxiliary
heating current: 500–700 A; working temperature, 950–1050 °C; working gas
pressure, 300–1000 Pa; carburizing time, 8–10 h; gas methane and nitrogen (trace).
The ion super-saturation carburizing was applied to the colloid mill after double
glow discharge plasma surface W–Mo co-diffusion treatment. Initially, the carbon
content on the surface of colloid mill was about 2.6%. After carburizing treatment,
the high content of alloying elements and carbon in the alloyed coating leads to the
increasing of carbides to 40 wt%. The morphology of carbides is granular, fine, and
dispersive, and its size is generally fewer than 2 lm. The microstructure of the
alloyed layer is martensite and alloyed carbide, plus a small amount of retained
austenite.
Fig. 12.17 Colloid mill rotor after all process treatments [6]
(3) High-Pressure Gas Quenching

At the end of carburizing, the nitrogen would be filled in the vacuum equipment
for 20 s immediately with a pressure of six bars. In this process, the centrifugal fan
was driven to rotate speed of 2900 RPM providing a cooling gas blow to the
working-piece in a circumferential direction of 360° with 40 m/s flow velocity. The
high pressure and a high flow rate gas cooled the work piece rapidly, from 1000 to
700 °C below within 2 min.
The rotor treatment is shown in Fig. 12.17, and the distribution of
micro-hardness in depth is illustrated in Fig. 12.18. The surface hardness of
working-piece has reached about HRC 64–67, comparing with the matrix hardness
at HRC 50–55. The surface of the treated rotor had high wear resistance due to its
high surface hardness and a number of alloyed carbides. The core of the rotor had
good toughness and strength. In all, an ideal-strengthened surface-alloyed layer
with wear resistance and uneasy cracked surface has formed on the surface of the
working-piece.
(4) Vacuum Positive Pressure Tempering
After cooling to room temperature, the working-piece was placed in a vacuum
tempering furnace. The chamber was pumped to vacuum to a base pressure of
0.1 Pa beforehand, and then filled with nitrogen to positive pressure of 1.5–2 Pa.
The furnace atmosphere was stirred uniformly by axial flow fan, and the work piece
was tempered at 180–200 °C for 2 h, with the aim of eliminating stress and
improving toughness.
Fig. 12.18 Depth

distribution of microhardness
in cross section
12.2.5 Assessment and Economic Benefits
(1) Resulting performance of Surface Alloying

• The total alloying element content of alloyed layer (W + Mo + Cr) 30%;
• The carbon content of alloyed layer: more than 2.6%;
• Depth of alloyed layer: above 150 lm;
• Depth of carburizing layer: above 500 lm;
• Surface hardness: above HRC 63;
• Hardness of substrate: HRC 50–55;
• Carbide size level: less than 2 grade.
(2) Economic Benefits
The wear resistance of the stainless steel colloid mill is greatly improved by
double glow plasma surface composite treatment. As is evaluated by the production
practice of Langfang General Machinery Co., Ltd. the average service life of colloid
mill has extended for more than five times, from 6–10 to 50 days.
The treatment process has brought the many economic benefits and application.
In addition to the service life extension for stainless steel colloid mill rotor and
stator, there results in a big material saving for rotor base stainless steel, estimating
to nearly RMB1.5 million per year for that plant. This change has also brought a
significant saving in labor power and machine down-time.
12.3 Plasma Surface Metallurgy Ni–Cr Corrosion

Resistant Alloy Plate
Back in the early 90s of last century, the famous Chinese material scientist,
Professor Hengde Li in Tsinghua University once pointed out: “The formation of
stainless steel on the surface of ordinary carbon steel is one of dream in the world’s
metallurgical steel industry for many years.”
The carbon steel has high strength and poor corrosion resistance, but the
stainless steel and nickel-based alloy have good corrosion resistance and lower
strength. If a stainless steel or nickel-based alloy is formed on the surface of
ordinary carbon steel, it will be a perfect combination. In 1986, we had successfully
prepared nickel-based alloy on the surface of low-carbon steel plate of a size in 1 m
long and 0.5 m wide, which was named the Xu-Tec alloy plate. Many development
activities on the double glow plasma surface nickel and chromium co-diffusion
process on carbon steel plate have been carried out, providing economic benefits in
the cost reduction and material saving of nickel and chromium precious metals
[7, 8].
Fig. 12.19 Cold-rolled Q235 steel plate before (left) and after Xu-Tec process (right) [5]
12.3.1 Plasma Surface Ni–Cr Alloying
As early as 1987, we successfully prepared nickel-based alloyed layer on the sur-

face of Q235 steel plate. Figure 12.19 shows the cold-rolled Q235 steel plate before
and after double glow plasma surface metallurgy treatment. Shown in the left side
of the picture is a cold-rolled steel plate, and the right side is alloyed steel plate.
Figure 12.20 shows a moment that the steel plate was just removed out from the
Xu-Tec furnace. The alloying element the depth distribution was illustrated in
Fig. 12.21.
12.3.2 Workpiece-Source Setup for Steel Plate Alloying
The working-piece-source structure for carbon steel plate is shown in Fig. 12.22.
The size of the alloyed carbon steel plate is 1000 mm 500 mm 5 mm. In the
center of the furnace body, two flat Ni80Cr20 alloy plates are set up in parallel as
source electrodes. The working-piece of a carbon steel plate is placed between the
two source electrodes. This setup is simple, with uniform temperature and sput-
tering yield, simplicity in manufacture and arrangement, long service time. After
plasma surface alloying, the Ni and Cr content on the surface of the carbon steel
plate maintains at 80 and 20%, respectively.
12.3 Plasma Surface Metallurgy Ni–Cr Corrosion Resistant Alloy Plate 243
Fig. 12.20 Xu-Tec Ni–Cr-alloyed steel plate removed out from the Xu-Tec large chamber [6]
Fig. 12.21 Ni–Cr

distribution of an alloyed
surface on an alloyed HSS
plate
12.3.3 Corrosion Resistance Test
The corrosion resistance of the Ni–Cr-alloyed steel plate is evaluated by

potential-dynamic polarization curves in 3.5 wt% NaCl solution, open to air at
25 °C. The results are showed in Fig. 12.23. The corrosion potentials (Ecorr),
corrosion current densities (icorr) and polarization resistance (Rpol) obtained from
these curves are presented in Table 12.2. The table shows that the corrosion
potential Ecorr increases with the Ni–Cr-alloyed layer on Q235 steel surface. The
Fig. 12.22 Working-piece-source structure for carbon steel plate
Fig. 12.23 Polarization test curves of a Ni–Cr-alloyed layer in a 3.5% NaCl solution
corrosion current density of the Ni–Cr-alloyed layer is approximately 9.227 10−8

A/cm2, which obviously lower than that of the substrate (approximately
1.760 10−5 A/cm2). This decrease in the corrosion current density confirms
12.3 Plasma Surface Metallurgy Ni–Cr Corrosion Resistant Alloy Plate 245
Table 12.2 Calculation Ecorr (V) icorr (A/cm2) Rp (X/cm2)

results of polarization curves
of Ni–Cr-alloyed layer in the Q235 −0.701 1.760E−05 1.862E+03
3.5% NaCl solution 316L −0.265 4.230E−07 7.854E+04
Ni80Cr20 −0.143 9.227E−08 1.582E+05
improvement in the corrosion resistance, even much better than 316L stainless
steel.
12.3.4 The Most Important Industry Application
The Xu-Tec process is a typical resource-saving and environment-friendly tech-

nology. As one of the most important industry applications, using the
Xu-Tec-alloyed carbon steel plate with high corrosion-resistant alloy surface to
replace a pure stainless steel bulk plate usage can bring significant benefit of cost
saving, while improving the surface utilization functions. A preliminary economic
calculation by Professor Yi Wang shows that, China in 2010 produced a total of
11.25 million tons of stainless steel, of which 85% is accounted for the plate. If the
plasma surface Ni–Cr alloying plate replaces 20% of stainless steel plates each year
for the country, it is about 1.9 million tons of HSS plates to be saved. Then, nickel
of 310 thousand tons and Chromium 220 thousand tons can be saved.
With the continuous consumption of alloy elements on the earth, the advantages
of double glow plasma surface metallurgy to save alloy resources will be more
prominent. This should stimulate more interest in the technology development.
12.4 Plasma Surface Metallurgy Chemical Valves

and Flanges
Many parts of pneumatic devices, such as valve body, fixing plate, valve cover,
flange, etc., require a use of stainless steel materials. It is a good opportunity for us
to apply plasma surface metallurgy Ni–Cr co-diffusion onto ordinary carbon steels
as a replacement product, providing that the treated product fully met the appli-
cation requirements. With this replacement, its service life and corrosion resistance
would be improved from the base carbon steel, even better than pure stainless steel,
but the cost is only one-third of standard stainless steel. Figure 12.24 shows the
flange parts after plasma surface metallurgy Ni–Cr co-diffusion treatment.
Fig. 12.24 Flange parts

before and after plasma
surface metallurgy Ni–Cr
co-diffusion treatment
12.5 Xu-Tec Equipment
Since the invention of double glow plasma surface metallurgy technology in 1980s,
we have been engaging in the development of the industrial applications and
equipment for the Xu-Tec. The Xu-Tec processing furnace is very similar to the
plasma nitriding furnace. The main difference is the Xu-Tec furnace has equipped
with two cathodes. One cathode is the working-piece to be treated, and the other is
the source electrode made of alloying elements. Double high-voltage DC power
supplies are needed for the cathode and source electrode.
12.5.1 Diagram of Xu-Tec Industrial Furnace
According to the mode of loading, the Xu-Tec industrial furnace can be classified
into horizontal and vertical furnaces. The vertical furnaces are suitable for the
surface alloying of long shaft working-pieces or the parts of large length–diameter
ratio. The horizontal furnaces are suitable for the surface alloying of small, flat, or
block working-piece [9–11].
The schematic diagram of Xu-Tec industrial furnace is shown in Fig. 12.25.
Inside a horizontal vacuum chamber, there are one source electrode and one cathode
electrode that is electrically connected to the working-piece. A set of metallic
radiation shields is used for temperature confinement.
12.5 Xu-Tec Equipment 247
Fig. 12.25 Diagram of Xu-Tec horizontal furnace. 1 Vacuum chamber; 2 metallic radiation
shields; 3 source electrode; 4 working-piece; 5 cathode electrode
12.5.2 Existing Furnaces and Its Applications
Until now, there have been six units of Xu-Tec industrial furnaces installed in
China. They were used for manufacturing various products, such as Xu-Tec
high-speed steel (HSS) handsaw blades, Xu-Tec HSS colloid mill and Xu-Tec alloy
plate as we present early. One picture of the Xu-Tec industrial furnaces of U1.5 m
2.5 m in size is shown in Fig. 12.26.
Fig. 12.26 One of Xu-Tec industrial furnaces built in China

Fig. 12.27 Typical vacuum system with mechanical and diffusion pumps, connection valves and
lines. 1 Main valve; 2 butterfly valve; 3 needle valve; 4 solenoid valve; 5 Pirani gauge; 6 ball
valve; 7 roots pump; 8 rotary vane pump; 9 holding pump; 10 diffusion pump
12.5.3 Composition and Function of Each Part
The main parts of a Xu-Tec industrial furnace are composed of the vacuum
chamber, power transmission device, pumping system, temperature measurement,
circulating water cooling system, gas supply, two DC power supplies, and control
system. Each of these parts will be discussed as below.
(1) Vacuum Chamber
The vacuum chamber body and door are water cooling sandwich structure which
is welded by the inner shell plates. On the furnace wall, the cathode and source
electrode, an extractor vent, an air inlet and a thermocouple temperature measuring
hole are arranged. Inside the chamber, there are heating chamber, radiation shield,
heat exchanger, air blower, and other components.
(2) Pumping System
When the iron and steel materials are treated by double glow plasma surface
metallurgy, the required limiting vacuum is less than 5 Pa. However, for active
metal materials, the required vacuum must be less than 10−3 Pa.
The pumping system of Xu-Tec industrial furnace is usually divided into two
subsystems, mechanical pumps for rough vacuum (about 5 Pa) and diffusion pumps
for high vacuum (about 10−3 Pa). For certain applications, a single pumping system
can handle the entire range and cycle. A typical pumping system is illustrated in
Fig. 12.27. The pressure is controlled by pumping speed and the conductance flow
through butterfly valves.
(3) Power Supply
In the Xu-Tec industrial furnace, to support electric bias on the source electrode
and the working-piece, both DC power and pulse power supplies can be used. To
Fig. 12.28 Typical structure of a power transmission device
avoid the arc discharge, the better selection of power supply is DC pulse power. For
the working-piece, because its high temperature and high current working condi-
tion, the pulse power can beneficial to suppress the arc discharge. However, the
pulse power will influence the hollow cathode, effecting the energy of ions from
plasma and the sputtering yield of the source electrode.
For the Xu-Tec industrial furnace, it is generally suggested that the source
electrode uses DC power supply for ion sputtering and the working-piece uses
pulsed power supply for heating.
(4) Structure of Power Transmission Device
Each cathode (working-piece) or source electrode has its own power transmis-
sion device to be connected with a power supply. The power transmission device is
one of the most important components in Xu-Tec industrial furnace. It includes
electric conductive structure, gap protection, insulation, vacuum sealing, water
cooling, and so on (see in Fig. 12.28). When the plasma surface alloying is oper-
ating, the electric current and voltage on both the working-piece and source elec-
trodes could be very high. If the design of power transmission device is not
appropriate, the problems such as arc discharge and short circuit can be easily
caused. We have made an introduction and discussion of the power transmission
device in Chap. 4. The design principles of the electrode structure are listed as
following:
• The power transmission device should be placed in the low-temperature zone so

the insulation and sealing parts would not be damaged by high temperature.
• At least one pair of combination of longitudinal and transverse gap protection
structure should be contained in the electrode structure.
• The powder of alloying elements produced by sputtering may be deposited on
the surface of the insulating material, which would cause the short circuit to the
power supply. The electrode structure should be designed as a labyrinth type
structure with groove, so as to avoid short circuit caused by a large amount of
sputtered metal powder.
• The structure of the power transmission device should be simple, convenient,
reliable and easy to disassemble and for maintenance clean.
• High-quality ceramic materials should be choose to meet higher insulation
requirements.
• Sometimes, the working-piece and source electrode are difficult to arrange. In
that case, they can be carried out by a single power supply at the same potential.
(5) Water Cooling System
The chilled water is used for cooling the body of the furnace and electrodes. The
circulating water system is generally recommended. For the large industrial furnace,
the pool is necessary. In order to reduce the volume of the pool, a cooling water
tower can be set. For the laboratory equipment, a small storage tank is enough for
circulation cooling. The cooling water of electrode is mainly used for cooling the
sealing ring and insulation part (such as ceramic tube). The sealing ring is made of
silicon rubber and its heat resistance ability is very low.
(6) Gas Supply System
In the Xu-Tec furnace, two gas supply systems with mass flow meters are
generally used for quantitative gas refill and pressure control. Argon gas is usually
chose as the main working gas, sometimes carbon or nitrogen is also chosen for
special treatment.
(7) Temperature Measurement System
For a Xu-Tec industrial furnace, the photoelectric pyrometer is used to measure
the temperature of the working-piece without contact. However, the temperature
detected by the noncontact photoelectric pyrometer is easily affected by the media,
the emissivity of material surface, glow emission, glass material of observation
windows, and other factors. Normally, this measurement error is large. Now we
have adopted a new system with the combination of photoelectric pyrometer and a
thermocouple reference. In this temperature measurement system, a simulated test
piece is placed near the working-piece, and a thermocouple with a gap protection is
inserted into the test piece. The test piece and working-piece are placed in the same
temperature field and heated together. Thus, the thermocouple can directly reflect
the heating temperature of the working-piece.
Fig. 12.29 Metallic radiation

shields Steel support
Stainless steel
Molybdenum
(8) Radiation Shields

Temperature of plasma surface alloying is generally high at about 1000 °C, and
the main form of heat conduction in a vacuum furnace is radiation. In order to
prevent the rise of temperature of the furnace body, the furnace body with water
cooling double walls is designed. At the same time, radiation shields for
anti-radiation must be set up in the inner wall of the vacuum chamber of the Xu-Tec
industrial furnace.
To increase the heat resistance, the metallic radiation shields design consists of a
stack of metal sheets with proper spacing between each sheet. For example, one
molybdenum shield backed by three stainless shields would be typical for 1150 °C
(see in Fig. 12.29). During the alloying process, the first layer of molybdenum
shield has an operating temperature of about 1000 °C, the second layer of stainless
steel shield has an operating temperature of about 700–800 °C, the third layer of
stainless steel shield is about 500–600 °C, and the last layer of stainless steel shield
is about 300 °C.
(9) Gas Cooling System
In order to improve the work efficiency and short the time of cooling process
after plasma surface alloying, the gas cooling system is generally suggested for the
large industrial furnace.
The gas cooling system mainly consists of a heat exchanger, blower, and gas
duct. The heat exchanger and blower are located at the end of the furnace body.
During the process of cooling, the hot gas is first cooled by the heat exchanger, and
then be driven by the blower to enter into the heating chamber through the air duct,
which can form the gas circulation in the furnace. For the industrial furnace with the
capacity of 400 kg, the gas cooling is usually performed under 600–700 Pa pres-
sure, and the power of the blower is suitable for 7.5–10 kW.
12.5.4 Technical Specifications
The technical specifications of the Xu-Tec industrial furnace are listed as following:
1. Limiting vacuum: 5 Pa (special requirement up to 1 10−3 Pa).
2. Leakage rate: 0.67 Pa/h.
3. DC (or pulse) power supply: working voltage range is 0–1200 V;
4. The insulation resistance between the cathode (working-piece) and source
electrode is more than 4 MX.
5. Working temperature range: 500–1200 °C.
6. The cathode and source electrode should obtain a reliable and stable power
transmission device with gap protection structure to prevent arc discharge.
7. Working gas pressure: 10–100 Pa.
8. The gas intake system: It controlled by multichannel mass flow meters.
9. Pumping system: It is composed of a mechanical pump and root pumps. The
small equipment can choose the mechanical pump, while the advanced
equipment should choose mechanical pump and diffusion pump (or turbo
molecular pump).
10. Vacuum measurement system: digital vacuum meters and other vacuum meters
are generally recommended.
11. Temperature measurement: The photoelectric thermometer with 300–1200 °C
test range or the thermocouple can be chosen.
12. Radiation shields: It consist of three–four metallic shields, some small equip-
ment choosing one–two metallic shields. The radiation shields with the effec-
tive heat insulation and reasonable heat dissipation should be arranged in the
hot zone.
13. Cold-wall: the furnace body, base, and the electrode are cooled with water and
are kept near ambient temperature during the process of diffusion metalizing.
14. Gas cooling: in order to obtain the required microstructure and decrease the
cooling time of the working-piece, the forced circulation gas cooling should be
adopted. The centrifugal gas cooling system is driven by the motor with 10–
15 kW power.
15. Heat exchanger system: the heat exchanger system with 2–6 tons per hour is
generally recommended.
16. Pump combination system: the butterfly valve, the valve closing system, the
bleeding valve, and others are usually chosen to the pump combination system.
17. Functional requirements: plasma surface alloying, nitriding, carburizing, and
carbonitriding.
18. Time of vacuum pumping: reach to the limiting vacuum in half an hour.
19. Heating-up time: generally in 3 h to predetermined temperature.
20. Gas cooling pressure: 7–9 104 Pa (when the design is a positive pressure
cooling, can be charged to 2–3 104 Pa).
21. Time of gas cooling: less than 1.5 h (the temperature of working-piece decrease
from the working temperature to 100 °C below under full load).
12.5.5 Differences Between Xu-Tec Furnace and Plasma

Nitriding Equipment
The double glow plasma surface alloying/metallurgy technology is invented on the

basis of plasma nitriding technology [12]. It is very similar to plasma nitriding
technology, such as processing under vacuum conditions, using glow discharge,
heating the working-piece by ion bombardment, diffusing the alloying elements into
the surface of the working-piece and forming a surface alloy layer. However, there
are still some main differences between the Xu-Tec process and plasma nitriding, as
are shown in the following aspects:
1. Plasma nitriding only uses single glow discharge while the Xu-Tec process
using double glow discharges.
2. In the equipment, plasma nitriding has only one cathode power transmission
device, while double glow plasma surface metallurgy technology must have two
cathode transmission devices: one cathode for the working-piece, and the other
one as source electrode.
3. Plasma nitriding only requires one DC variable voltage power supply (0–
1000 V), while the double glow technology must have two independent DC
variable voltage supplies (0–1200 V).
4. The alloying temperature range of plasma nitriding is 300–650 °C, while the
temperature range of Xu-Tec plasma alloying is 800–1200 °C.
5. Both furnace body of plasma nitriding and Xu-Tec process need double-layer
furnace body structure with water cooling. The temperature of Xu-Tec is much
higher than that of plasma nitriding, so the anti-radiation shields of three–four
layers must be set inside the furnace body.
Nowadays, plasma nitriding technology has been widely used in the world.
According to a rough estimate, there are more than 10,000 units of plasma nitriding
equipment in the world. Manufacturers and companies which produce plasma
nitriding equipment are also in a great number.
Although the technology and equipment of Xu-Tec process and plasma nitriding
have many differences, but the Xu-Tec and its equipment design are relatively easy
to be grasped by plasma nitriding researchers and manufacturing operators.
12.6 Prospect and Outlook
This chapter has shown some of the achievements we have made with the Xu-Tec
process over the past years. Its industrial application includes a bundle of small
handsaw blades, large-diameter colloidal mills, and large steel plates, etc. The scale
of the alloying furnace ranges from 4 to 6 colloid mill holdings, to ten thousand
handsaw blades.
In the recent years, the application of high-speed steel has been gradually
extended from manufacturing tools to many important parts in the mechanism
engineering field, such as gears, shafts, rollers, and colloid mills. If the use of
plasma surface metallurgy high-speed steel to replace pure HSS bulk materials, it
will greatly reduce the consumption of high-speed steel and save a large amount of
priciest metals, such as tungsten and molybdenum, chromium, cobalt and other
alloy elements. Furthermore, for plasma surface metallurgy high-speed steel with
very fine carbide grains along with the outstanding uniformity and dispersion, its
performance will go beyond the traditional and powder metallurgy high-speed steel.
For example, with the rapid development of ocean engineering and ship manu-
facturing industry, plasma surface metallurgy corrosion resistance steel plate will
have a broad application potential.
Through the introduction in Chap. 10, we can see that the Xu-Tec process has
been expanded in the field of copper and copper alloy, high melting point metal,
precious metal materials, rare metal materials, and carbon–carbon materials. It will
be a very significant development in the space industry.
In Chap. 11, the results have shown that the double glow technology is a new
method to form gradient alloy ceramics on the surface of metal materials. The
combination of high hardness, wear resistance, corrosion resistance of ceramics and
high strength, high toughness of metal materials, is bound to be a very important
research direction in the development of materials science and technology. The
metalizing of the ceramic material can provide a new way for solving the welding
problem between metal and ceramic.
In summary, we believe that the Xu-Tec Process is an excellent surface alloying
technology that can comprehensively improve the surface properties and quality of
all kinds of metal parts and solid products. Its industry application prospect is very
broad, with the economic value that is unlimited.
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Chapter 13
Other Technologies by Double Glow
Discharge Plasma Phenomenon
Abstract Inspired by double glow plasma surface metallurgy technology, a series

of other innovative technologies were developed based on the double glow dis-
charge phenomenon, such as the double glow-added arc plasma surface alloying
technology and double glow plasma brazing. All the inventions have further
enriched the class of double glow plasma surface alloying/metallurgy technology;
expanded the scope of its research and applications. The basic principle, main
functionality and characteristics of each technology are briefly introduced in this
chapter.
13.1 Arc Plasma Added Double Glow Surface Alloying

Technology
Based on the glow discharge with arc discharge, the arc plasma added double glow
discharge surface alloying technology [1] has been invented by Prof. Pan JD,
Fan BH, and Xu Z in Taiyuan University of Technology [2]. The multi-arc plasma
surface alloying technology is developed by Prof. Wang [3].
The hardware setup of arc plasma added double glow surface alloying tech-
nology is shown in Fig. 13.1. A set of the cold cathode arc sources is added to the
double glow plasma surface alloying equipment, seeing the components 9–11 on
the wall of the vacuum vessel. This arc target is set to supply a plurality of alloying
elements through the arc discharge, in addition to those from the source electrode in
double discharge plasma mode. The working-piece is still heated by the double
discharge plasma to alloying temperature, to drive element inter-diffusion for the
formation of surface alloyed layer. By the arc discharge, many metallic element
source supplies can be easily generated, such as high-melting point metals and solid
graphite. With this addition element source and addition of reaction gas, a variety of
metal carbide, nitride compound, and compound thin film can form on the surface
of the working-piece [4–9].
DOI 10.1007/978-981-10-5724-3_13
258 13 Other Technologies by Double Glow Discharge Plasma Phenomenon
Fig. 13.1 Schematic of the setup of arc-added glow plasma surface alloying technology [10]
Arc plasma added double glow surface alloying technology has been applied to
carbon steel, titanium alloy, and copper alloy for improving the material’s
mechanical properties, wear resistance, corrosion resistance.
13.2 Double Glow Plasma Brazing Technology
Vacuum brazing is an important connecting technique for the complex

high-precision waveguide assembly. During a brazing process, the strict precision
control of vacuum and temperature is a need. There are several other short backs,
such as low thermal efficiency, low joint strength, and false welding with aluminum
oxides contamination at the joints and complicated cleanup after welding [10].
To solve the above-mentioned issues, double glow discharge plasma has been
employed as a clean, dry, and efficient vacuum blazing process, where the glow
discharge plasma is used as the heat source for brazing. Alloy materials supplied by
sputtering of the source target are used as a part of blazing filling materials for
alloying. Figure 13.2 shows the schematic of brazing using the double glow plasma
technology. The working-piece 3 was connected with cathode 1. And auxiliary
cathode 8 and additional cathode 2 were set as the requirement of double glow
hollow cathode discharge.
The localized hollow cathode discharge between the auxiliary cathode and the
working-piece helps to generate localized heat to the brazing filler metal. Strong ion
bombardment has high thermal efficiency for heating the working-piece and melting
filler metal to realize brazing. The operation pressure in a range of 10–150 Pa for
brazing is reduced for low vacuum requirements, comparing to traditional high
vacuum brazing furnace. In addition, early stage ion bombardment on the surface of
13.2 Double Glow Plasma Brazing Technology 259
Fig. 13.2 Schematics of brazing process setup with the double glow plasma technology [10]
the working-piece has also provided a highly efficient surface cleaning, to achieve a
better welding quality.
Double glow plasma brazing technology has been successfully applied in fab-
ricating multiple blazing products. One of advantages for double glow plasma
brazing technology is the localized heating of the brazing parts, instead of the whole
one. This can reduce a chance of the working-piece deformation and also greatly
shorten the time of soldering. As for the general vacuum brazing, it is at least 6–8 h,
while it is less than 2 h for double glow discharge brazing.
13.3 Double Glow Plasma Sintering Technology
Sintering is a standard process for the producing powder metallurgy materials.

Many metals with strong oxidation-ability, such as aluminum and titanium, are
processed by vacuum powder metallurgy process in order to minimizing oxidation
and reducing the manufacturing cost. To achieve the possible high density to be
close to that of fully dense material for a better mechanical and physical properties,
high-temperature sintering or super solid-phase sintering become the preferred
choice. For example, for high-strength iron base structural parts, the sintering
temperature is set at 1300–1350 °C which is much higher than the traditional
process of 1100 °C. Accordingly, it brings higher requirement to the sintering
equipment.
Double glow discharge plasma sintering technology [11] is a novel technology
of energy intensified high-temperature sintering process with high efficiency and
reliability. The schematic diagram of this technology is shown in Fig. 13.3.
Several aluminum–iron–boron magnetic material rods are placed in the auxiliary
cylinder as the working-piece. The strong hollow cathode discharge plasma
between the workpiece and specimen provides thermal energy to heat the
working-piece to high temperature (above 3000 °C) for sintering.
Fig. 13.3 Schematic diagram of double glow discharge plasma sintering [11]
In addition, if the auxiliary cylinder is made of the required alloying elements,

the double glow discharge plasma generates an alloy element supply to carry out
surface alloying at the same time. For example, we have used the double glow
sintering technology for sintering and at the same time also for surface alloying
with Ni–Cr to improve the surface performance of corrosion resistance.
13.4 Double Glow Plasma Nano-Powder Technology
In the double glow plasma discharge, the source material is sputtered to form a large
number of atoms, atom group, ions, and pellets. In a cool environment, the sput-
tering species would be quenched down to form atom clusters and powders. Most
of those particles are in a nano-scale dimension [12].
Figure 13.4 gives a schematic of an apparatus for producing nano-materials by
double glow hollow cathode discharge. The bulk materials of the supply cathode
can be sputtered to form nano-powders. A typical supply cathode structure is as grid
shape, the distance between each other is 5–30 mm. As the other cathode, col-
lection container is placed below the supply cathode. Cooling device with rapid
cooling capacity is set between the two cathodes. The container itself has a strong
cooling ability and generally cooled by chill water or liquid nitrogen. The main
processing parameters are shown as following:
13.4 Double Glow Plasma Nano-Powder Technology 261
Fig. 13.4 Schematic of

nano-materials production by
double glow plasma
sputtering [10]
Argon pressure: 20–50 Pa;

Supply cathode voltage: −800 to −1500 V;
Collect cathode voltage range: −100 to −500 V;
Under these conditions, strong hollow cathode discharge is generated at the
supply cathode surface and plasma sputtering is taking in place. Under the effect of
bias field, these sputtered particles quickly migrate towards the collect cathode, then
rapidly cooled by a cooling device and eventually deposit in the collection container
as the form of solid nano-particles.
Double glow hollow cathode discharge plasma nano-materials technology has
the following advantages:
(1) Supply cathode can be made of pure metal, or alloy, or other powder metallurgy
materials;
(2) Non-metallic materials and non-conductive materials can be also used as a
supply cathode material;
(3) The size of nano-particles is much smaller than others;
(4) There are no emissions and pollution.
13.5 Double Glow Plasma Thin Diamond Film

Technology
Diamond film has many optimal properties, such as chemical inert and stable,
mechanical hard, wear resistance, corrosion resistance, insulation and high light
transmittance and refractive index, etc. Since 1980s, the diamond thin film synthesis
technology, such as plasma-assisted CVD, has attracted wide attention in the
material engineering field all over the world.
Upon the hollow cathode discharge plasma, carbon–hydrogen gas would be
activated and dissociated. Then carbon in SP3 bonding state would deposit on the
pretreated substrate and form a diamond thin film on the surface. Synthesis of
diamond thin film with the double glow plasma technology has been experimented
in our laboratory [13]. Figure 13.5 is the schematic diagram of the setup for this
Fig. 13.5 Schematic diagram of the system setup for diamond thin film growth with double glow
discharge plasma technology [10]
technology. Using hollow cathode discharge plasma, grid cathodes 7 can be heated
to 1000–2000 °C. The workpiece 4 is an anode and can be heated to 800–1000 °C
with the double glow discharge plasma heating as well as thermal radiation from the
grid cathode. The working gas, a mixture of methane, H2 and O2, would be fully
activated and ionized, and transport through the plasma zone between the perforated
flat cathode and grid cathodes. Under the effect of electric field, plasma-activated
SP3 carbon radicals would migrate to the workpiece and form thin diamond film on
the surface. The workpiece [4] can be silicon wafer, W, Mo, Ti, hard alloy, or
ordinary carbon steel with W, Mo, Ti film on surface.
Thin diamond film synthesized by double glow plasma surface alloying tech-
nology has advantages such as simple equipment, easy process control, and low
manufacture cost, etc.
13.6 Double Glow Plasma Sputter Cleaning Technology
In the thin film deposition process, in order to increase the coating adhesion to the
substrate, it is useful to clean its surface before deposition and coating. Chemical
cleaning is normally used to remove the dirt, rust, or oil/grease from the surface of
the substrate before entering the vacuum deposition system. Plasma cleaning is
typically designed to remove the surface oxide (“native oxide”) which exists nearly
on all metal surfaces when they are exposed to air and other contaminates that
cannot be easily removed using chemical cleaning [14].
13.6 Double Glow Plasma Sputter Cleaning Technology 263
Fig. 13.6 Schematic for plasma cleaning by double glow discharge
Figure 13.6 gives the schematics of plasma cleaning by double glow discharge.
Two parallel plates in a vacuum chamber are biased with negative voltage as is
illustrated. Glow discharge plasma may be formed in the space between two plates.
Plasma sputtering would take in place for cleaning the surface. It should be noted
that such plasma is relatively intense. High electric currents can be obtained from
both power supplies.
Due to high energy and high density plasma produced by double glow discharge,
double glow plasma sputter cleaning has the advantages of quick and thorough
cleaning and purification.
One application example is demonstrated by Wei et al. [14] in Southwest
Research Institute, as disclosed in a USA patent (No.: US 8,747,631 B2) on June
10, 2014. They developed an apparatus and method utilizing double glow discharge
for sputter cleaning of a selected surface inside a hollow substrate such as tubes or
pipes before coating. Figure 13.7 duplicates their process setup, where a shield tube
is provided as the second cathode inside a gun tube. Two negative bias power
supply are applied on, a higher voltage for the gun tube, a low one for the shield
tube. In this way, hollow glow discharge plasma is generated in the space between
two tubes. Sputter cleaning takes place on the inner surface of the gun tube.
Fig. 13.7 A device setup using double glow discharge plasma for inner surface sputter cleaning
before coating by magnetron sputter deposition [14]
13.7 Double Glow Plasma Chemistry
In 1967, Mctaggart [15] proposed a concept of “plasma chemistry” to classify all

chemical reactions in the gas discharge. In fact, the plasma chemistry concept was
originated T. Andrews in 1856, when he first produced ozone by gas discharge.
Afterwards, in 1874, P.A. Thenard was successfully obtained organic thin films in
gas discharge. In 1905, J.N. Collie made the ethylene to be liquid synthesis in gas
discharge. Nowadays, with the deep research and development of vacuum tech-
nology and gas discharge, plasma chemistry has made great progress.
It is expected that the phenomenon of double glow discharge will be applicable
in plasma chemistry. Its application can strengthen the glow discharge and enhance
its controllability, and also to supply metallic elements in the glow discharge for the
chemical reaction.
13.8 Prospect 265
13.8 Prospect
As an innovative complimentary technology, we have developed the double glow

plasma surface metallurgy technology, which can process almost with any solid
materials as an alloying source supply. Later, the arc discharge plasma surface
alloying technique was developed. Furthermore, we developed the arc plasma
added double glow surface alloying technology. Since then, a series of new
extension technology from double glow plasma technology has been experimented,
such as double glow brazing technology, double glow nano-technology, double
glow diamond thin film technology and so on. Recently in the year 2014, the United
States had a US patent about an invention of sputter cleaning technology by using
double glow discharge phenomenon, it is convinced to us that double glow phe-
nomenon and associated surface modification process technologies are a scientific
discovery and engineering innovation.
The double glow discharge phenomenon is the basis and starting point of a series
of innovative technologies. It is a new discovery with important scientific signifi-
cance. It is believed that the double glow discharge phenomenon will have more
application potential with more new version of Xu-Tec technologies in other areas
in the future. More of our attention and effort for further research and exploration
are urgently needed in this new field.
References
1. Pan JD, Fan BH, Xu Z (1991) Arc-added glow plasma surface alloying technology and its
equipment. CN Patent CN1057073
2. Xu Z (1985) Xu Tec process. US Patent 4.520.268
3. Wang FZ (1992) Multi-arc ion infiltrating metals technique. Heat Treat Met 4:3–7
4. Xu Z, Gao Y (2002) The modern surface engineering technique. Shanxi Science and
Technology Publishing House, Taiyuan
5. Pan JD (2002) Surface alloying by glow-discharge plasma with arc source. J Yunnan Univ 24
(1):163–166
6. Pan JD, Fan BH, Xu Z (1993) Arc-added glow plasma surface alloying technology. Acta
Metall Sin 29(9):424–426
7. Pan JD, Fan BH (1993) Arc-added glow plasma surface titaniuming research. Acta
Armamentarii 3:60–66
8. Pan JD, Fan BH (1994) Research of modified layer by arc-added glow plasma surface
aluminuming. Acta Armamentarii 4:53–57
9. He Q, Pan JD (1997) Microstmcture of modified layer by Arc-added glow plasma surface
nickel-chromiuming. Acta Mettall. Sin. 33(4):406–408
11. Wang CA, Su YA. (1990) Double glow plasma sintering technology. CN Patent CN1044609
12. Gao Y, Xu Z (2001) Technology of preparing nano-powders by double glow plasma. CN
Patent CN1316309
13. Pan JD. Fan BH, He Q (1995) Thin diamond film synthesized by double glow plasma
technology. CN Patent CN1103900
14. Wei RH, Langa E, Lee SL (2010) Apparatus and method utilizing a double glow discharge
plasma for sputter cleaning. US Patent US 8,747,631 B2
15. McTaggart FK (1970) Plasma chemistry in electrical discharges. Elsevier, Amsterdam
Closing Remarks
Now this is not the end. It is not even the beginning of the end. But it is, perhaps, the end of
the beginning.
Winston Churchill
November, 10, 1942
Mansion House, London
By this point, it is close to the end of our writing on this book. However, this is
not the end, even not the beginning of the end, for the development of the Xu-Tec
process—surface metallurgy technology with the double glow discharge plasma.
I am glad to see that, in the past almost 50 years in my life, our great effort have
been devoted whole-heartedly to the development of surface metallurgy technol-
ogy, from experimenting plasma nitriding technology to understanding this science,
from discovering the double glow discharge phenomena to engineering develop-
ment of Xu-Tec process for surface metallurgy applications, and from fundamental
understanding of double glow discharge plasma technology to exploring its
industrialization for new material products with better surface performance. We
have advanced through a long journey with many challenges and hard-working, and
also many encouragements and supports.
Looking back to the 1970s, so many researchers were actively engaged in the
research and promotion of plasma nitriding technology in China. A special
“Academic Committee for Ion Bombardment Chemical Heat Treatment” was
established by Ministry of Machinery Industry of China, responsible for leading
and promoting the development of plasma nitriding technology.
Compared with Plasma nitriding technology which can only be applied to a few
gaseous non-metal elements, the double glow discharge plasma surface metallurgy
technology has led us applying almost all chemical elements in the periodic table
for the surface alloying modification of solid materials. It is considered as the major
breakthrough in the materials industry.
Double glow plasma surface metallurgy technology has been proofed to be a
typical resource saving and environmental friendly technology. With the continuous
consumption of alloying elements on the earth, the advantages of the Xu-Tec
process will be more prominent to save alloy material resources. And it will be an
Z. Xu and F.F. Xiong, Plasma Surface Metallurgy with Double
Glow Discharge Technology, DOI 10.1007/978-981-10-5724-3
268 Closing Remarks
important development direction in the future, to be beneficial to our materials

industry and the mankind in the world.
At the close of this writing, I have been full of excitements and thoughts.
Looking back on my life and the trail of the Xu-Tec development, I feel deeply to
have owned to many people who have given me knowledge, encouragement,
support, and a concept of life as well.
First, I am very grateful to my alma mater—Beijing Fourth High School. During
my three-year study in this school, I set up a healthy and optimistic outlook on the
life. The spiritual belief and the guiding philosophy of the life have laid out a
foundation for my life.
Secondly, I will never forget my mentor Professor Gaomei Cheng. In that critical
moment when I just graduated from the college, he came forward with overcoming
all difficulties, and determinedly left me in the university as a teacher determined
my road of life and enabled me to engage my favorite educational and scientific
work which had satisfied my love and interest for science and technology. I deeply
miss Mr. Mei Liu and Professor Guitong Yang, two former presidents of the
Taiyuan Institute of Technology (now Taiyuan University of Technology). They
had always given their beliefs, encouragement and support on me at the crucial
moment, or in a trouble time. In addition, Professor Hengde Li from Tsinghua
University, Professor Yi Wang from Central Iron & Steel Research Institute, and
Mr. Zongrong Wang from Ministry of Science & Technology of China, are very
important Bole-type characters in my life, to make me deeply understand of a
person's growth and development with the help and support of others.
Dr. Roland Lau, a Chinese-American in USA, is deeply grateful for his initial
recognition of the significance of the Xu-Tec process and help for applying the first
patent of this technology in the United States, as well as his contribution of winning
two U.S. government research funding for the technological development project.
I would also like to give my out-of heart gratitude to Professor James Thompson
and Professor Robert Tzou at University of Missouri for their care, encouragement
and help to me in many years to now.
Furthermore, I would also want to give my deep appreciation to Dr. Frank Fulin
Xiong, the co-author of this book, for his encouragement, patience, and many
fruitful and knowledgeable discussions during the book writing and in the cause of
the technology development, and also for his long-term friendship and open
mind-sharing communication with me.
Finally, I would like to express my sincere gratitude to my wife and two sons for
their love, encouragement and support for all of my life.
The momentum to drive me to write this book is relying on my firm belief in this
surface technology. From the technological success of plasma nitriding to many
experimental accomplishments of the double glow discharge plasma metallurgy
process, I believe that this technology can comprehensively improve the perfor-
mance and quality of machinery manufacturing parts, saving a lot of precious metal
elements for the materials industry, and for the benefit of our global society.
Now, this is to end of the book writing. It would be the end of the beginning of
the Xu-Tec technology’s research and development. However, this is, perhaps, the
Closing Remarks 269
real beginning of its technological industrialization. We are looking forward for its
bright and fruitful future.
November 18, 2016 David Zhong Xu
Taiyuan, China

Plasma Surface Metallurgy: Zhong Xu Frank F. Xiong

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Zhong

Plasma Surface Metallurgy

ISBN 978-981-10-5722-9 ISBN 978-981-10-5724-3 (eBook)

Jointly published with Science Press, Beijing, China

Library of Congress Control Number: 2017948213

Printed on acid-free paper

This Springer imprint is published by Springer Nature

The modiﬁcation of metal surfaces is used to increase surface hardness, improve

The book is particularly useful in that it describes industrial applications of

The “Plasma Nitriding” process, invented by German Bernard Berghaus in 1930,

18. China Knowledge Resource Integrated Database (CNKI) (中国期刊全文数据

2.3.3 Plasma Sulphurizing . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

4.8 Cathode Power Transmission Device and Gap Protection . . . . . . 53

6.3 Multiple-Element Plasma Surface Metallurgy . . . . . . . . . . . . . . . 97

7.6 Plasma Surface Metallurgy Mo–Cr Low Alloy HSS . . . . . . . . . . 124

9.2 Plasma Surface Metallurgy of TiAl . . . . . . . . . . . . . . . . . . . . . . 165

11.3.1 Zirconia Functional Ceramics . . . . . . . . . . . . . . . . . . . . 218

13 Other Technologies by Double Glow Discharge Plasma

Abstract In the long-term industrial engineering development practice, the

1.1 Engineering Materials and Its Surface

1.2 Surface Engineering and Its Classiﬁcation

1.2.1 Concept of Surface Engineering

In order to meet the requirements of material service and engineering applications,

In general, the surface engineering system is composed of the following three

1.2.2 Surface Hardening Technology

The surface hardening technology, as one of common material surface engineering

1.2.3 Surface Covering Technology

1.2.4 Surface Alloying/Metallurgy Technology

Surface alloying or surface metallurgy technology is to use physical or chemical

All surface technologies concerning the alteration of surface composition or

1.2.5 Classiﬁcation Table

In summary, the classiﬁcation of surface engineering technology is given in

Fig. 1.1 The classiﬁcation of surface engineering technology

1.3 Existing Surface Alloying Technology

Surface alloying technology has a long development history. Back to China’s

1.3.1 Conventional Surface Alloying Technology

3. Gas surface alloying: The working-piece is treated in an atmosphere containing

1.3.2 Modern Surface Alloying Technology

1.3.3 Concept of Plasma Surface Metallurgy

Discharge and Electrical Insulation in Vacuum” held in Columbia, South Carolina,

1.4 Glow Discharge and Plasma Nitriding

1.4.1 History of Glow Discharge

1.4.2 Concept of Plasma

1.4.3 Advent of Plasma Nitriding in Germany

Abstract Plasma nitriding technology, developed based on the glow discharge

2.1 Glow Discharge and Its Characteristics

2.1.1 Characteristics of Glow Discharge

Plasma nitriding is a surface alloying technology which is developed based on the

2.1.2 Stratiﬁed Phenomenon

Fig. 2.2 Qualitative characteristics (stratiﬁed phenomenon) of a dc glow discharge [1]

2.1.3 Interactions Between Ions and Material Surface

Fig. 2.3 Schematic illustration of ion-surface interactions

2.2 Plasma Nitriding Process

Plasma nitriding was invented by Berghaus [4]. It is considered as “the Foundation

2.2.1 Basic Principle

Fig. 2.4 Schematic diagram of plasma nitriding experimental setup [1]

Commonly used plasma nitriding process parameter range:

2.2.3 Industrial Applications

machinery, petroleum, chemical industry, metallurgy, automobile, aviation and

2.3 Other Plasma Surface Alloying Technology

2.3.1 Plasma Carburizing

2.3.2 Plasma Nitro-Carburizing

Plasma nitro-carburizing is processed in the condition of plasma nitriding with