Laser Applications in Surface Modification: Jianhua Yao Qunli Zhang Rong Liu Guolong Wu

Advanced Topics in Science
and Technology in China 65
Jianhua Yao · Qunli Zhang ·
Rong Liu · Guolong Wu
Laser Applications
in Surface
Modification
Advanced Topics in Science and Technology
in China
Volume 65
Zhejiang University is one of the leading universities in China. In Advanced Topics
in Science and Technology in China, Zhejiang University Press and Springer jointly
publish monographs by Chinese scholars and professors, as well as invited authors
and editors from abroad who are outstanding experts and scholars in their fields.
This series will be of interest to researchers, lecturers, and graduate students alike.
Advanced Topics in Science and Technology in China aims to present the latest
and most cutting-edge theories, techniques, and methodologies in various research
areas in China. It covers all disciplines in the fields of natural science and
technology, including but not limited to, computer science, materials science, the
life sciences, engineering, environmental sciences, mathematics, and physics.
This book series is indexed by the SCOPUS database.
More information about this series at https://link.springer.com/bookseries/7887

Jianhua Yao · Qunli Zhang · Rong Liu ·
Guolong Wu
Laser Applications in Surface

Modification
Jianhua Yao Qunli Zhang
Institute of Laser Advanced Manufacturing Institute of Laser Advanced Manufacturing
Zhejiang University of Technology Zhejiang University of Technology
Hangzhou, Zhejiang, China Hangzhou, Zhejiang, China
Rong Liu Guolong Wu

Department of Mechanical and Aerospace Institute of Laser Advanced Manufacturing
Engineering Zhejiang University of Technology
Carleton University Hangzhou, Zhejiang, China
Ottawa, ON, Canada
ISSN 1995-6819 ISSN 1995-6827 (electronic)

Advanced Topics in Science and Technology in China
ISBN 978-981-16-8921-5 ISBN 978-981-16-8922-2 (eBook)
https://doi.org/10.1007/978-981-16-8922-2
Jointly published with Zhejiang University Press, China

The print edition is not for sale in China Mainland. Customers from China Mainland please order the
print book from: Zhejiang University Press.
© Zhejiang University Press 2022

This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether
the whole or part of the material is concerned, specifically the rights of reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or
information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
The publishers, the authors, and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publishers nor the authors or
the editors give a warranty, express or implied, with respect to the material contained herein or for any
errors or omissions that may have been made. The publishers remain neutral with regard to jurisdictional
claims in published maps and institutional affiliations.
This Springer imprint is published by the registered company Springer Nature Singapore Pte Ltd.
The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721,
Singapore
Preface
In the service process of mechanical parts, key basic parts are prone to failure and
cause equipment failure, which brings huge economic losses. Among them, more than
80% of the failures are caused by local surface wear and corrosion. Therefore, it is of
great significance to adopt advanced surface modification technology to improve the
surface performances of key basic parts. As one of the advanced surface engineering
technologies, laser surface modification technology has the characteristics of high
performances, low deformation, high bonding strength, green, and intelligence. It
can achieve strengthening effects that traditional surface technology cannot meet
and has been widely used in many areas of the national economy.
Laser cladding of Stellite alloys and metal-ceramic composites were put forward in
this book. Besides, nanomaterials including carbon nanotubes and Al2 O3 nanopar-
ticles were introduced into laser processing to form high-temperature resistance,
chemical stability, wear- and oxidation-resistant composite coatings. The contents
of this book include recent research outcomes of the authors’ group, in various
aspects such as theoretical analysis and experimental data, presented with the assis-
tance of figures and tables, so as to help readers understand the advanced laser surface
modification processes easier.
From this book, the readers can get more knowledge about the basic principle
and application of the two main laser-assisted surface modification technologies,
i.e., laser cladding and laser surface hardening, and gain a deep insight into the
process and characteristics of the nanomaterial-assisted laser surface enhancement.
The book is aimed to provide the guidance and reference for the researchers, engi-
neers, and students in the fields of mechanical engineering, laser processing, and
material engineering.
This book is written by Prof. Jianhua Yao, Prof. Qunli Zhang, Prof. Rong Liu,
and Associated Prof. Guolong Wu, Zhejiang University of Technology, China. Prof.
Yi Pan, Dr. Zhehe Yao, Dr. Liang Wang, Dr. Yuan Chen, Dr. Yinping Ding, and
Dr. Jie Zhang have also contributed to the research and relevant experiments. For
systematical integrity, this book has cited the research results published in book,
journal, and conference articles from international and domestic experts in the related
fields; hence, we wish to express sincere thanks to them. The research projects
v
vi Preface
covered in this book have been sponsored and supported by the National Key R&D
Program of China (2018YFB0407300), the National Natural Science Foundation of
China (52075495, 51975533), and the Key R&D Program of Zhejiang Province,
China (2019C04004). Here, we all express our great appreciation.
There are inevitably mistakes and errors in the book due to our oversight; please
feel free to make comments and criticization.
Hangzhou, China Jianhua Yao

Qunli Zhang
Rong Liu
Guolong Wu
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Hardfacing via Laser Cladding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 Materials for Hardfacing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.2 Stellite Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.3 Hardfacing Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.4 Hardfacing from Laser Process . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2 Surface Hardening by Laser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.1 Features and Advantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.2 Applications on Steel and Cast Iron . . . . . . . . . . . . . . . . . . . . . 6
1.3 Laser Treatment of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.1 Characteristics of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.2 Beneficial Effects of Nanoparticles . . . . . . . . . . . . . . . . . . . . . 7
1.3.3 Nanoparticles in Surface Coatings . . . . . . . . . . . . . . . . . . . . . . 8
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2 Laser Cladding of Stellite Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1 Stellite Alloy Hardfacing for Control Valves . . . . . . . . . . . . . . . . . . . . 11
2.1.1 Sealing Surface Enhancement . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1.2 Improvement of Stellite Alloy Hardfacings . . . . . . . . . . . . . . 13
2.2 Stellite 6 Hardfacing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.1 Problems in Amine Environment . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.2 Fabrication of Hardfacings . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.3 Microstructure and Carbide Ratio . . . . . . . . . . . . . . . . . . . . . . 16
2.2.4 Hardness and Wear Properties . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.5 Corrosion Behavior Under Polarization Test . . . . . . . . . . . . . 19
2.2.6 Corrosion Behavior Under Failure Test . . . . . . . . . . . . . . . . . . 27
2.3 Stellite Alloy Mixture Hardfacing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.3.1 Laser Hardfacing Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.3.2 Microstructure Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.3.3 Hardness and Wear Resistance . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.3.4 Cavitation-Erosion Performance . . . . . . . . . . . . . . . . . . . . . . . . 39
vii
viii Contents
2.3.5 Electrochemical Corrosion Behavior . . . . . . . . . . . . . . . . . . . . 40

2.4 Molybdenum Stellite Alloy Hardfacings . . . . . . . . . . . . . . . . . . . . . . . 42
2.4.1 Laser Creation of Hardfacings . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.4.2 Microstructural Characterization . . . . . . . . . . . . . . . . . . . . . . . 44
2.4.3 Hardness and Wear Performance . . . . . . . . . . . . . . . . . . . . . . . 46
2.4.4 Corrosion Resistance of Hardfacings . . . . . . . . . . . . . . . . . . . . 47
2.5 Summary of Stellite Alloy Hardfacings . . . . . . . . . . . . . . . . . . . . . . . . 52
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3 Laser Cladding of Metal-Ceramic Composites . . . . . . . . . . . . . . . . . . . . 59
3.1 Surface Enhancement with Composite Coatings . . . . . . . . . . . . . . . . . 59
3.1.1 Laser Deposition of Metal-Ceramic Composite
Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.1.2 Improvement of Metal-Ceramic Composite Coatings . . . . . . 61
3.2 Nickel Alloy Composite Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.2.1 Laser Cladding of WC/NiCrMo Composite . . . . . . . . . . . . . . 61
3.2.2 Morphology of Coating Specimens . . . . . . . . . . . . . . . . . . . . . 63
3.2.3 Microstructure of Coating Specimens . . . . . . . . . . . . . . . . . . . 65
3.2.4 Elemental Dilution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.2.5 Coating Hardness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.2.6 Coating Wear Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.3 Steel Composite Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3.3.1 Laser Cladding of TiC/H13 Composite . . . . . . . . . . . . . . . . . . 74
3.3.2 Microstructure of TiC/H13 Composite Coating . . . . . . . . . . . 75
3.3.3 Tribological Behavior of TiC/H13 Composite Coating . . . . . 76
3.3.4 Thermal Stability of TiC/H13 Composite Coating . . . . . . . . . 77
3.4 Summary of Composite Coating via Laser Cladding . . . . . . . . . . . . . 78
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
4 Laser Surface Hardening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
4.1 Surface Hardening of Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
4.1.1 Methods of Surface Hardening . . . . . . . . . . . . . . . . . . . . . . . . . 83
4.1.2 Surface Hardening via Laser Process . . . . . . . . . . . . . . . . . . . . 84
4.2 Surface Hardening of 17-4PH Stainless Steel . . . . . . . . . . . . . . . . . . . 85
4.2.1 Laser Hardening Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
4.2.2 Microstructure of Hardened Surface . . . . . . . . . . . . . . . . . . . . 86
4.2.3 Hardness of Hardened Surface . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.2.4 Mechanical Properties of Hardened Surface . . . . . . . . . . . . . . 87
4.2.5 Cavitation-Erosion Resistance of Hardened Surface . . . . . . . 89
4.2.6 Extreme Value Analysis (EVA) Model . . . . . . . . . . . . . . . . . . 91
4.3 Surface Hardening of Cast Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4.3.1 Laser Surface Remelting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4.3.2 Microstructure of Hardened Layer . . . . . . . . . . . . . . . . . . . . . . 95
4.3.3 Hardness and Wear Resistance of Hardened Layer . . . . . . . . 98
4.4 Summary of Laser Surface Hardening . . . . . . . . . . . . . . . . . . . . . . . . . 100
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
Contents ix
5 Laser-Processed Coatings Involving Nanoparticles . . . . . . . . . . . . . . . . 103

5.1 Laser Process of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
5.1.1 Application of Nanoparticles in Material Development . . . . 103
5.1.2 Laser Process of Nanoparticle-Containing Materials . . . . . . 104
5.2 Carbon Nanotubes Containing Superalloy Coating . . . . . . . . . . . . . . 106
5.2.1 Strengthening of Inconel 718 Alloy . . . . . . . . . . . . . . . . . . . . . 106
5.2.2 Preparation of Coated Carbon Nanotubes (CNTs) . . . . . . . . . 106
5.2.3 Laser Cladding Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
5.2.4 Morphology of Ni-Coated MWCNTs Powder . . . . . . . . . . . . 108
5.2.5 Microstructure of Cladded Specimens . . . . . . . . . . . . . . . . . . . 110
5.2.6 Laves Phase Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
5.3 Coating Prepared Using Nano-Al2 O3 . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5.3.1 Preparation of Coating with Fine Grains . . . . . . . . . . . . . . . . . 117
5.3.2 Microstructures of Ni–P–Al2 O3 Plating and Coating . . . . . . 119
5.3.3 Microhardness of Plating and Coating . . . . . . . . . . . . . . . . . . . 122
5.4 Coatings Prepared with Different Laser Powers . . . . . . . . . . . . . . . . . 124
5.4.1 Coating Preparation Processes . . . . . . . . . . . . . . . . . . . . . . . . . 124
5.4.2 Coatings Prepared with Low Laser Power . . . . . . . . . . . . . . . 125
5.4.3 Coatings Prepared with High Laser Power . . . . . . . . . . . . . . . 126
5.4.4 Microhardness and Wear Resistance of Coatings . . . . . . . . . . 128
5.5 Cracking of Nano-Al2 O3 Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
5.5.1 Nano-Al2 O3 Coating Preparation . . . . . . . . . . . . . . . . . . . . . . . 131
5.5.2 Crack Examination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
5.5.3 Laser Process Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
5.5.4 Ratio of Nano-Al2 O3 Particle . . . . . . . . . . . . . . . . . . . . . . . . . . 134
5.5.5 Overlapping of Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
5.6 Summary of Laser Cladding of Nanomaterials . . . . . . . . . . . . . . . . . . 139
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
Chapter 1
Introduction
Abstract Laser as a high energy source has been extensively utilized in various
surface modifications such as hardfacing, hardening and coating. Laser cladding or
hardfacing, which is a welding-related technique, is applied on surface enhance-
ment by depositing various Stellite alloys, WC/NiCrMo composite and TiC/H13
composite on steels. Laser hardening is a heat treatment process and it is adopted to
increase the wear resistance of 17-4PH stainless steel and infinite chilling medium
NiCr cast iron. The microstructures and associated properties such as hardness and
wear resistance of the fabricated coatings and hardened layers are characterized and
evaluated. With the advance in nanotechnology, nanoparticles have been involved in
forming surface coatings, because compared to large particles nano-scaled objects
possess better surface properties due to large surface to volume ratio. These surface
properties play a crucial role in the performance of the particles in different stages
of production, processing and final application. One of the applications of nanopar-
ticles is incorporating nickel-coated carbon nanotubes (CNTs) into the gas atomized
spherical Inconel 718 superalloy powder to create a composite coating which has
minimum brittle Laves phase in nickel-based Inconel 718 alloy during laser cladding.
Preparation of nano SiC and SiO2 coatings on graphite is achieved via laser irradi-
ation to protect the oxidation of graphite at high temperature. The effects of laser
energy density on the microstructure, quality and high temperature oxidation resis-
tance of the cladding layer are systematically studied. Additionally, nano Al2 O3 is
used for preparing wear- and oxidation-resistant coatings with fine grains by co-
depositing Al2 O3 and Ni-P via electroless plating, combining with laser treatment
on the Ni-P-Al2 O3 plating.
1.1 Hardfacing via Laser Cladding
1.1.1 Materials for Hardfacing
Hardfacing is a metalworking process to apply harder or tougher materials to a base

metal in order to increase its wear resistance. This technique can be employed on a
new part during manufacturing production or be used to repair a worn-down surface
[1]. In other words, hardfacing process is to deposit hard, wear-resistant materials
© Zhejiang University Press 2022 1
J. Yao et al., Laser Applications in Surface Modification, Advanced Topics in Science
and Technology in China 65, https://doi.org/10.1007/978-981-16-8922-2_1
2 1 Introduction
on a worn or new component surface to achieve thick coatings for resisting severe
wear in service [2]. There are many means to produce hardfacing layers, commonly
including thermal spraying, spray–fuse, welding, and laser cladding [3].
A wide range of materials can be selected for depositing hardfacing layers, but the
main categories of materials are hard metals or alloys, ceramics, and metal-ceramic
composites. For hard alloys, there are three general groups: first, low-alloy iron-based
alloys, which are composed of 12% alloy components in maximum, usually including
chromium, molybdenum, and manganese [4]; second, high-alloy iron-based alloys,
containing 12–50% alloy content; chromium is added in all iron-based hardfacing
alloys, but nickel or cobalt is often added in some of these alloys [5]; and third,
cobalt-based and nickel-based alloys, which contain relatively small amounts of iron
(1.3 to 12.5%) [6]. Among these alloys, the most costly, but also the most versatile,
are the cobalt–chromium–tungsten alloys [7]. Cobalt-based and nickel-based alloys
possess excellent resistance to corrosion and oxidation and have low coefficients of
friction, which make these alloys especially applicable in the environments involving
metal-to-metal wear [8] at high temperatures above 600 °C [9]. Cobalt-based alloys
can retain much of their room-temperature hardness at high temperatures up to 1200°
[10].
Cemented tungsten carbide (WC) and tungsten carbide composites are deemed
typical ceramic-based materials for hardfacings [11], but other ceramic materials
such as alumina and silica are also often used. Tungsten carbide has several favorable
features; in particular, it is one of the hardest materials available for industrial appli-
cation; therefore, it is often referred to as a hard metal owing to a very high hardness
value of 1600 HV, compared to mild steel which has the hardness in the region of 160
HV [12]. For the use for hardfacing, WC is crushed and employed in conjunction with
a binding metal. Cemented carbides are composite materials consisting of individual
tungsten carbide particles imbedded in a ductile metal binder matrix of either cobalt
or nickel. Various properties of a particular grade of carbide, in particular, the physical
and metallurgical, are governed by many factors, especially, the chemical composi-
tion of the carbide, the type and content of the binder metal, the hardfacing process,
etc. [13]. Hard alloys can also be enhanced by adding a certain amount (usually less
than 30 wt%) of WC to hard alloy powders, which creates metal-ceramic composite
hardfacings. The hardness of the obtained composite coating highly depends on the
amount of WC in the composite powder. For high-temperature wear applications,
titanium carbide (TiC) with a high melting point (3065 °C), low density (4.94 g/cm3 ),
and high hardness (3200 kg/mm2 ) is very popular as the reinforcement of composite
hardfacings [14]. The binder materials are usually metallic elements such as Fe, Co,
or Ni, present as a ductile second phase to improve the fracture toughness of the
composites [15].
1.1.2 Stellite Alloys
Stellite alloys are a group of cobalt-based alloys, mainly in two composition

systems: Co–Cr–W–C and Co–Cr–Mo–C. With exceptional properties, these alloys
1.1 Hardfacing via Laser Cladding 3
are favorable hardfacing materials [16]. The designed compositions of Stellite alloys
are primarily for wear resistance, but these alloys also display excellent high-
temperature properties, good corrosion, and oxidation resistance [17]. In addition
to Co, chromium (Cr) is the main alloying element of Stellite alloys, but they
also contain tungsten (W) or molybdenum (Mo) and a small amount of carbon (C)
[18]. The Stellite alloy family consists of a large number of various Stellite alloys
with different proportions of cobalt, chromium, tungsten, molybdenum, nickel, iron,
aluminum, boron, carbon, manganese, etc., but most alloys contain four to six of
these elements [19]. The main identifications of current Stellite alloy grades are
carbon and tungsten or molybdenum contents; hence, the amount and type of carbides
are precipitated in the microstructures of the alloys during solidification [20]. The
major difference among individual wear-resistant Stellite alloys is carbon content
and thus carbide volume fraction in the materials. For Stellite 3 which has a very
high carbon content of 2.4 wt%, the carbides constitute about 30 wt% of the material.
These carbides are of the M7 C3 (chromium-rich primary) and M6 C (tungsten-rich
eutectic) types, where M represents the metal components. For Stellite 6 with 1.2
wt% carbon, the carbides constitute approximately 16 wt% of the material, which
are predominantly chromium-rich eutectic carbides of the M7 C3 type [18].
The main alloying element Cr in Stellite alloys plays several roles. First, it is one of
the carbide formers; that is, there are Cr-rich carbides in Stellite alloys such as Cr7 C3
and Cr23 C6 . Second, it is also the strengthener of solid solution as a solute. Third,
it provides corrosion and oxidation resistance by forming Cr-rich oxide films. Other
alloying elements W and Mo have a key function in Stellite alloys; both strengthen the
solid solution matrix due to large atomic size, which impedes dislocation flow when
present as solute atoms [21], but they also create carbides in high-carbon Stellite
alloys when added in large quantities (>5 wt%). These carbides are of M6 C and M3 C
types where M represents metal [22], although the carbides in Stellite alloys are
mainly Cr-rich such as Cr7 C3 and Cr23 C6 [18]. It is possible to tailor the properties
of Stellite alloys by switching W content for Mo, but this change will not affect the
strengthening effect to the solid solution. In the meanwhile, Mo can also improve the
corrosion resistance of Stellite alloys in reducing environments [21] and increasing
the Mo content influences the type of carbide formation in high-carbon Stellite alloys
as well [23].
Differently, in low-carbon (<0.25 wt%) Stellite alloys, when the Mo content is
at a level less than 5.5 wt%, such as Stellite 21, the eutectic phase contains Cr-rich
carbides and minor Co3 Mo intermetallic compounds. It was also found that when
the Mo content was doubled (11 wt%) in Stellite alloys, designated as Stellite 22,
the amount of Co3 Mo intermetallic compound was increased considerably [24]. This
differs from that in high-carbon (>1 wt%) Stellite alloys, where adding excessive Mo
(>5 wt%) can promote the formation of Mo-rich carbides [25]. High-molybdenum
Stellite alloys have been developed in recent years, which include low-carbon Stellite
22 and Stellite 728, and high-carbon Stellite 712 and Stellite 720. It was shown in
previous studies that Stellite 22 and Stellite 728 differ from low-molybdenum, low-
carbon Stellite 21 in microstructure, mechanical properties, erosion, wear and corro-
sion performance [23–30]. The experiments revealed that increase of Mo content in
4 1 Introduction
a low-carbon Stellite alloy generated some new phases—intermetallic compounds

(Co3 Mo and Co7 Mo6 ), which were brittle but can enhance the wear resistance of the
alloy significantly.
1.1.3 Hardfacing Process
Hardfacing can be applied on a surface by a number of different welding processes.

Depending on many factors such as nature of work to be hardfaced, function of the
component, base metal composition, size and shape of component, accessibility of
weld equipment, state of repair of worn components, number of same or similar
items to be hardfaced, etc., the most suitable welding process can be selected for a
given job. Various processes for hardfacing can be categorized as follows [31]:
• Arc welding—shielded metal, flux-cored, and submerged arc welding
• Gas welding—deposition by oxygen–acetylene gas welding
• Combination of arc and gas—tungsten-inert gas welding and gas metal arc
welding
• Powder spraying—flame spraying, high velocity oxygen fuel process, electric arc
spraying, and plasma transferred arc
• Laser cladding.
When minimal thermal distortion of the component and good process control are
required, thermal spraying is a better selection for depositing a coating or hardfacing.
Common materials deposited by thermal spraying for hardfacing can be cermets
including WC–Co and alumina-based ceramics. The coatings from thermal spray
process can achieve a thickness of about 0.3 mm [32]. Spray–fuse coatings, also
known as self-fluxing overlay coatings, are first applied to the component surface
using a flame spraying process and then subsequently fused using an oxyacetylene
torch or a radio-frequency induction coil. A coating that is produced by fused deposi-
tion forms a metallurgical bond to the substrate and is free of porosity via wetting the
substrate surface. Various types of alloys can be used with the spray–fuse process,
but the most important group is from Ni–Cr–B–Si–C alloy system, which has a
melting temperature in the range of 980–1200 °C [33], depending on the chemical
composition.
Weld hardfacing can achieve very thick (1–10 mm) dense coatings of wear-
resistant materials with high bond strength. Various welding techniques can be
employed to produce hardfacings, including metal-inert gas (MIG), tungsten-inert
gas (TIG), plasma transferred arc (PTA), submerged arc (SAW), and manual metal arc
(MMA). A wide range of materials can be used for weld hardfacing, which include
cobalt-based alloys (Stellite alloys), martensitic and high-speed steels, nickel alloys,
and WC–Co cemented carbides. The component surface from weld hardfacing is
often machined to achieve required finish for final use.
1.1 Hardfacing via Laser Cladding 5
1.1.4 Hardfacing from Laser Process
Laser cladding or hardfacing is a welding-related technique which is mainly utilized

to repair worn surfaces of used components by depositing a welded overlay to
provide hardness, abrasion, erosion, galling, impact, corrosion, or heat resistance.
The cladding layers perform better in a harsh environment for longer time and with
less maintenance [2]. When applied to new parts, laser cladding protects the substrate
material with a layer of a complex alloy coating which improves chemical, physical,
and mechanical properties of the substrate.
Laser hardfacing uses a high-power laser beam to fuse coating materials onto
substrates; hence, a coating layer is produced with excellent wear resistance. This
process is able to deposit hard materials onto engineering components of low-grade
steels, thus extending the service life of the parts. This technique is complementary
to or even substitutional to the manual gas metal arc welding (GMAW), gas tungsten
arc welding (GTAW), plasma arc welding (PAW), and other welding processes [34].
Laser hardfacing study has attracted much attention of researchers in recent years
because of the advantage in saving strategic materials, compared to conventional
coating processes. It can also provide better dimensional precision of the components
owing to less thermal load on the bulk material.
In this book, the studies of the microstructure, wear and corrosion performances
of the hardfacings of various Stellite alloys, which are prepared via laser cladding,
are presented. These Stellite alloys include conventional Stellite 6 and Stellite 21 and
newly developed Stellite 22 and Stellite 728 as well as novel Stellite alloy mixture
(70 wt% Stellite 3 and 30 wt% Stellite 21). Meanwhile, the WC/NiCrMo composite
hardfacing and TiC/H13 steel composite hardfacing fabricated from laser process
are studied, focusing on the comparison in microstructure, hardness, and wear resis-
tance of the WC/NiCrMo composite hardfacing prepared using circular laser spot
and wideband laser spot, respectively, and the microstructural nonuniformity of the
TiC/H13 hardfacing due to the temperature gradient of the cladding layer during the
laser process and the thermal stability of the TiC/H13 hardfacing at high temperature.
1.2 Surface Hardening by Laser
1.2.1 Features and Advantages
Laser hardening is considered as a heat treatment process or surface hardening

process in which the surface of a metal part is heated by a laser beam and then
the surface is cooled down rapidly in surrounding air [35]. This process is used
exclusively on ferrous materials which are able to be hardened, including steels and
cast iron with a carbon content greater than 0.2 wt%. The parts from laser hardening
process do not require much refinishing work, and this technique enables the work
6 1 Introduction
on irregular, three-dimensional workpieces. Laser hardening can improve the hard-

ness and wear resistance of the workpiece, thus reducing abrasive wear. Another
advantage of laser hardening technique is that it allows for absolute control on the
surface hardness and texture. The process consists of rapidly heating the material
surface by laser beam, short holding at the target temperature, and intensive cooling
due to the high thermal conductivity of the material. During the cooldown period, a
process called self-quenching takes place, resulting in fine-grained structure within
the thin layer on the surface of the part [36]. The modified microstructure can alter
the mechanical and tribological properties of the surface of the treated parts.
Laser hardening is employed to locally improve the wear resistance and service
life of parts for a wide variety of applications, from press-forming tools to oil-drilling
equipment. This technology is especially suitable for the applications where minimal
heat input into the surrounding material is critical. It offers many advantages over
conventional heat treatment processes such as high throughput, reproducibility, and
product quality. In many industrial applications, localized treatment with minimal
heat input is required, which results in reduced distortion of the part; meanwhile, the
rapid quench rate produces a fine microstructure.
1.2.2 Applications on Steel and Cast Iron
In this book, the research in the laser surface treatment of 17-4PH stainless steel and
infinite chilling medium NiCr cast iron is reported. The heat treatment applied on the
surface of 17-4PH stainless steel via laser process was strengthening precipitation
hardening, which included laser solid solution treatment of the steel surface, followed
by aging the steel at 460 °C for 3 h, then cooling it by water. The microstructures,
mechanical properties, and cavitation-erosion behavior of the laser-treated 17-4PH
stainless steel were investigated. Laser surface remelting treatment was conducted
on infinite chilling medium NiCr cast iron to modify surface properties. The laser-
modified surface was microstructurally analyzed to identify three distinct zones:
melting zone, transition zone, and heat-affected zone (HAZ). The hardness and wear
resistance of the cast iron after the surface treatment were evaluated.
1.3 Laser Treatment of Nanomaterials
1.3.1 Characteristics of Nanomaterials
Nanoparticles are defined as ultrafine particles sized between 1 and 100 nm in diam-
eter. In recent decades, considerable scientific research has been conducted in various
uses of nanoparticles in many fields such as construction, electronics, manufac-
turing, cosmetics, and medicine. The advantages of adding nanoparticles in structure
1.3 Laser Treatment of Nanomaterials 7
materials are immense, including promising extraordinary physical, chemical, and

mechanical properties [37]. Among the many different types of nanoparticles, tita-
nium dioxide, carbon nanotubes, silica, copper, and alumina are the most popular in
mechanical applications.
Nanoparticles and nanostructured materials represent an active research area
spreading and expanding in many application fields. These materials have gained
prominence in technological advancements due to their tunable physicochemical
characteristics such as melting point, wettability, electrical and thermal conductivity,
catalytic activity, light absorption, and scattering, resulting in enhanced performance
over their bulk counterparts [38].
There are four material-based categories of nanoparticles and nanostructured
materials. (1) Carbon-based nanomaterials contain carbon and are found in geome-
tries such as hollow tubes, ellipsoids, or spheres. The main production methods
of these materials are laser ablation, arc discharge, and chemical vapor deposi-
tion (CVD) [39]. (2) Inorganic-based nanomaterials include metal and metal oxide
nanoparticles. For metals, Au or Ag nanoparticles are popular, and for metal oxides,
TiO2 and ZnO nanoparticles are commonly used. There are also semiconductors such
as silicon and ceramics [40]. (3) Organic-based nanomaterials are made mostly from
organic matters, which find applications mainly in biomaterials [41]. (4) Composite-
based nanomaterials are multi-phase nanoparticles and nanostructured materials with
one phase on the nanoscale dimension. These nanomaterials can form by combining
nanoparticles with other nanoparticles or nanoparticles combined with larger or bulk-
type materials or even more complicated structures [42]. The composite types are
in a wide range, which can be any combinations of carbon-based, metal-based, or
organic-based nanomaterials with any form of metal, ceramic, or polymer bulk mate-
rials. Nanomaterials are synthesized in various shapes and geometries depending on
the application requirements.
1.3.2 Beneficial Effects of Nanoparticles
Particle size determines the ratio of surface area to volume. Powders of small particle
size possess high specific surface areas. Therefore, the specific surface area of a
powder particle is considered a dimensional property. In many applications, high
specific surface area is attractive and desired. In general, nanomaterials used for
surface coatings are to selectively change or influence distinct particle properties.
Compared to large particles, nanoscaled objects possess better surface properties, in
particular, if they are smaller than 10 nm, because of large surface-to-volume ratio.
These surface properties are crucial for the behavior of the particles during different
stages of production, processing, and final application.
Nanotechnology is beneficial because it possibly tailors the structures of materials
at extremely small scales so as to achieve specific properties. The materials made
using nanotechnology can be much stronger, lighter, more durable, more reactive, etc.
For instance, nanostructured ceramic coatings exhibit much higher fracture toughness
8 1 Introduction
than conventional wear-resistant coatings on machine parts. It has also been reported
that nanotechnology-enabled lubricants and engine oils significantly reduce wear
and tear, which definitely extends the service lives of moving components in various
applications, for example, power tools, joint parts, and industrial machinery [43].
Regarding lightweight issues on many mechanical systems such as cars, trucks,
airplanes, boats, and spacecraft, nanoscale additives in polymer composite mate-
rials can result in significant fuel savings. Other applications of nanoparticle-based
composites include baseball bats, tennis rackets, bicycles, motorcycle helmets, auto-
mobile parts, and power tool housings, which are of lightweight, high stiffness, good
endurance, and resilience [44].
1.3.3 Nanoparticles in Surface Coatings
The progressive deterioration of metallic surfaces due to corrosion and wear is crucial
for many components during service, in particular, in major industrial plants, because
it can cause great loss of plant efficiency and at worst a shutdown. Using wear and
corrosion-resistant coatings is one of the most effective means for metal surface
protection. Additives containing nanoscale materials in various coatings have long
been recognized to be promising for surface enhancement. Nanomaterial-containing
coatings offer much better material and processing properties than conventional coat-
ings, for instance, increased indentation and cracking resistance, improved elasticity
and plasticity, etc. [45].
It has also been found that nanomaterial-containing coatings can improve the
scratch resistance of a surface and increase hardness [46]. The presence of nanopar-
ticles in coatings represents a highly innovative application of nanotechnologies, in
line with the requirements of surface protection. Adding nanoparticles into galvanic
coatings allows the replacement of the chrome surface passivation, preserving the
features of resistance to corrosion and wear, owing to the decrease of the friction
coefficient [47]. According to various studies reported in literature, nanocoatings
certainly show undisputed advantages, compared to conventional coatings, among
which the most interesting is higher homogeneity versus microscale, low thermal
conductivity, enhanced hardness and fracture toughness, the independence between
toughness and hardness, improved resistance to wear and corrosion.
In this book, the study in minimizing the formation of brittle Laves phase in
nickel-based Inconel 718 alloy during laser cladding by incorporating nickel-coated
carbon nanotubes (CNTs) into the gas atomized spherical Inconel 718 superalloy
powder to create a composite coating is reported. It was found that the addition of
nickel-coated CNTs can suppress the effect on the element segregation and Laves
phase formation of laser-clad IN718 superalloy significantly. The studies of nano-
Al2 O3 used for preparing wear- and oxidation-resistant coatings with fine grains by
co-depositing Al2 O3 and Ni–P via electroless plating, combining with laser treatment
on the Ni–P–Al2 O3 plating, are also detailed in this book. Minimization of cracking
in the cladding layer of Ni-coated nano-Al2 O3 is delineated.
References 9
References
1. Gualco A, Svoboda HG, Surian ES, de Vedia LA (2010) Effect of welding procedure on wear
behaviour of a modified martensitic tool steel hardfacing deposit. Mater Des 31(9):4165–4173
2. Kwok CT, Man HC, Cheng FT (2001) Cavitation erosion–corrosion behaviour of laser surface
alloyed AISI 1050 steel using NiCrSiB. Mater Sci Eng A 303(1–2):250–261
3. Buchely MF, Gutierrez JC, León LM, Toro A (2005) The effect of microstructure on abrasive
wear of hardfacing alloys. Wear 259(1–6):52–61
4. Berns H, Fischer A (1997) Microstructure of Fe-Cr-C hardfacing alloys with additions of Nb,
Ti and B. Mater Charac 39:499–527
5. Fouilland L, El Mansori M, Massaq A (2009) Friction-induced work hardening of cobalt-base
hardfacing deposits for hot forging tools. J Mater Process Technol 209(7):3366–3373
6. El Mansori M, Nouari M (2007) Dry machinability of nickel-based weld-hardfacing layers for
hot tooling. Int JMach Tool Manuf 47(11):1715–1727
7. Riddihough M (1970) Stellite (Cobalt-Chromium-Tungsten alloy) as a wear-resistant material.
Tribology 3(4):211–215
8. D’Oliveira ASCM, Vilar R, Feder CG (2002) High temperature behaviour of plasma transferred
arc and laser Co-based alloy coatings. Appl Surf Sci 201(1–4):154–160
9. Drapier JM, Davin A, Magnee A, Coutsouradis D, Habraken L (1975) Abrasion and corrosion
resistant cobalt base alloys for hardfacing. Wear 33(2):271–282
10. Yaedu AE, D’Oliveira ASCM (2005) Cobalt based alloy PTA hardfacing on different substrate
steels. Mater Sci Technol 21(4):459–466
11. Blombery RI, Perrott CM (1974) Wear of sprayed tungsten carbide hardfacing deposits. Wear
29(1):95–109
12. Jankauskas V, Antonov M, Varnauskas V, Skirkus R, Goljandin D (2015) Effect of WC grain
size and content on low stress abrasive wear of manual arc welded hardfacings with low-carbon
or stainless steel matrix. Wear 328:378–390
13. Nagentrau M, Mohd Tobi AL, Kamdi Z, Ismail MI, Sambu M (2017) A study on wear failure
analysis of tungsten carbide hardfacing on carbon steel blade in a digester tank. J Fail Analy
Preven 17:861–870
14. Wang XH, Song SL, Zou ZD, Qu SY (2006) Fabricating TiC particles reinforced Fe-based
composite coatings produced by GTAW multi-layers melting process. Mater Sci Eng A 441(1–
2):60–67
15. Wang XH, Zou ZD, Qu SY, Song SL (2005) Microstructure and wear properties of Fe-based
hardfacing coating reinforced by TiC particles. J Mater Process Technol 168(1):89–94
16. Wu YX, Bousser E, Schmitt T, Tarfa N, Khelfaoui F, Rene R, Klemberg-Sapieha JE, Brochu M
(2019) Thermal stability of a Stellite/steel hardfacing interface during long-term aging. Mater
Charac 154:181–192
17. Ahmed R, De Villiers HL (2017) Friction and wear of cobalt-base alloys. Frict Lubr Wear
Technol 18:487–501
18. Davis JR (2000) Cobalt-base alloys, in Nickel, Cobalt, and their alloys. ASM International,
Materials Park, p 362–406
19. Boeck BA, Sanders TH Jr, Anand V, Hickl AJ, Kumar P (1985) Relationships between
processing, microstructure, and tensile properties of a Co-Cr-Mo alloy. Powd Metall 28(2):1–10
20. Kapoor S, Liu R, Wu XJ, Yao MX (2013) Microstructure and wear resistance relations of
Stellite alloys. Int J Adv Mater Sci 4(3):231–248
21. Liu R, Yao MX (2012) High-temperature wear/corrosion resistant Stellite alloys and Tribality
alloys. In: CRC handbook on aerospace and aeronautical materials. CRC Press, Taylor &
Francis, p 151–235
22. Jiang WH, Yao XD, Hu ZQ (1999) Secondary M6 C precipitation in a cobalt-base superalloy.
J Mater Sci Lett 18(4):303–305
23. Kamal K, Ding YP, Liu R, Yao JH, Yao MX (2019) Corrosion performance of 700 series Stellite
alloys in various media. J Mater Eng Perform 28(9):5605–5615
10 1 Introduction
24. Huang P, Liu R, Wu XJ, Yao MX (2007) Effects of molybdenum content and heat treatment
on mechanical and tribological properties of a low-carbon Stellite alloy. J Eng Mater Technol
129(4):523–529
25. Liu R, Yao JH, Zhang QL, Yao MX, Collier R (2015) Microstructures and hardness/wear
performance of high-carbon Stellite alloys containing molybdenum. Metall Mater Trans A
46(12):5504–5513
26. Liu R, Yao JH, Zhang QL, Yao MX, Collier R (2015) Effects of molybdenum content on the
wear/erosion and corrosion performance of low-carbon Stellite alloys. Mater Des 78:95–106
27. Yao JH, Ding YP, Liu R, Zhang QL, Wang L (2018) Wear and corrosion performance of
laser-clad low-carbon high molybdenum Stellite alloys. Opt Laser Technol 107:32–45
28. Collier R, Liu R, Wu XJ, Zhang XZ, Yao MX (2020) Dry-sliding wear performance of
molybdenum-containing Stellite alloys. Wear 29:1384–1399
29. Nsoesie S, Liu R, Chen KY, Yao MX (2013) Erosion resistance of Stellite alloys under solid-
particle impact. J Mater Sci Eng B 3(9):555–566
30. Nsoesie S, Liu R, Chen KY, Yao MX (2014) Analytical modeling of solid-particle erosion of
Stellite alloys in combination with experimental investigation. Wear 309(1–2):226–232
31. Pradeep GRC, Ramesh A, Prasad BD (2010) A review paper on hardfacing processes and
materials. Inter J Eng Sci Technol 2(11):6507–6510
32. Tucker RC Jr (1994) Thermal spray coatings. In: ASM handbook, surface engineering, vol 5.
ASM International, USA, p 497–509
33. Valean PC, Kazamer N, Muntean R, Pascal DT, Marginean G, Serban VA (2018) Investigation
on the characteristics of thermally sprayed NiCrBSi coatings fused by flame and inductive
processing. IOP Conf Series: Mater Sci Eng 416:1–5
34. Ming Q, Lim LC, Chen ZD (1998) Laser cladding of nickel-based hardfacing alloys. Surf Coat
Technol 106(2–3):174–182
35. Babu PD, Balasubramanian KR, Buvanashekaran G (2011) Laser surface hardfacing: a review.
Int J Surf Sci Eng 5(2–3):131–151
36. Moradi M, Arabi H, Nasab SJ, Benyounis KY (2019) A comparative study of laser surface
hardfacing of AISI 410 and 420 martensitic stainless steels by using diode laser. Opt Laser
Technol 111:347–357
37. Khan I, Saeed K, Khan I (2019) Nanoparticles: properties, applications and toxicities. Arabian
J Chem 12(7):908–931
38. Jeevanandam J, Barhoum A, Chan YS, Dufresne A, Danquah MK (2018) Review on nanopar-
ticles and nanostructured materials: history, sources, toxicity and regulations. Beilstein J
Nanotechnol 9:1050–1074
39. Aqel A, Abou El-Nour KM, Ammar RA, Al-Warthan A (2012) Carbon nanotubes, science and
technology part (I) structure, synthesis and characterization. Arabian J Chem 5:1–23
40. Li JH, Hong RY, Li MY, Li HZ, Zheng Y, Ding J (2009) Effects of ZnO nanoparticles on the
mechanical and antibacterial properties of polyurethane coatings. Prog Org Coat 64:504–509
41. Virlan MJR, Miricescu D, Radulescu R, Sabliov CM, Totan A, Calenic B, Greabu M (2016)
Organic nanomaterials and their applications in the treatment of oral diseases. Molecules
21(2):207–229
42. Tjong SC (2007) Novel nanoparticle-reinforced metal matrix composites with enhanced
mechanical properties. Adv Eng Mater 9:639–652
43. Zhou JF, Wu ZS, Zhang ZJ, Liu WM, Xue QJ (2000) Tribological behavior and lubricating
mechanism of Cu nanoparticles in oil. Tribo Lett 8:213–218
44. Gupta M, Wong WLE (2015) Magnesium-based nanocomposites: lightweight materials of the
future. Mater Charac 105:30–46
45. Singh SK, Chattopadhyaya S, Pramanik A, Kumar S, Gupta N (2018) Influence of nanoparticle
on the wear behavior of thin film coatings: a review. Inter J Appl Eng Res 13(6):4053–4058
46. Li XH, Cao Z, Zhang ZJ, Dang HX (2006) Surface-modification in situ of nano-SiO2 and its
structure and tribological properties. Appl Surf Sci 252(22):7856–7861
47. Wang HJ, Chen T, Cong WL, Liu DF (2019) Laser cladding of Ti-based ceramic coatings
on Ti6Al4V alloy: effects of CeO2 nanoparticles additive on wear performance. Coatings
9:109–125
Chapter 2
Laser Cladding of Stellite Alloys
Abstract Metal components often operate in a corrosion and wear combined

environment, which results in surface-initiated failure. Therefore, any approach
that improves surface performance can extend the service life of the compo-
nents. Laser cladding (LC) as an advanced surface modification technique has been
widely employed in surface engineering. Stellite alloys are cobalt-based superal-
loys, displaying exceptional properties such as high-temperature strength, corro-
sion/oxidation, and wear/erosion resistance. They have a wide range of applications,
for example, Stellite 6 a common material for the seat surface enhancement of various
control valves, and Stellite 21 is often used for valve trims under high-pressure
steam. In this chapter, the wear and corrosion performances of conventional and
novel Stellite alloy hardfacings, which are prepared via laser cladding, are studied.
The microstructures of the hardfacings are characterized using scanning electron
microscopy (SEM) with an EDAX energy-dispersive X-ray (EDX) spectroscopy and
X-ray diffraction (XRD). The wear properties of the hardfacings are evaluated on a
pin-on-disk tribometer in dry-sliding mode. The corrosion performance of the hard-
facings is investigated under electrochemical tests in various corrosive media such
as morpholine solution with pH 9.5, to simulate the amine environment of boiler
feedwater in power generation industry, 3.5 wt% NaCl solution, which is a common
corrosive solution used to rank materials for corrosion resistance, and Green Death
solution, representing the typical industry corrosive environment. It is demonstrated
that novel Stellite alloy mixture (70 wt% Stellite 3 and 30 wt% Stellite 21) hard-
facings, Stellite 22 and Stellite 728, are all superior to corresponding conventional
Stellite 6 and Stellite 21 hardfacings, respectively, with respect to hardness, wear,
and corrosion resistance.
2.1 Stellite Alloy Hardfacing for Control Valves
2.1.1 Sealing Surface Enhancement
The sealing is a crucial issue for a control valve because it is directly related to
the reliability of the valve operation. Therefore, the sealing surface is required to

12 2 Laser Cladding of Stellite Alloys
possess sufficient resistance to wear, in order to work along with cyclic metal-to-
metal contact operation. In coal power plants, the seat and trim faces of control
valves must be capable of withstanding very high-contact stress without cracking,
severe wear, corrosion, and cavitation without damage. Consequently, the major
consideration in the valve design is to minimize the sealing surface damage in the
working condition of high-impact loads and severe environments have. To devise
a means to cope with this thorny problem, a hardfacing layer is usually promising,
which can be applied on the sealing surfaces via various processes. Thus, the service
life of a control valve relies significantly on the extent of sealing surface damage
and the impact toughness of the hardfacing layer. Stellite 6 alloy (29% Cr, 4.5% W,
1.5% Mo, 1.2% C, in weight) and Stellite 21 alloy (27% Cr, 5.5% Mo, 0.25% C, Co
balance, in weight) have been popularly employed as the hardfacing materials for
the seat surfaces and trim surfaces of various control valves, respectively, due to their
unique chemical compositions and excellent combined mechanical, anti-corrosion,
anti-wear, and high temperature properties [1–3]. They are frequently deposited via
conventional welding processes, such as tungsten-inert gas and plasma transferred
arc (PTA) welding methods.
Laser cladding utilizes laser technology, combined with the welding process to
create a wear-resistant surface layer. It is an advanced hardfacing technique that
can deposit hard materials on a tough metal surface with controlled thickness in the
selected area of the metal substrate. The process requires a low energy input, thus
causing less heat-induced distortion of the component as compared to conventional
welding methods [4–6]. Many studies in Stellite 6 hardfacing of valve seats have
been reported [4–11]. For example, according to the laser beam interaction time,
the dendrite structure formation in laser cladding of Stellite 6 on mild steel and Cr-
Ni base materials was investigated, with the focus on the influence of various laser
process parameters such as heat input, beam interaction time, scanning frequency,
and transverse speed on the microstructure development [4]. The friction behavior
at the interface between the valve disk and the valve body seat of a gate valve during
operation, whose surfaces were hardfaced with Stellite 6, was also studied analyti-
cally. A more accurate estimate of the friction coefficient between the disk and seat
was needed to predict the valve thrust accurately [7]. The microstructure, compo-
sition distribution, and mechanical properties of Stellite 6 hardfacing on austenitic
engine valve via PTA were studied via various means such as optical microscope,
scanning electron microcopy (SEM), field emission electron probe analyzer (EPMA)
and nanoindentation [11].
The microstructure and mechanical properties of laser-clad joint of Stellite 21
on AISI 316L stainless steel were investigated concerning the gradient in chemical
composition across the substrate/clad interface. It was found that the interdendritic
carbides generated low-energy fracture path in the laser cladding, and the Stellite
21 coating exhibited superior fatigue strength to the AISI 316L substrate [12]. The
fatigue resistance of Stellite 21 cladding on S355 structural steel substrate was eval-
uated using four-point bending and torsion fatigue tests. The results revealed that
the fatigue life of S355 structural steel was not improved at all the applied loads
with the application of Stellite 21 cladding [13]. This was attributed to significant Fe
2.1 Stellite Alloy Hardfacing for Control Valves 13
dilution from the S355 steel substrate during the laser cladding process, which had
a detrimental influence on the fatigue strength of Stellite 21 cladding. There was an
obvious thin Fe-rich layer in the Stellite 21 coating close to the fusion line, which
was the main cause of the fatigue fracture of the Stellite 21 cladding in intergranular
rupture mechanism [14].
2.1.2 Improvement of Stellite Alloy Hardfacings
Stellite 6 is the most popular in Stellite alloy family, which finds application in
various fields of industry. However, it was reported from the valve industry recently
that in the working conditions involving metal-to-metal sealing of the valve Stellite
6 hardfacing was found deficient when subjected to high loading and high-cycle
operating due to insufficient hardness and wear resistance. This would cause leaking
of liquid from the valve after operation for a period of time. For such severe service
conditions, the hardness of the sealing hardfacing is required to be at least HRC50,
while the hardness of Stellite 6 alloy is only about HRC40. Therefore, pure Stellite
6 hardfacing definitely cannot meet the requirements of the valves, which pushed
material engineers to find a harder and more wear-resistant Stellite alloy for such
applications. Stellite 3 (30.5% Cr, 12.5% W, 2.4% C, Co balance, in weight) with
very high carbon content is a good candidate because of its high hardness (about
HRC52) and excellent wear resistance [3, 15]. The wear tests demonstrated that
the sliding wear resistance of Stellite 3 is more than three times better than that
of Stellite 6 [1], but this alloy was very sensitive to cracking during the deposition
process of hardfacing due to large volume fraction of carbides (about 33%) present.
Therefore, a more effective approach to solving this problem is necessary. Since
Stellite 21 is the most applicable low-carbon Stellite alloy, it was proposed that
adding a small amount of Stellite 21 powder into Stellite 3 powder may create a novel
alloy mixture hardfacing, which would be superior both to Stellite 6 in hardness and
wear resistance and to Stellite 3 in prevention of cracking during hardfacing [16].
In the Stellite alloy family, Stellite 21 has unique properties such as creep resistance
and mechanical strength at elevated temperatures, good corrosion resistance, and
strain or work hardening capacity [15–20], which make this alloy popular material
for valve trims of high-pressure steam, oil and petrochemical processes, forging or
hot stamping dies, medical implants, and prosthetics.
It has also been recognized that for valve trims where enhanced wear resistance is
required while good corrosion resistance must be maintained, Stellite 21 is found defi-
cient due to small amount of carbides precipitated in the alloy. However, the increase
in hardness by raising carbon content in Stellite 21 may deteriorate anti-corrosion
properties, because the carbides in Stellite 21 are Cr-rich. The more the carbides
in Stellite 21, the less the Cr in the solid solution is. Thus in the Cr-rich regions,
Cr depletion will occur. Therefore, two new alloys which are modified Stellite 21
alloys, designated as Stellite 22 and Stellite 728, have been proposed and created with
increased Mo content (from 5.5 to 11 wt%) [19–22]. This special chemical compo-
sition results in large amounts of Co3 Mo intermetallic compound precipitated in
the alloys. The experimental results confirmed that Co3 Mo intermetallic compound
has a similar function to the carbides in Stellite alloys in enhancing the hardness
and wear resistance. Due to large atom size, molybdenum in Stellite alloys provides
additional strength to the solid solution matrix when present as a solute atom, which
impedes dislocation flow [23]. On the other hand, when added to low-carbon Stellite
alloys in large quantities, molybdenum participates in the formation of intermetallic
compounds (Co3 Mo or/and Co7 Mo6 ) [19, 20].
2.2 Stellite 6 Hardfacing
2.2.1 Problems in Amine Environment
As mentioned above, Stellite 6 is usually overlay-welded on valve seats as a hard-

facing layer for the valve disk and body, owing to its excellent combined mechan-
ical, corrosion, wear, and high temperature properties, via welding or laser cladding
processes. However, the problem in the practical application of Stellite 6 hardfacing
has been reported from the valve industry [24], when boiler feedwater is treated with
hydrazine (N2 H4 ) and other types of amine derivatives, which says that Stellite 6
hardfacing could fail in such corrosive environment with wear also involved, charac-
terized by the cracking of the hardfacing. Although various comments on this issue
had been noticed, it was still not understood why this failure occurred on Stellite
alloy, because it contains high chromium and can form an oxide film on its surface
to protect corrosion of the substrate.
To help the industry solve this problem, the corrosion performance of Stellite 6
hardfacing prepared via laser cladding in an amine environment, saline (3.5 wt%
NaCl) and Green Death solution, was investigated. The last two solutions are a
common corrosive medium used to rank materials for corrosion resistance and the
typical industry corrosive environment, respectively [25], which were used in this
study for comparison with an amine solution. Cast Stellite 6 was also tested in
parallel for comparison with hardfaced Stellite 6. Meanwhile, the hardness and wear
resistance of Stellite 6 prepared via the two different processes were evaluated to
response the real operation scenario of the alloy in the valve industry where wear
and corrosion are synergetic.
2.2.2 Fabrication of Hardfacings
The cast Stellite 6 specimens and Stellite 6 powder used in this research were all
supplied by Kennametal Stellite Inc., with the chemical compositions given in Table
2.2 Stellite 6 Hardfacing 15
2.1. The morphology of the powder was examined with SEM, which shows a perfectly
spherical shape, and the powder sizes vary in the range of 45–150 µm (Fig. 2.1).
The substrate was a stainless steel 316 plate having the dimensions of 100 × 60 ×
10 mm. Before the hardfacing process, the stainless steel 316 plate was grit-blasted
using 24-mesh alumina and ultrasonically cleaned in absolute ethyl alcohol.
Stellite 6 hardfacing was processed using a LDF400-2000 high-power flexible
fiber-coupled diode laser, as schematically shown in Fig. 2.2. The laser beam profile,
showing energy distribution across the beam in the system, is given in Fig. 2.3. It
is apparent that the energy density of the laser beam is uniformly distributed, which
meets the requirement for producing hardfacing. The system parameters of the laser
device are the output power of 2 kW, the output wavelength of 900–1070 nm, and
the IRB2400/16 robot motion device with six degrees of freedom. Stellite 6 powder
was fed by a powder feeder (GTV-PF-Twin2/2), which was supplied by GTV GmbH,
Germany. The laser cladding process was performed under argon gas shielding. The
process parameters were selected as the laser energy density of 56.25 J/mm2 and
the feeding rate of 13 g/min. In order to obtain optimal process parameters, which
would be used to prepare the Stellite 6 hardfacing specimens, single-track specimens
were prepared first with different process parameters and then laid for examining the
physical appearance of the clad layers. Laser tracks were laid at ~50% overlapping
to achieve a uniform clad thickness. The powder aligning with the laser beam was
focused on the surface of the specimen by using a coaxial cladding head.
Table 2.1 Chemical compositions of Stellite 6 materials (wt%, Co in balance)

Element Cr W Mo C Ni Mn Si Fe
Cast Stellite 6 28.87 4.31 <1 1.2 2.41 0.49 1 2.95
Stellite 6 powder 29 4.5 1.5 1.2 1.8 0.13 0.84 2.01
Fig. 2.1 SEM microscopic

morphology of Stellite 6
powder: a at low
magnification and b at high
magnification [25].
Reprinted from Ding et al.
[25], Copyright (2020), with
permission from Springer
Nature
Fig. 2.2 Schematic diagram

of laser cladding system
[25]. Reprinted from Ding
et al. [25], Copyright (2020),
with permission from
Springer Nature
Fig. 2.3 Energy distribution

across the circular spot laser
beam [25]. Reprinted from
Ding et al. [25], Copyright
(2020), with permission
from Springer Nature
2.2.3 Microstructure and Carbide Ratio
The cast and laser-clad Stellite 6 specimens were cut into pieces for various studies
using the line-cutting method. The surfaces of the metallographic samples were
prepared following the mechanical polishing procedures and then etched with
marble’s corrosive (a mixture of 10 g CuSO4 , 50 ml deionized water, and 50 ml
hydrochloric acid) to reveal the microstructures. The morphologies and microstruc-
tures of the specimens were analyzed using a ZEISS EVO18-type field emission scan-
ning electron microscopy (SEM) with the energy spectrometer (EDS). The volume
fractions of carbides in the Stellite 6 specimens were quantified using the system
software of optical microscopy.
The SEM microstructure of cast Stellite 6 is shown in Fig. 2.4, which consists
of primary Co solid solution with eutectic carbides. Three distinct areas marked
in Fig. 2.4 were analyzed for elemental concentration with EDS, and the results are
presented in Table 2.2. Area 1 (gray) contains very high Co content but low C content;
therefore, it should be Co solid solution, while area 2 (black) containing high Cr and
C contents should be Cr7 C3 carbide, and area 3 (white) contains high W and C as
well as Co contents; it should be (W, Co)6 C carbide [1].
The similar microstructure can be observed for laser-clad Stellite 6, but the Cr7 C3
and (W, Co)6 C carbides are apparently finer and less in this alloy, compared to the
cast Stellite 6, as shown in Fig. 2.5. From the EDS analysis results in Table 2.3, in
correspondence to the areas marked in Fig. 2.5, Cr7 C3 and (W, Co)6 C carbides are
embedded in Co solid solution matrix.
The volume fractions of carbides were quantified using the special software in
optical microscopy. The estimated results are 21.76% and 15.94% carbides in the
cast and in the laser-clad Stellite 6 specimen, respectively. This implies that high
cooling rate in the laser cladding process suppressed the precipitation of carbides
and the growth of grains.
Fig. 2.4 SEM

microstructure of cast Stellite
6 [25]. Reprinted from Ding
Springer Nature
1
3 (W,Co)6C
2 Cr7C3
Table 2.2 EDS elemental concentrations (wt%) of the selected areas in cast Stellite 6 alloy
specimen [25]
Element Co Cr W Mo C Ni Mn Si Fe
Area 1 63.03 25.47 3.71 0.07 3.42 1.63 0.38 1.04 1.23
Area 2 12.57 71.99 2.44 0.37 8.25 0.13 – – 0.37
Area 3 58.73 19.98 6.76 0.20 9.52 1.47 0.81 1.14 1.40
Reprinted from Ding et al. [25], Copyright (2020), with permission from Springer Nature
Fig. 2.5 SEM

microstructure of laser-clad
Stellite 6 [25]. Reprinted 2 1
from Ding et al. [25],
Cr7C3
Copyright (2020), with
Nature
3 (W,Co)6C
Table 2.3 EDS elemental concentrations (wt%) of the selected areas in laser-clad Stellite 6 alloy
specimen [25]
Element Co Cr W Mo C Ni Mn Si Fe
Area 1 46.90 23.08 0.46 0.46 5.57 3.89 0.14 0.50 19.00
Area 2 34.35 35.71 1.84 0.91 7.50 2.71 0.27 0.43 14.91
Area 3 44.05 24.06 3.21 0.28 6.35 3.75 0.10 0.64 18.92
2.2.4 Hardness and Wear Properties
Hardness test was conducted on the laser-clad Stellite 6 and cast Stellite 6 specimens
using a Rockwell hardness tester (HR-150DT Model) with the load capacity of
1471 N and the loading time of 5 s. Ten measurements were made on each specimen
surface at a constant distance of 10 mm, and the average value was taken as the
hardness of the specimen. The hardness of the cast Stellite 6 specimen was evaluated
to be HRC42 and that of the laser-clad one HRC41. The two Stellite 6 specimens
have similar hardness.
The wear resistance of laser-clad Stellite 6 and cast Stellite 6 was investigated
using a ball-on-disk tribometer in dry-sliding mode at room temperature. The pin
was a Si3 N4 ceramic ball (hardness 1300 HV0.2 ) with a diameter of 5 mm, and the
disk was the Stellite 6 specimen. The test was performed under a normal load of 25 N
at a rotational speed 350 rpm of the specimen. The test durations were 1 h, 4 h, and
10 h, respectively. The diameter of the resulting circular wear track was 3 mm, which
was measured at the middle of the wear track width. Four tests were performed on
each specimen. The cross-sectional profile of the wear track was simulated at four
locations of each wear track using a CONTOURECORD 1700SD surface texture so
that the average wear loss of the specimen can be quantified which is the volume of
the wear track, calculated as the area of the cross-sectional profile multiplied by the
periphery of the wear track.
The samples of cross-sectional profile of wear track for each specimen are
presented in Fig. 2.6. It is evident that the wear track depth and width of laser-
clad Stellite 6 are much larger than those of cast Stellite 6. Accordingly, as reported
in Fig. 2.7, the wear loss of cast Stellite 6 is much less than that of laser-clad Stellite
6 and the difference in wear loss between these two specimens increases with the
wear test duration. In other words, cast Stellite 6 exhibited better wear resistance
than laser-clad Stellite 6; in particular, when the wearing time was extended, this
tendency was more pronounced.
In order to better understand the wear loss results, associated with the wear mech-
anisms of cast and laser-clad Stellite 6, the worn surfaces of the specimens were
analyzed using SEM. As shown in Figs. 2.8 and 2.9, the wear track size of laser-clad
Stellite 6 is apparently larger than that of cast Stellite 6, which is consistent with the
wear loss results in Fig. 2.7. In addition, the wear track size of laser-clad Stellite 6
increases with wear test duration. For cast Stellite 6, comparing the wear track width
from the three test durations, it increased obviously from 1 to 4 h, but it only showed
a small increase from 4 to 10 h. Accordingly, the worn surfaces of cast Stellite 6 from
4 h wear and 10 h wear exhibited large plastic flow, in particular, for the longer wear
duration. This suggested that the cast Stellite 6 surface experienced severe strain
hardening during the wear process, which strengthened the surface against wear.
Differently, the laser-clad Stellite 6 exhibited typical abrasion wear characteristics
with obvious plowing scars; the wear track width increased dramatically with wear
test duration. No obvious plastic deformation was observed on this surface. The worn
surface morphology agreed with the wear loss.
2.2.5 Corrosion Behavior Under Polarization Test
Electrochemical tests such as potentiodynamic polarization and cyclic polarization

were used to evaluate the corrosion resistance of cast and laser-clad Stellite 6. The
testing facilities included a Solartron 1287 potentiostat, 1255 frequency response
analyzer (FRA) system, and K0047 corrosion cell kit which consisted of a counter
electrode (carbon rod), a reference electrode (standard calomel), a working electrode
(tested sample mounted on the Teflon holder with the aperture about 10 mm in
diameter), and a bridge tube. The potential versus current density curve, known as
polarization curve, can be obtained from the potentiodynamic polarization test. The
important parameters such as corrosion potential E corr , current density Icorr , and
polarization resistance Rp , which characterize the corrosion behavior of the tested
material, can be determined through analysis of the polarization curve, utilizing the
Tafel extrapolation approach [26].
Three types of electrolyte (corrosive media) were used in this study, which are
6 ppm morpholine solution (pH 9.5), 3.5% (in weight) sodium chloride (NaCl) solu-
tion, and Green Death solution consisting of 11.5% sulfuric acid +1.2% hydrochloric
Fig. 2.6 Comparison of 4

cross-sectional area of wear
0
track between cast and
Wear track depth (μm)

laser-clad Stellite 6 -4
specimens after wear for a
-8 Cast Stellite 6
1 h, b 4 h, and c 10 h [25].
Reprinted from Ding et al. -12
permission from Springer -16
Laser-clad
Nature -20 Stellite 6
-24
200 400 600 800 1000 1200

Wear track width (μm)
(a)
0
-10
Cast Stellite 6
-20
-30
-40 Laser-clad
Stellite 6
-50
-60
400 600 800 1000 1200 1400 1600 1800
(b)
20
0
-20 Cast Stellite 6
-40
-60
-80
Laser-clad
-100 Stellite 6
-120
-140
-160
400 800 1200 1600 2000 2400
(c)
Fig. 2.7 Comparison of 4

wear loss between cast and 1 hour
laser-clad Stellite 6 [25]. 4 hours
Reprinted from Ding et al. 10 hours
3
Wear Volume loss (mm3)

Nature
2
0
Cast Stellite 6 Laser-clad Stellite 6
acid +1% ferric chloride +1% cupric chloride. In the electrochemical tests, the spec-
imen was immersed into the corrosive medium for a few minutes until the solution
achieved a balance to build the steady state, known as open-circuit potential (OCP),
which is defined as the equilibrium potential when the system current measured at
the metal or/and electrolyte interface is zero [27]. The corrosion potential of the
specimen in the test cell was monitored until a fluctuation of OCP within 10 mV for
a period of 1000 s became stable before any electrochemical measurement started
[28, 29]. The potential versus current density curve, also called polarization curve,
can be obtained from the potentiodynamic polarization test, which was made in the
voltage range of −250 mV to 250 mV versus OCP at 0.1667 mv/s. The potentiody-
namic polarization scan started from −0.4 V versus OCP and ended at 0.6 V versus
SCE at a low-constant scan rate of 0.1667 mV/s.
Different from potentiodynamic polarization, cyclic polarization has both forward
and backward scans, which creates a hysteresis loop. This hysteresis loop character-
izes the localized corrosion performance of the material. If the current density of the
forward curve is larger than that of the reverse curve at the same potential, the tested
material exhibits localized corrosion resistance. More offset of the electropositive
loop indicates better localized or pitting corrosion resistance of the material [26]. In
the cyclic polarization tests, the scan started at −0.4 V versus SCE and ended at a
higher potential of +1.2 V versus SCE with the scan rate of 0.1667 mV/s. In this
case, if the current density reached a value of 1 mA/cm2 , the scan process would
be terminated. The obtained current density data were collected and then processed
with CorrWare and CorrView software packages. Three specimens were tested for
each condition.
The potentiodynamic polarization curves of the cast and laser-clad Stellite 6 spec-
imens tested in morpholine solution are presented in Fig. 2.10. As indicated by the
tendency of the current density increasing with the applied potential, both cast and
laser-clad Stellite 6 do not exhibit obvious passivation, which implies that under low
Fig. 2.8 SEM morphology of worn surface of cast Stellite 6 after wear for a 1 h, b 4 h, and c 10 h
[25]. Reprinted from Ding et al. [25], Copyright (2020), with permission from Springer Nature
Fig. 2.9 SEM morphology of worn surface of laser-clad Stellite 6 after wear for a 1 h, b 4 h, and c
10 h [25]. Reprinted from Ding et al. [25], Copyright (2020), with permission from Springer Nature
Fig. 2.10 Potentiodynamic

polarization curves of cast
and laser-clad Stellite 6 in
morpholine solution [25].
Potential (V)
Cast Stellite 6
Nature
Laser-clad Stellite 6
Current density I (A/cm2)
potentials oxide film is forming dynamically on the specimen surface. The two Stel-
lite 6 specimens prepared from different processes behaved similarly in this solution,
but according to the corrosion parameters calculated from the potentiodynamic polar-
ization curves, reported in Table 2.4, laser-clad Stellite 6 exhibited better corrosion
resistance or electron transferring resistance because of the larger Rp value, smaller
I corr value, and higher E corr .
The cyclic polarization curves of the cast and laser-clad Stellite 6 specimens tested
in morpholine solution are presented in Fig. 2.11. Between these two specimens, cast
Stellite 6 performs better in regard of pitting corrosion, because it does not have an
electronegative hysteresis loop. The laser-clad Stellite 6 specimen has a distinct
electronegative hysteresis loop, indicating that pitting corrosion may occur on it in
morpholine solution.
The polarization curves of cast and laser-clad Stellite 6 tested in 3.5% NaCl
solution are presented in Fig. 2.12, and the calculated values of parameters from
the polarization curves are summarized in Table 2.5. Similar to the behavior in
morpholine solution, both cast and laser-clad Stellite 6 display dynamic passivation,
indicating oxide film forming continuously on the specimen surface. There is no
obvious difference in corrosion potential between the two specimens, and they have
similar resistance to initial corrosion, but cast Stellite 6 has higher current density
and less polarization resistance than laser-clad Stellite 6.
Table 2.4 Polarization parameters of Stellite 6 specimens in morpholine solution [25]

Specimen E corr I corr Rp βa βc
(V versus SCE) (A/cm2 ) ·cm2 V/decade V/decade
Cast Stellite 6 −9.64E−02 2.07E−08 2.72E06 0.241 0.281
Laser-clad Stellite 6 −1.17E−01 1.53E−08 5.52E06 0.389 0.39
Fig. 2.11 Cyclic

polarization curve of a cast
Stellite 6 and b laser-clad
Stellite 6 in morpholine
solution [25]. Reprinted from
Potential (V)
Ding et al. [25], Copyright Backward
Forward

(a)
Potential (V)
Backward
Forward

(b)
It was observed in the corrosion tests that the specimen surface for both cast and
laser-clad Stellite 6 did not change after tested in morpholine solution, but the speci-
mens tested in 3.5 wt% NaCl solution showed a visible change in surface morphology.
To better understand this change and the corrosion mechanism of the materials, the
corroded surfaces of the Stellite 6 specimens from the tests in 3.5 wt% NaCl solution
were analyzed using SEM/EDS. The SEM morphologies of the corroded surfaces are
shown in Figs. 2.13 and 2.14, which appear apparently rugged, having experienced
more severe corrosion. However, the oxide layers are still retained on the surfaces
although they are seriously fractured.
The potentiodynamic polarization curves of the two Stellite 6 specimens tested
in Green Death solution are presented in Fig. 2.15. It is found that there is a signifi-
cant difference in corrosion behavior of these specimens in this solution from that in

and laser-clad Stellite 6 in
3.5% NaCl solution [25].
Potential (V)
Nature Laser-clad Stellite 6
Cast Stellite 6
Table 2.5 Polarization parameters of Stellite 6 specimens in 3.5 wt% NaCl solution [25]
Specimen E corr I corr Rp βa βc
(V versus SCE) (A/cm2 ) ·cm2 V/decade V/decade
Cast Stellite 6 −0.39 4.62E−05 2.64E03 0.37 0.19
Laser-clad Stellite 6 −0.33 1.45E−05 8.42E03 0.33 0.13
morpholine and 3.5 wt% NaCl solution. A distinct passivation region on the polar-
ization curve can be seen for both specimens, but a transpassivation region occurs
when the applied potential is increased to 0.9 V, which reveals that cast and laser-
clad Stellite 6 are able to form a perfect oxide film in Green Death solution, resisting
electron transferring. However, with further increase in the potential the oxide film
can break down. Continuously increasing potential can eventually remove the oxide
film from the specimen surfaces, leading to the current increase. This is characterized
by the transpassivation region on the polarization curves.
The surface morphologies of the specimens tested in Green Death solution are
shown in Figs. 2.16 and 2.17. These surfaces appear almost naked, and only little
residual oxide debris is left on the surfaces. The corroded surfaces and the polarization
curves agree well. Between cast and laser-clad Stellite 6, the latter was initially
corroded at a higher rate, but it was then passivated with a reduced rate by forming a
perfect oxide film, as shown in Fig. 2.15. For the former, the passivation region was
formed dynamically at a lower rate.
Fig. 2.13 SEM morphology

of corroded surface of cast
Stellite 6 in 3.5% NaCl
solution: a at low
magnification [25].
Nature
2.2.6 Corrosion Behavior Under Failure Test
The primary polarization test is considered nondestructive. Since cast and laser-clad
Stellite 6 did not show visible damage in the surfaces under the primary polarization
test in morpholine solution at pH 9.5, in order to investigate the corrosion mechanisms
of the materials and examination whether Stellite 6 hardfacing can fail in an amine
environment or not, failure test, in which the potential was set to be at a higher level,
4 V, with a high scan rate of 10 mv/s, thus to catch the damaged surface quickly, was
also performed on the cast and laser-clad Stellite 6 specimens. The aim of the failure
test was to eventually fail the specimen surface in the tested solution. The corroded
surfaces of the specimens after the failure tests were analyzed using SEM/EDS.
The cyclic polarization curves of cast and laser-clad Stellite 6 obtained from the
failure tests, which was performed at high potentials, in morpholine solution are

of corroded surface of
laser-clad Stellite 6 in 3.5%
NaCl solution: a at low
magnification [25].
Nature
presented in Fig. 2.18. It is found that the passivation tendency of both specimens
became pronounced with increasing the potential up to 4 V; additionally, the curves
of both specimens have an electronegative hysteresis loop, indicating occurrence of
pitting corrosion; in particular, for cast Stellite 6 the significant fluctuation of current
is observed on the polarization curve at the maximum potential. This suggests that
rupture of the oxide film had occurred on the specimen surface, resulting in formation
of a relatively small anode and large cathode. Because of this inequality in surface
area and the fact that the rates of both reactions must be equal, the anodic regions
underwent significant dissolution, causing formation of pits [26].
The corroded surfaces of the Stellite 6 specimens from the failure tests were
analyzed using SEM/EDS. The surface morphology of the cast specimen can be seen
in Fig. 2.19, which shows severe damage of the surface, covered with a fractured
layer. It was confirmed by the EDS analyses that the fractured surface layer is Cr-rich
Fig. 2.15 Potentiodynamic 1.2

Stellite 6 and laser-clad 1.0
Stellite 6 in Green Death
solution [25]. Reprinted from
Potential (V)
0.8
(2020), with permission Cast Stellite 6
from Springer Nature 0.6
0.4
Laser-clad Stellite
0.2
0.0
-7 -6 -5 -4 -3 -2 -1 0
oxide film. The debris area 1 (white) contains very high O content, which should be
oxides, while area 2 (black) contains very high Co content but little O, which should
be Stellite 6 alloy substrate, according to Fig. 2.20 and Table 2.6. Observed on the
polarization curve in Fig. 2.32a, at the initial stage of the failure test the preformed
oxide film in air on the specimen surface was broken with the increasing potential, but
the oxide film had the ability of self-repair, characterized by the increasing tendency
of passivation on the polarization curve. However, when the applied potential was
very high (near 4 V), the oxide film could not be self-repaired. As a result, the
substrate was not protected by the oxide film and pitting corrosion occurred.
For laser-clad Stellite 6, as shown in Fig. 2.21, the corroded surface shows a slight
difference in morphology from the cast one. A network structure with the white area
surrounding the black area can be observed in the former. According to the EDS
analysis results in Table 2.7, the white area contains little O but high Cr, Co, and C so
that this area would not be oxides; instead, it should be carbides. On the contrary, the
black area contains high O; therefore, it should be oxides. Also, this area is obviously
cracking, indicating the damage of the oxide film. However, the overall oxide film on
the laser-clad Stellite 6 specimen looks retained better than that on the cast specimen,
because although it was cracked it was not spalled off.
2.3 Stellite Alloy Mixture Hardfacing
2.3.1 Laser Hardfacing Process
The Stellite 6, Stellite 3, and Stellite 21 powders used to create the Stellite alloy
mixture hardfacing were all supplied by Kennametal Stellite Inc, with the main
chemical compositions of these powders presented in Table 2.8. The morphologies

Stellite 6 in Green Death
solution: a at low
magnification [25].
Nature
2.3 Stellite Alloy Mixture Hardfacing 31

laser-clad Stellite 6 in Green
Death solution: a at low
magnification [25].
Nature
Backward
Forward
(a)
Backward
Forward
(b)
Fig. 2.18 Cyclic polarization curve of a cast Stellite 6 and b laser-clad Stellite 6 under failure test
in morpholine solution [25]. Reprinted from Ding et al. [25], Copyright (2020), with permission
of these powders were examined with SEM, which showed that all powders had a
perfectly spherical shape, and the particle sizes varied in the range of 45–150 µm. The
substrate was a stainless steel 316 plate. Three hardfacing specimens were prepared
via laser cladding: (1) pure Stellite 3, (2) pure Stellite 6, and (3) mixture of 70 wt%
Stellite 3 with 30 wt% Stellite 21.
The hardfacing specimens were produced also using the LDF400-2000 high-
power flexible fiber-coupled diode laser. The capacity and process parameters of

Stellite 6 from failure test in
morpholine solution: a at
low magnification and b at
high magnification [25].
Nature
(b)
this system have been introduced previously. The multi-track claddings were made
at 40% overlapping to obtain a uniform clad thickness about 2.2 mm. The fabri-
cated hardfacings are photographically shown in Fig. 2.22, with color indication for
cracking examination using liquid penetrant tests. The Stellite 3 hardfacing spec-
imen is found seriously cracked, but no visible cracking is observed in the Stellite
6 hardfacing and the Stellite alloy mixture hardfacing specimens. This confirmed
the expectation that mixing Stellite 21 powder with Stellite 3 powder did minimize
cracking of the hardfacing during laser cladding.
Fig. 2.20 EDS spectrum for corroded surface of cast Stellite 6 from failure test in morpholine
solution: a area 1 and b area 2 [25]. Reprinted from Ding et al. [25], Copyright (2020), with
permission from Springer Nature
Table 2.6 Elemental concentrations (wt%) of the selected areas in the corroded surface of cast
Stellite 6 specimen from failure test in morpholine solution [25]
Element O Co Cr W Mo C Ni Mn Si Fe
Area 1 33.74 4.86 21.97 18.93 0.28 7.32 0.15 0.33 1.66 10.75
Area 2 3.23 65.05 21.21 1.64 – 3.14 2.38 0.67 0.84 1.85

laser-clad Stellite 6 from
failure test in morpholine
solution: a at low
magnification [25].
Nature
(a)
(b)
Table 2.7 Elemental concentrations (wt%) of the selected areas in the corroded surface of laser-clad
Stellite 6 specimen from failure test in morpholine solution [25]
Element O Co Cr W Mo C Ni Mn Si Fe
Area 1 2.95 34.43 37.44 3.73 1.15 9.24 2.15 0.16 0.56 8.20
Area 2 16.49 34.23 21.45 3.15 0.21 7.18 3.13 0.11 0.58 13.47
Table 2.8 Main chemical compositions of Stellite alloy powders (wt%, Co balance)
Alloy Cr W Mo Ni Fe Mn C Si B
Stellite 6 29 4.5 1.5 1.8 2.01 1.5 1.2 0.84
Stellite 3 30.5 12.5 1.88 0.97 0.54 2.4 0.69 1
Stellite 21 27 5.5 2.53 0.85 0.46 0.25 1.49
2.3.2 Microstructure Characteristics
The microstructures of the hardfacing specimens via laser cladding were studied with
SEM/EDS/XRD. The SEM image of the microstructure of the Stellite 6 hardfacing
specimen in Fig. 2.23a shows three distinct phases in gray, black, and white, respec-
tively. The EDS/XRD analyses reveal that the gray phase is face-centered cubic (fcc)
Co solid solution, the black phase is M7 C3 carbide, and the white phase is (W, Co)6 C
carbide. This hardfacing has a hypoeutectic microstructure with the Co solid solution
being the primary phase and the carbides embedded in the solution matrix.
Similar to the Stellite 6 hardfacing specimen, the Stellite alloy mixture hard-
facing specimen has a microstructure also consisting of three distinct phases in gray,
black, and white, respectively, as shown in Fig. 2.23b. However, the dendrites in
this hardfacing are the mixture with major black phase and minor white phase. The
EDS/XRD results reveal that the gray phase is fcc Co solid solution, the black phase is
M7 C3 carbide, and the white phase consists of (W, Co)6 C and (Co, Mo)3 C carbides.
Different from Stellite 6 hardfacing, the mixture hardfacing has a hypereutectic
microstructure with the carbides being the primary phase. The (Co, Mo)3 C carbide
phase precipitated in the Stellite alloy mixture hardfacing specimen is attributed to
higher Mo content of Stellite 21.
The volume fractions of total carbides in the hardfacing specimens were quantified
using SEM and the associated software, which showed about 16% in the Stellite 6
hardfacing and 40% in the Stellite alloy mixture hardfacing.
2.3.3 Hardness and Wear Resistance
The hardness of the hardfacing specimens was measured, and the average hardness
values of the Stellite 6 and Stellite alloy mixture hardfacings were about HRC40
and HRC50, respectively. With respect to hardness, definitely, the Stellite alloy
mixture is a good replacement of Stellite 6 for the valve seat hardfacing. Further-
more, the hardness of the hardfacing specimens was evaluated in cross section using a
Victorinox microhardness tester, which has the load capacity of 3 N. The indentation
was performed from the cladding layer surface to the substrate, crossing the interface
at a constant interval of 0.1 mm. The hardness profiles of the two hardfacings are
presented in Fig. 2.24. In consistence to the macrohardness test results, the Stellite
alloy mixture hardfacing has much higher hardness than the Stellite 6 hardfacing. For
Fig. 2.22 Photographic

hardfacing specimens: a
Stellite 3 hardfacing with
color indication for cracking,
b Stellite 6 hardfacing
showing no cracking, and c
Stellite alloy mixture
hardfacing showing no
cracking [16]. Reprinted
permission from Elsevier
Fig. 2.23 SEM

microstructure of a Stellite 6
hardfacing and b Stellite
alloy mixture hardfacing
Elsevier
both claddings, hardness keeps nearly constant within 2-mm thickness from the top
surface and there is a transition zone about 0.2 mm near the interface where hardness
drops gradually, which indicates that Fe dilution had occurred in the claddings during
the laser processing.
Ball-on-disk wear test was conducted on the hardfacing specimens in dry-sliding
mode at room temperature. A Si3 N4 ceramic ball (hardness 1300 HV0.2 ) with 5-mm
diameter was used as the pin, and the hardfacing specimen was the disk. The test was
run under a normal load of 9.8 N at a rotational speed of 350 rpm of the specimen.
The test duration was 120 min, and the diameter of the resulting circular wear track
was 6 mm. The cross-sectional profile of the wear track was simulated using a three-
dimensional microscopic system with super depth of field, and then, the wear loss,
which is the volume of the wear track, can be quantified. Four locations on each wear
Fig. 2.24 Microhardness

profiles in cross section of
the cladding specimens [16].
Fig. 2.25 Wear loss

comparison between the
hardfacings [16]. Reprinted
track were selected to determine the cross-sectional area. Three repeated tests were
performed on each hardfacing, and the average wear losses of the two hardfacings
were obtained, as reported in Fig. 2.25, with the standard deviation bars attached
for error analyses. It is shown that the wear resistance of the Stellite alloy mixture
hardfacing is much higher (about 5 times) than that of Stellite 6 hardfacing.
2.3.4 Cavitation-Erosion Performance
To respond the amine corrosion problem raised from industrial boiler feedwater, the
cavitation-erosion behavior of the hardfacings in NaOH solution of 10–4.5 mol/L at pH
Fig. 2.26 Weight losses of

Stellite 6 hardfacing and
hardfacing under cavitation
erosion in NaOH solution of
10–4.5 mol/L at pH 9.5 [16]. Stellite alloy Mixture
Stellite 6
9.5 was investigated using an Intelligent Temperature Control Ultrasonic Cavitation

Material Testing Machine (XOQS-2500 Model). The cavitation tip is made of a
commercially pure titanium and has the dimensions of 15 mm in diameter and 6 mm
in height. During the test, the cavitation tip was placed at a distance of 1 mm ±
100 µm from the specimen surface, and both the tip and specimen were immersed
into the NaOH solution which was maintained at the temperature of 25 ± 1 °C by a
cooling bath. The ultrasonic power was 1.5 kW, and the vibrational frequency was
20 kHz with an amplitude of 50 µm. The test was stopped every 60 min for taking the
weight change data of the specimen within the entire test duration of 12 h for each
specimen. Before the specimen was weighed using an electronic weighing scale with
the accuracy of 0.1 mg, it was cleaned ultrasonically and dried. The eroded surfaces
were examined with SEM.
The weight changes of the two specimens are hardly identified, as shown in
Fig. 2.26, because both hardfacings display very good resistance to cavitation erosion
in the tested solution, but the weight loss of the Stellite alloy mixture hardfacing is
slightly larger than that of Stellite 6 hardfacing with the testing time increased. More-
over, the SEM examinations of the eroded surfaces show that Stellite 6 hardfacing
is less damaged because its surface looks smoother, while that of the Stellite alloy
mixture hardfacing is rugged, as shown in Fig. 2.27, and much material removal at
grain boundaries is observed where chemical reactions would be more active during
the cavitation-erosion test.
2.3.5 Electrochemical Corrosion Behavior
Electrochemical corrosion test was also performed on the hardfacing specimens

using a Solartron potentiostat system, which was composed of a three-electrode

of eroded surface of a
Stellite 6 hardfacing and b
hardfacing [16]. Reprinted
electrochemical cell and a data acquisition/analysis control device. The hardfacing

specimen has the dimensions of 16 mm in diameter and 1.6 mm in thickness. In the
test, it was mounted on a Teflon holder and the tested surface was pressed against an
O-ring, which resulted in a surface area to the electrolyte through the aperture about
10 mm in diameter. The electrolyte or corrosive medium was morpholine with pH
9.5, to simulate the amine environment of industrial boiler feedwater. Morpholine is
an organic chemical compound having the chemical formula O(CH2 CH2 )2 NH. The
heterocycle features both amine and ether functional groups. Because of the amine,
morpholine is a base; its conjugate acid is called morpholinium.
The potentiodynamic polarization curves of the Stellite 6 hardfacing and Stel-
lite alloy mixture hardfacing, obtained from the electrochemical corrosion test in
morpholine with pH 9.5, are plotted in Fig. 2.28, and the calculated values of the
corrosion parameters from the polarization curves are summarized in Table 2.9. Both

polarization curves of the
hardfacings in morpholine
solution with pH 9.5 [16].
Table 2.9 Summary of

Alloy E corr I corr Rp
potentiodynamic polarization
(mV versus SCE) (A/cm2 ) k·cm2
parameters [16]
Stellite 6 −117.09 2.47E−8 5524
Stellite alloy mixture −27.39 1.56E−7 6385
Reprinted from Ding et al. [16], Copyright (2017), with permission
from Elsevier
curves show a tendency to passivate, but no evident passivation region is observed,

which indicates the dynamic oxidation behavior of the hardfacing surfaces. Further-
more, the Stellite alloy mixture hardfacing has better resistance to initial corrosion
because of the larger E corr value, but the corrosion would proceed more rapidly once
it occurs since the I corr value is larger. Since the Rp value is larger, the Stellite alloy
mixture hardfacing is generally more resistant to corrosion in morpholine solution
than the Stellite 6 hardfacing.
2.4 Molybdenum Stellite Alloy Hardfacings
2.4.1 Laser Creation of Hardfacings
Stellite 22 and Stellite 728 were deposited on stainless steel via laser cladding [21];
both are new hardfacing materials in the Stellite alloy family. Stellite 21 hardfacing
was also prepared under the same condition for comparison. The Stellite 21, Stellite
22, and Stellite 728 powder used in this research were all supplied by Kennametal
Stellite Inc. The morphologies of these powders, examined with SEM, showed a
shape close to sphere, as shown in Fig. 2.29. The powder sizes varied between 45
and 150 µm. The main chemical compositions of Stellite 22 and Stellite 728 powder
2.4 Molybdenum Stellite Alloy Hardfacings 43
Fig. 2.29 SEM microscopic

morphology of a Stellite 21
powder, b Stellite 22 powder,
and c Stellite 728 powder
[21]. Reprinted from Yao
Elsevier
Table 2.10 Main chemical compositions of Stellite alloy powders (wt%, Co balance)
Alloy Cr Mo Ni Fe Mn C Si Nb
Stellite 22 27 11 2.75 3 1 0.25 1
Stellite 728 24 11.8 3.8 1 0.52 0.35 0.45 2.07
are given in Table 2.10. Stellite 22 has double Mo content, compared to Stellite 21.
The Stellite 728 powder has a slightly higher C content than the Stellite 21 powder,
and it also has 2.07 wt% Nb. The substrate was a stainless steel 316 plate having the
dimension of 100 × 60 × 10 mm. The surface of the substrate specimen was grit-
blasted using 24-mesh alumina and ultrasonically cleaned in absolute ethyl alcohol
before applying the hardfacing.
The Stellite 21, Stellite 22, and Stellite 728 hardfacing were prepared also using
the LDF400-2000 high-power flexible fiber-coupled diode laser, with the similar
process parameters used previously. Before multiple scanning, single-track cladding
specimens were prepared with different process parameters and examined for phys-
ical appearance. Further examination was carried out on the single-track cladding
specimens using SEM for investigation of porosity, cracking, and slag. The optimal
process parameters were obtained based on the examination results. Laser tracks
were laid at ~50% overlapping to achieve a uniform clad thickness (about 2.5 mm).
2.4.2 Microstructural Characterization
The microstructural analyses of the hardfacing specimens were performed using

SEM/EDS/XRD. The microstructure of the Stellite 21 hardfacing consists of primary
solid solution (gray) and a mixture of eutectic Cr23 C6 carbide (black), Co3 Mo inter-
metallic compound (white), and Co solid solution, as shown in Fig. 2.30a. The
primary phase is identified to be fcc solid solution. Additionally, this alloy contains
a very small amount of Cr-rich carbide and Mo-rich intermetallic compound, due to
low C and Mo contents.
Similar microstructure was observed on Stellite 22 hardfacing, which consists
of primary Co solid solution (gray) and a mixture of eutectic Cr-rich carbide
(black), Mo-rich intermetallic compound (white), and Co solid solution, as shown
in Fig. 2.30b. The XRD analyses reveal that the carbide is Cr23 C6 , the intermetallic
compound phase is Co3 Mo, and the primary phase is fcc solid solution. However,
compared to Stellite 21, the amount of Co3 Mo intermetallic compound is much larger
in this alloy due to the increase of Mo content.
Different from Stellite 21 and Stellite 22, owing to the increase of C content (from
0.25 to 0.35 wt%) and Nb addition, the amount of eutectic phase in Stellite 728 is
increased largely, as shown in Fig. 2.30c. The EDS and XRD analyses revealed
that both Cr23 C6 and NbC exist in this alloy, the intermetallic compound phase is
also Co3 Mo, and the primary phase is fcc Co solid solution. To further investigate
Fig. 2.30 SEM

microstructure of a Stellite
21 hardfacing, b Stellite 22
hardfacing, and c Stellite 728 Cr23C6 carbide and Co3Mo
hardfacing [21]. Reprinted intermetallic compound
from Yao et al. [21],
Solid solution
(a)
Cr23C6 carbide
Co3Mo intermetallic
compound
Solid solution
(b)
Cr23C6 carbide, Co3Mo

intermetallic compound and
NbC carbide
Solid solution
(c)
Fig. 2.31 EDS elemental mapping analysis of Stellite 728 hardfacing: a SEM microstructure,
b element Mo distribution, and c element Nb distribution [21]. Reprinted from Yao et al. [21],
Copyright (2018), with permission from Elsevier
the influence of Nb addition on the microstructure of Stellite 728, EDS elemental

mapping was conducted on this alloy for elements Nb and Mo. According to the
element Mo mapping shown in Fig. 2.31b, the intermetallic compound phase Co3 Mo
is in light under SEM; thus, the carbide Cr23 C6 is in dark, which is consistent with
previous study results [20]. According to the element Nb mapping in Fig. 2.31c,
NbC carbides disperse uniformly within the intermetallic compound Co3 Mo and the
carbide Cr23 C6 . NbC carbide is in light under SEM, which was confirmed by previous
research [20]. Therefore, Co3 Mo and NbC are in the same color under SEM.
2.4.3 Hardness and Wear Performance
The average hardness values of the hardfacing specimens were obtained from macro-
hardness test; they are about HRC35 for Stellite 21, HRC41 for Stellite 22, and
HRC44 for Stellite 728. Clearly, the Stellite 22 and Stellite 728 hardfacing with large
amounts of the intermetallic compound Co3 Mo are much harder than the Stellite 21
Fig. 2.32 Comparison of

wear rate between the Stellite
alloy hardfacings [21].
Reprinted from Yao et al.
hardfacing. Therefore, they are a good replacement of Stellite 21 for applications

where hardness is the main requirement. Certainly, the increased C content also
contributes to hardness improvement of Stellite 728.
Pin-on-disk wear test was conducted on the hardfacing specimens at room temper-
ature in dry-sliding mode. The testing machine and parameters used in this study were
the same as those detailed previously. The wear test results of the hardfacings are illus-
trated as specific wear rates in Fig. 2.32, with the standard deviation bars attached
for indication of testing error. Stellite 22 and Stellite 28 hardfacings demonstrate
much better (about 2 times and 3 times, respectively) wear resistance than Stellite 21
hardfacing, which suggests that in addition to carbides the intermetallic compound
Co3 Mo can also enhance the wear resistance of Stellite alloys.
2.4.4 Corrosion Resistance of Hardfacings
The corrosion resistance of the hardfacing specimens in 3.5 wt% sodium chloride
(NaCl) aqueous solution and in Green Death solution was evaluated using electro-
chemical tests. The testing equipment, parameters, and procedures used in this inves-
tigation were the same as those detailed previously. The potentiodynamic polarization
curves of the hardfacings, obtained from the tests, are presented in Fig. 2.33. In 3.5
wt% NaCl solution, all the hardfacings exhibit certain passivation characteristics,
because the polarization curve has a region where current is kept unchanged with
the potential increased, as demonstrated in Fig. 2.33a. This is an indication of the
formation of oxide film on the hardfacing surface, which can protect the substrates
against further corrosion. Passivation characteristic in Green Death solution is more
pronounced for these hardfacings, as shown in Fig. 2.33b. The calculated corrosion
parameters from the potentiodynamic polarization curves are summarized in Table
2.11.

curve between the Stellite
alloy hardfacings in a 3.5
wt% NaCl solution and b
Green Death solution [21].
In 3.5 wt% NaCl solution, the different hardfacings show little difference in corro-
sion potential, which indicates similar corrosion resistance of the hardfacings, but
Stellite 728 hardfacing has the highest current density I corr and the least polarization
resistance Rp among the hardfacings and Stellite 22 hardfacing is the opposite; there-
fore, in general, the Stellite 22 hardfacing is the best and the Stellite 728 hardfacing
is the worst for corrosion resistance in this solution. However, in Green Death solu-
tion, Stellite 728 hardfacing has slightly higher E corr and much higher I corr than the
other two hardfacings. This means that Stellite 728 hardfacing is more resistant to
corrosion initially, but the corrosion proceeded more rapidly once it started. On the
contrary, oxidation occurred more likely on Stellite 21 hardfacing in Green Death
solution, but the corrosion proceeded slower. According to the Rp values, Stellite 21

Condition E corr I corr Rp
(V versus SCE) (A/cm2 ) (k·cm2 )
parameters [21]
Stellite 21 −0.213 2.337E−008 746
3.5 wt% NaCl
solution
Stellite 22 −0.218 1.879E−008 883
3.5 wt% NaCl
solution
Stellite 728 −0.2 3.311E−008 511
3.5 wt% NaCl
solution
Stellite 21 0.365 1.007E−006 38
Green Death
solution
Stellite 22 0.408 1.607E−006 23
Green Death
solution
Stellite 728 0.439 3.475E−006 11
Green Death
solution
Reprinted from Yao et al. [21], Copyright (2018), with permission
from Elsevier
hardfacing is the best and Stellite 728 hardfacing is the worst in corrosion resistance
to Green Death solution.
The surface morphologies of the corroded hardfacing specimens examined with
SEM/EDS are shown in Figs. 2.34 and 2.35. All hardfacings were observed with
severe corrosion during the polarization test, because the original microstructures
are no longer visible, heavily covered with corrosion products. In the SEM images
at high magnification, two distinct regions in dark and light, respectively, can be
identified on the corroded surfaces. EDS analysis was conducted on the two regions
marked for elemental concentrations. The corresponding elemental concentrations
are reported in Tables 2.12 and 2.13. For all corroded surfaces, the main difference is
oxygen content, which represents the oxide film behavior on the surface. According
to the elemental concentrations, area 2 contains much higher O content than area
1. According to the surface morphologies and oxygen concentrations, the region in
light (area 2) should be residual oxide films and that in dark (area 1) may be the
substrate exposed after the oxide films were broken and removed.
It is evident that the oxide film on Stellite 21 hardfacing was retained much better
than that on the other hardfacings during the polarization tests, because the corroded
Stellite 21 hardfacing surface has larger light region (oxide), whereas the oxide film
on Stellite 22 hardfacing and Stellite 728 hardfacing was largely damaged, because
only oxide film fragments (discontinuity) are observed on the corroded surfaces.

of corroded surface of a
Stellite 21 hardfacing, b
Stellite 22 hardfacing, and c
Stellite 728 hardfacing in 3.5
wt% NaCl solution [21].

of corroded surface of a
Stellite 21 hardfacing, b
Stellite 22 hardfacing, and c
Stellite 728 hardfacing in
Green Death solution [21].
Table 2.12 Elemental concentrations (wt%) of the selected areas on the corroded surfaces of the
hardfacings in 3.5 wt% NaCl solution [21]
Alloy Area C O Si Cr Mn Fe Co Ni Mo Nb
Stellite 21 1 2.79 0.55 1.74 24.25 0.49 9.33 52.77 3.27 4.82
2 6.06 1.02 1.52 23.87 0.44 9.02 50.43 3.25 4.39
Stellite 22 1 2.56 1.84 0.31 25.99 0.15 12.39 46.18 2.29 8.28
2 6.33 5.31 1.25 34.29 0.23 7.76 31.34 1.70 11.79
Stellite 728 1 3.6 3.54 0.57 23.02 0.33 10.58 44.69 4.39 8.87 0.42
2 10 36.98 0.57 21.72 0.44 4.64 8.95 0.92 14.15 1.63
Reprinted from Yao et al. [21], Copyright (2018), with permission from Elsevier
Table 2.13 Elemental concentrations (wt%) of the selected areas on the corroded surface of the
hardfacings in Green Death solution [21]
Alloy Area C O Si Cr Mn Fe Co Ni Mo Nb
Stellite 21 1 2.12 0.92 1.26 22.44 0.63 9.27 56.7 3.24 3.42
2 3.64 4.6 2.85 33.41 0.44 5.86 32.46 1.56 15.18
Stellite 22 1 2.38 2.99 0.24 24.66 0.29 12.76 47.2 2.62 6.86
2 4.28 13.4 5.61 31.6 4.42 5.92 21.7 1.44 11.64
Stellite 728 1 3.02 0.98 0.34 22.05 0.57 9.1 52.14 4.6 7.17 0.02
2 7.66 5.04 0.7 21.59 0.03 6.3 37.48 2.73 19.88 2.6
The surface morphologies of the hardfacings in the two solutions are similar, but
the surface damages are relatively serious in Green Death solution, since less oxide
films remain on the corroded surfaces.
2.5 Summary of Stellite Alloy Hardfacings
As a surface protection, both wear and corrosion resistance of Stellite 6 alloy hard-
facing are crucial. Due to rapid heating and cooling in the laser cladding process, the
laser-clad Stellite 6 specimen had finer microstructure compared to the cast Stellite
specimen, but both had similar hardness. However, it is interesting to note that the
laser-clad specimen was much less wear-resistant than the cast specimen, especially,
when the wear duration was increased. The possible reason for the lower wear resis-
tance of the laser-clad specimen is the finer carbides which are more vulnerable under
the wear load and spall off from the solid solution matrix. On the contrary, the bulky
carbides in the cast specimen can bear the wear load, thus reducing the material loss.
In the meanwhile, with the wearing proceeding, the strain hardening of solid solution
2.5 Summary of Stellite Alloy Hardfacings 53
matrix was more pronounced on the cast specimen surface because of the large size,
resulting in the reduction of wear rate.
Stellite 6 is generally corrosion-resistant owing to high Cr content, which enables
formation of a dense and adherent oxide film on its surface to protect the substrate
against corrosion; therefore, the corrosion resistance of this alloy strongly depends on
the behavior of the oxide film on the alloy surface. As demonstrated in the polarization
tests, both the cast and laser-clad Stellite 6 specimens were prone to form an oxide
film in morpholine and 3.5 wt% NaCl solution, but not a perfect oxide film can
form because the current continuously rose at a low rate with the potential increased.
Comparing the cast and laser-clad specimen, in general, the oxide film on the latter
remained better so that it was more resistant to electron transferring from the I corr and
Rp values. In the Green Death solution, the laser-clad specimen showed a complete
passivation region, further indicating better oxide film performance; however, the
oxide film on both specimens can break down when the applied potential was larger
than 0.9 V. According to the Pourbaix diagram of the deaerated chromium–water
system [30] in Fig. 2.36, with the pH increase from Green Death solution, then NaCl
solution, to morpholine solution, Stellite 6 in the solution had less possibility to
create ions or more chance to form Cr oxide with increase of the potential. In other
words, Stellite 6 is more corrosion-resistant to the solution with higher pH than that
with lower pH.
Although nominal compositions of the cast and laser-clad specimens are the same,
the carbide volume fraction of the latter was less than that of the former due to rapid
cooling in laser cladding which suppressed precipitation of carbides. Since the Cr
oxide in Stellite 6 was generated by the oxidation of Cr in the solid solution, thus
more solid solution would result in more Cr oxide. Therefore, the Cr oxide film on the
laser-clad specimen surface behaved better than that on the cast specimen surface.
Fig. 2.36 Pourbaix diagram

for the deaerated
chromium–water system at
25 °C [30]. Reprinted from
Beverskog et al. [30],
Stellite 6 and the Stellite alloy mixture are all carbide-strengthened alloys so that
the amount of carbides in the alloy determines its properties. In general, the hardness
and wear resistance of Stellite alloys increase with the amount of carbides present. As
demonstrated by the microstructural analyses, the Stellite alloy mixture hardfacing
has a larger volume fraction of carbides (40 vol%) than the Stellite 6 hardfacing
(16 vol%); consistently, the former is much harder and more wear-resistant than
the latter, as shown by the hardness and wear tests. For the cavitation-erosion tests
in morpholine solution, the eroded surface analyses reveal that the Stellite alloy
mixture hardfacing is less resistant to NaOH pH 9.5 cavitation erosion with the
erosion damage occurring preferentially at grain boundaries. This is because the
Stellite alloy mixture hardfacing has more grain boundaries due to more carbides
present, where atoms have higher energy so that they are more active to react with
the NaOH pH 9.5 cavitation-erosion environment.
As concerns the corrosion of the Stellite 6 and Stellite alloy mixture hardfacing in
morpholine solution at pH 9.5, Stellite 6 and the Stellite alloy mixture contain nearly
the same Cr content (~30 wt%). The high Cr content secures formation of dense
and protective Cr2 O3 films on their surfaces when they are exposed to morpholine
solution. The Cr in Cr2 O3 comes from the solute Cr in the solid solution but not from
the Cr-rich carbides. Since the Stellite alloy mixture contains more Cr-rich carbides
than Stellite 6, the solute Cr in solid solution would be relatively less in this alloy,
resulting in less Cr2 O3 formed. Therefore, the E corr of the Stellite alloy mixture is
higher and the Rp is larger. However, once the corrosion occurs, it proceeds at a higher
rate, indicated by the larger I corr . This may be due to the fact that more carbides create
more grain boundaries which promote the chemical reaction between the alloy and
the corrosive medium. Since the Stellite 6 and Stellite alloy mixture hardfacing are all
able to form protective Cr2 O3 films, the corrosion resistance of these alloys mainly
depends on the bonding strength of the films on their surfaces. With Cr2 O3 films
bonded on the alloy surfaces, the two hardfacings should have equivalent corrosion
resistance. However, if the oxide films are broken, either formation of new oxides or
formation of ions (CrO4 2− ) and compounds Co(OH)3 will cause material loss, that
is, corrosion loss.
The Stellite alloy mixture exhibited much better laser cladding behavior than
Stellite 3 due to adding Stellite 21, which reduced the volume fraction of carbides
in the alloy, but compared with Stellite 6, the volume fraction of carbides in the
Stellite alloy mixture is still much larger, leading to much higher hardness and better
wear resistance. To testify the effectiveness of the Stellite alloy mixture hardfacing,
valve switch test was performed on the butterfly valve seat sealing surface, which
was applied with the Stellite alloy mixture hardfacing via laser cladding, as shown in
Fig. 2.37. No leakage was found on the sealing surface under the specified duration
of 30,000 cycles, which confirmed that the Stellite alloy mixture hardfacing was
superior to the existing sealing hardfacings.
Stellite 21, Stellite 22, and Stellite 728 are all low-carbon (<0.35 wt%) Stellite
alloys. The low C content limits the amount of carbides formed in the alloys. Molyb-
denum, with a large atom size, plays dual functions in Stellite alloys. One is as a solute
to strengthen the solid solution, and the other is to form intermetallic compounds
2.5 Summary of Stellite Alloy Hardfacings 55
Hardfacing
Sealing plate
(a) (b)
Fig. 2.37 Application test of Stellite alloy mixture hardfacing: a butterfly valve having sealing
plates and b sealing plate surface with laser cladding of the Stellite alloy mixture [16]. Reprinted
from Ding et al. [16], Copyright (2017), with permission from Elsevier
(Co3 Mo and Co7 Mo6 ) when present in large quantities in low-carbon Stellite alloys.
In the Stellite 22 and Stellite 728 hardfacings, Mo content is increased to 11 wt%,
which exceeds its solubility in the Co solid solution, which results in precipitation of
the intermetallic compounds (Co3 Mo). It was estimated that the volume fraction of
Co3 Mo in Stellite 22 hardfacing increased to about 6.7%, compared with Stellite 21
hardfacing (~1%). The volume fraction of Co3 Mo in Stellite 728 hardfacing cannot be
quantified accurately because NbC and Co3 Mo are in the same color under SEM, but
since Stellite 728 contains similar Mo content to Stellite 22, it can be assumed that
they have similar volume fraction of Co3 Mo. The presence of these intermetallic
compounds does strengthen the alloys with increased hardness and sliding wear
resistance, as various carbides in Stellite alloys do. The volume fraction of Cr23 C6 in
Stellite 21 hardfacing was estimated to be ~4.8% and that in Stellite 22 hardfacing
~5.2%. They are close because these two alloys contain the same C and Cr contents.
For Stellite 728 hardfacing, with the slight increase in C content and addition of Nb,
the carbides in this alloy differ from those in the other two. As discussed above, the
carbides in Stellite 728 hardfacing include Cr23 C6 and NbC. In this alloy, a small
quantity of C (0.35 wt%) is easier to form carbides with Nb rather than with Cr; the
reason for this is that element Nb has a stronger affinity to C than element Cr [31]
and very fine NbC could be formed, replacing coarse Cr23 C6 when a small amount
of Nb (1.5 at.%) was added in Stellite 21 [32]. However, whether Cr23 C6 can be
formed in Stellite 728 or not also depends on the solidification condition. In laser
cladding process, local heating and rapid cooling can cause unbalanced solidifica-
tion. The formation of Cr23 C6 carbides in Stellite 728 hardfacing may be due to the
rapid cooling of laser process, where Nb did not have enough time to fully form
NbC; thus, Cr had chances to form Cr23 C6 with the rest of C, leading to coexistence
of NbC and Cr23 C6 in Stellite 728 hardfacing. The sliding wear test found that the
dispersed NbC carbides within the eutectic did contribute to the wear resistance of
Stellite 728 hardfacing.
As concerns the corrosion of the hardfacings in 3.5 wt% NaCl solution and in
Green Death solution, Stellite 21, Stellite 22, and Stellite 728 all contain high Cr
content, which allows the alloys to form Cr-rich oxides when they are in oxygen-
containing environments. These oxide films are strong and dense, and considered to
have protective effects on the substrates against corrosion. The hardfacing specimens
may be previously oxidized after polishing and were then further oxidized in the solu-
tions during the corrosion tests. From the polarization curves, the three hardfacings
are all able to form protective oxide films in the tested solutions; thus, the corrosion
resistance of the hardfacings strongly depends on the bonding strength of the oxide
films to the substrates. From the morphologies of the corroded surfaces, under higher
potentials, the oxide films can break, leading to corrosion of the substrates. However,
the oxide film on Stellite 21 hardfacing was retained better than that on the other two
hardfacings. This may be attributed to the less volume fraction of carbides present in
this alloy, which allows its microstructure nearly identic and thus the oxide film more
homogeneous. Comparing the effect between carbides and intermetallic compounds
on the corrosion behavior of Stellite alloys, the former is generally Cr-rich, which
reduces the Cr content of the solid solution and causes Cr depletion near the carbides.
On the contrary, the latter is Mo-rich, so that it does not change the Cr content of
the solid solution. Therefore, in consideration of the protective oxide film (Cr-rich)
formation and repair, intermetallic compounds are superior to carbides in Stellite
alloys.
References
1. Liu R, Yao MX (2012) High-temperature wear/corrosion resistant Stellite alloys and Tribaloy
alloys. In: CRC handbook on aerospace and aeronautical materials. CRC Press, Taylor &
Francis, pp 151–235
2. Kapoor S, Liu R, Wu XJ, Yao MX (2013) Microstructure and wear resistance relations of
Stellite alloys. Int J Adv Mater Sci 4(3):231–248
3. Liu R, Yao JH, Zhang QL, Yao MX, Collier R (2015) Microstructures and hardness/wear
performance of high-carbon Stellite alloys containing molybdenum. Metall Mater Trans A
46(12):5504–5513
4. Kathuria YP, Tsuboi A (1996) Laser cladding of Stellite #6: a detailed analysis. In: Proceedings
of the SPIE—the international society for optical engineering, pp 86–92
5. Chang SS, Wu HC, Chen C (2008) Impact wear resistance of Stellite 6 hardfaced valve seats
with laser cladding. Mater Manufac Process 23(7):708–713
6. Nicholls JR (1994) Coatings and hardfacing alloys for corrosion and wear resistance in diesel
engines. Mater Sci Technol 10(11):1002–1012
7. Watkins JC, DeWall KG (2001) Stellite 6 friction changes due to aging and in-service testing,
vol 426. ASME Pressure Vessels and Piping Division (Publication) PVP, pp 169–173
8. Anon (1957) Hardfacing service for industry. Weld Met Fabri 25(3):91–97
9. Hansen JS (1979) Ball-valve wear tests in a coal gasifier lock-hopper simulator. Electric Power
Research Institute Report, pp 330–335
References 57
10. Zhao R, Barber GC, Wang YS, Larson JE (1997) Wear mechanism analysis of engine exhaust
valve seats with a laboratory simulator. Tribol Trans 40(2):209–218
11. Lou M, Xu YX, Ouyang HW, Du Y (2013) Comparison of microstructure and mechanical
properties of Co-based and Fe-based alloy coatings deposited by PTA. Adv Mater Res 834–
836:617–622
12. Ganesh P, Moitra A, Tiwari P, Sathyanarayanan S, Kumar H, Rai SK, Kukreja LM (2010)
Fracture behavior of laser-clad joint of Stellite 21 on AISI 316L stainless steel. Mater Sci Eng
A 527(16):3748–3756
13. Tuominen J, Näkki J, Poutala J, Miettinen J, Peltola T, Vuoristo P, Rasehorn I, Alam MM,
Kaplan AFH (2015) Fatigue behavior of laser clad round steel bars. J Laser Appl 27(1):1–9
14. Wang D, Zhao HX, Wang H, Hogmark S (2017) Failure mechanism of a Stellite coating on
heat-resistant steel. Metall Mat Trans A Phys Metall Mat Sci 48(9):4356–4364
15. Liu R, Yao JH, Zhang QL, Yao MX, Collier R (2015) Relations of chemical composition
to solidification behavior and associated microstructure of Stellite alloys. Metallo Microstruc
Analy 4(3):146–157
16. Ding YP, Liu R, Yao JH, Zhang QL, Wang L (2017) Stellite alloy mixture hardfacing via laser
cladding for control valve seat sealing surfaces. Surf Coat Technol 329:97–108
17. Aizaz A, Kumar P (1985) Properties of Stellite alloy No. 21 made via pliable powder technology.
Met Powd Rep 40(9):507–510
18. Liu R, Yao MX, Patnaik PC, Wu XJ (2006) An improved wear-resistant PTA hardfacing—
VWC/Stellite 21. J Comp Mater 40(24):2203–2215
19. Huang P, Liu R, Wu XJ, Yao MX (2007) Effects of molybdenum content and heat treatment
on mechanical and tribological properties of a low-carbon Stellite alloy. J Eng Mater Technol
129(4):523–529
20. Liu R, Yao JH, Zhang QL, Yao MX, Collier R (2015) Effects of molybdenum content on the
wear/erosion and corrosion performance of low-carbon Stellite alloys. Mater Des 78:95–106
21. Yao JH, Ding YP, Liu R, Zhang QL, Wang L (2018) Wear and corrosion performance of
laser-clad low-carbon high molybdenum Stellite alloys. Opt Laser Technol 107:32–45
22. Collier R, Liu R, Wu XJ, Zhang XZ, Yao MX (2020) Dry-sliding wear performance of
molybdenum-containing Stellite alloys. Wear 29:1384–1399
23. Davis JR (2000) Cobalt-base alloys, in Nickel, Cobalt, and their alloys. ASM International,
Materials Park, p 362–406
24. Bush DR (1991) Be alert to new valve threat: erosion/corrosion in feedwater. Pow Mag
135(1):30–32
25. Ding YP, Liu R, Wang L, Li JH, Yao JH (2020) Corrosion and wear performance of Stellite
alloy hardfacing prepared via laser cladding. Protect Metals Phys Chem Surf 56(2):392–404
26. Perez N (2004) Electrochemistry, electrochemistry and corrosion science. Kluwer Academic
Publishers, Assinippi Park, p 27–70
27. Grips VKW, Barshilia HC, Selvi VE, Rajam KS (2006) Electrochemical behavior of single
layer CrN, TiN, TiAlN coatings and nanolayered TiAlN/CrN multilayer coatings prepared by
reactive direct current magnetron sputtering. Thin Solid Films 514(1–2):204–211
28. Hu PS, Liu R, Liu J, McRae G, Yao MX, Collier R (2014) Advanced Stellite alloys with
improved metal-on-metal bearing for hip implants. Mater Des 60:424–432
29. Anisur MR, Banerjee PC, Easton CD, Raman RKS (2017) Controlling hydrogen environment
and cooling during CVD graphene growth on nickel for improved corrosion resistance. Carbon
127:131–140
30. Beverskog B, Puigdomenech I (1997) Revised Pourbaix diagrams for chromium at 25–300 °C.
Corr Sci 39(1):43–57
31. Callister WD Jr, Rethwisch DG (2010) Materials science and engineering—an introduction.
John Wiley & Sons, Inc., New York, p 18–43
32. Youdelis WV, Kwon Q (1983) Carbide phases in cobalt base superalloy: role of nuleation
entropy in refinement. Met Sci 17:379–384
Chapter 3
Laser Cladding of Metal-Ceramic
Composites
Abstract Metal-ceramic composite coatings are often applied on metal surface to

enhance wear and corrosion resistance. Laser cladding, owing to metallurgical reac-
tion occurring in the laser process, creates better interface bonding of the coating
than other deposition techniques such as plasma spray, cold spray, high-velocity
oxygen-fuel (HVOF), and slurry sintering, which form the interface bonding mainly
by diffusion or mechanical interlocking. In this chapter, the studies of WC/NiCrMo
composite coating and TiC/H13 steel composite coating via laser cladding are
presented. WC-NiCrMo powder was pre-alloyed, and then, it was cladded on SS316L
using circular and wide-band laser spot, respectively, and TiC/H13 composite powder
is deposited on H13 steel with circular laser spot. Optical microscope (OM), X-
ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive
spectrometer (EDS) were used to observe the microstructure and distribution of the
reinforcement particle. Dry sliding wear test was used to study the wear behavior of
the coatings. The results show that the WC particles which were partially dissolved
were uniformly distributed in the two coatings. The coatings mainly contain WC,
M23 C6 carbides, and γ -(Ni, Fe) solid solution matrix. The different hardness and
wear resistance of the two coatings result from the different microstructure, which
are caused by the different dilution of Fe. The property of the coating produced
by wide-band spot laser presents better than the coating produced by the circular
spot laser. The microstructure of the TiC/H13 coating is not uniform because of the
temperature gradient of the coating during the laser cladding process. The thermal
stability of the TiC/H13 coating is investigated by examining the hardness change at
the high temperature of 873 K.
3.1 Surface Enhancement with Composite Coatings
3.1.1 Laser Deposition of Metal-Ceramic Composite Coatings
The surfaces of tools and components exposed to severe wear and corrosion condi-
tions need coating protection with high hardness and anti-wear/anti-corrosion char-
acteristics. Various types of materials can be employed as the coatings deposited on

60 3 Laser Cladding of Metal-Ceramic Composites
metal substrates for such applications, for example, hard metals, ceramics and metal-
ceramic composites, etc. Compared with other material coatings, metal-ceramic
composite coatings display exceptional mechanical performance, excellent wear and
corrosion resistance owing to the special structure of the high strength and hardness of
the ceramics enhance the ductility and toughness of the metal matrix. They improve
the properties of their base materials and are applicable in many situations [1]. The
metal-ceramic composite coating technology was developed to meet the industry’s
needs for coatings. The specifications of these coatings surpass the capabilities of
traditional coating technologies. They can work in extreme environments and face
temperature, corrosion, abrasion, fatigue, and other challenges [2].
Metal-ceramic composite coatings can be deposited on metal substrates by many
means such as thermal spray, welding, and slurry sintering but laser cladding is widely
used in the manufacture of various heavy coatings, which can effectively protect the
substrate from the influence of harsh service conditions [3]. It is an advanced surface
modification technique by using the laser as a heat source to add one material to
the surface of another in a controlled manner [4]. Laser cladding can selectively
deposit materials, accurately and with minimal heat input just where it is required.
The advantages of this technique include allowing additional materials are placed
exactly where needed, making a very wide selection of different materials both
deposited and deposited, so that the deposits are completely fused to the substrate
with little or no porosity, minimal heat input resulting in a narrow heat-affected zone
and limited deformation substrate [5].
WC [6], SiC [7], Cr3 C2 [8], and other ceramic particle reinforced nickel-based
composite coatings have high hardness and good wear resistance. The Ni-WC
composite coating prepared by laser cladding was studied, and it was found that
the addition of nano-WC, La2 O3 , and Mo significantly improved the hardness, wear
resistance, and corrosion resistance of the substrate [9]. The WC/Ni60 composite
coating via laser cladding was found to have a core-like eutectic structure, with good
wear resistance and high hardness [10].
H13 steel is an excellent hot work die steel with dimensional stability, high quality
surface, and toughness at high temperature [11]. However, it is often found that the
surface failure of the H13 mold leads to a shortened service life. Therefore, various
solutions have been designed to solve this problem, such as carburization, nitriding,
carbonitriding, boriding, metallic cementation, plasma immersion, and conventional
coatings to improve surface characteristics [12–15]. Among them, applying metal-
ceramic composite coatings is considered the most effective approach, which can
be achieved via laser cladding process. Because of the distinct features such as high
power density, low heat input, and minimization of the substrate effect, laser beam
has been used to modify surface properties of H13 steel [16]. For instance, the
CO2 laser was used for laser glazing and alloying of TiC on H13 steel to improve
the property and extend the life of die-casting owing to uniform and homogeneous
microstructures, increased hardness and resistance to both corrosion and erosion
[17]. It was also reported that TiC-H13 steel composite coating was deposited on
AISI4140 steel via laser cladding, where fine TiC precipitates were evenly distributed
3.1 Surface Enhancement with Composite Coatings 61
[18]. The TiC-reinforced H13 coating prepared using a continuous wave CO2 laser
was also studied in thermal stability and anti-wear performance [19].
3.1.2 Improvement of Metal-Ceramic Composite Coatings
Although metal-ceramic composite coatings have been successfully fabricated via

laser process. Because of the different gravity densities of each phase in the
composite, it is difficult to always obtain the composite coating with uniform distri-
bution of reinforced particles. As found in the previous experiments, WC particles
easily sank to the bottom of the WC/Ni coating owing to its higher density than the
Ni matrix [20, 21]. Recent studies have shown that the microstructure evolution of
ceramic reinforced composite coatings can be controlled by the use of several newly
developed techniques, such as induction heating [22], mechanical vibration [23],
ultrasonic [24], and magnetic field [25] to achieve uniform distribution of ceramic
particles in the metal matrices. However, because of the limitations of equipment and
environment, there are still problems in applying these methods to practical industrial
applications.
Fortunately, it has been reported that using coated powders, especially Ni-coated
WC particles, in laser cladding of metal-ceramic composite coatings may solve the
particle distribution problem [26]. The morphology and properties of laser cladding
NiCrBSi matrix reinforced by WC were studied. It was found that the WC parti-
cles were uniformly distributed in the coating and the tribological properties of the
Ni matrix were effectively improved by introducing the Ni-coated WC reinforce-
ment [27]. Although the research had examined the properties of Ni-coated WC and
the obtained composite coating had improved WC distribution, it was possible to
gain even more uniform WC particle distribution in Ni alloy matrix by using pre-
alloyed WC-NiCrMo powder to replace a mixed powder of Ni-coated WC powder
and NiCrMo alloy powder to create the composite coating with laser cladding [28].
3.2 Nickel Alloy Composite Coatings
3.2.1 Laser Cladding of WC/NiCrMo Composite
An effective approach to achieving a microstructure with uniformly distributed rein-

forcements for WC/NiCrMo composite by laser cladding was proposed, which used
pre-alloyed WC-NiCrMo powder as the coating feedstock [28]. The coating was
deposited on stainless steel 316L plate. The pre-alloyed WC-NiCrMo powder parti-
cles had a spherical shape with a size of −53 + 30 µm, as shown in Fig. 3.1a. The
SEM image in BSE mode of the powder particle cross section is shown in Fig. 3.1b.
Fig. 3.1 Pre-alloyed

WC-NiCrMo powder
particles: a SEM
morphology and b SEM
BES image of the powder
particle cross section [28].
The main chemical compositions of the stainless steel 316L plate and pre-alloyed
WC-NiCrMo powder are given in Table 3.1.
A LDF400-2000 flexible fiber coupled diode laser system with 2000 W maximum
power, 980 nm wavelength, 4 mm circular spot, a FL-DLight-3000–976 diode laser
system with 3000 W maximum power, 976 nm wavelength, and 12 × 2 mm rect-
angular spot, was used in this research. The laser beam profiles (energy distribution
across the beam) of both systems are shown in Fig. 3.2, showing uniformly distributed
energy densities. Argon gas was used as the protective and shielding gas to avoid
Table 3.1 Main chemical compositions of raw materials (wt%)

Material C Si Mn Cr Ni Mo S P Fe B W
Substrate 0.03 1 2 18 14 3 ≤0.03 ≤0.035 Bal
Powder 0.8 4 15 56.7 5 3.5 3 17
3.2 Nickel Alloy Composite Coatings 63
Fig. 3.2 Energy distribution across the beam a circular spot laser and b wide-band spot laser [28].
oxidation during the laser cladding processes. The powder was fed into the laser spot
of the projection head using a boiling type powder feeding system.
The laser processes were optimized for the porosity and cracks in the coatings
microstructures to determine optimal processing parameters. The results for circular
laser spot and wide-band laser spot prepared specimen are as follows: For the former,
laser power was 1.6 kW, and laser scanning speed was 420 mm/min. For the latter,
laser power was 2.4 kW, and laser scanning speed was 180 mm/min. Powder feeding
rate was 10 g/min for both. For the following property, characterization of the coat-
ings, 10 single clad tracks with a 50% overlap between two adjacent tracks were
prepared using the two laser spots, respectively.
3.2.2 Morphology of Coating Specimens
The photographical morphologies of the coating cross sections are shown in Fig. 3.3.
Significant differences in coating/substrate interface between the specimens prepared
with circular laser spot and wide-band laser spot, respectively, can be observed. The
fusion line is arc with the former while that with the latter is straight. This suggests that
wide-band (rectangular) laser spot has a more uniform energy distribution and laser
power density than circular laser spot, which is consistent with the result of previous
study [10]. The average width and maximum thickness of the coating prepared by
circular spot laser are about 5 mm and 0.86 mm, respectively, while the average
width and maximum thickness of the coating prepared by the wide-band spot laser
are about 9.2 mm and 1.27 mm, respectively. The maximum penetration depth of the
circular spot laser prepared coating is about 0.62 mm, which is obviously larger than
that of the wide-band laser prepared coating (0.1 mm).
To investigate the dilution of the coatings during the laser cladding process, the
dilution rates β were calculated according to the following equation [29]
Fig. 3.3 Cross-sectional photograph of the coating fabricated with a circular laser spot and b
wide-band laser spot [28]. Reprinted from Yao et al. [28], Copyright (2018), with permission from
Elsevier
S2
β= × 100% (3.1)
S1 + S2
where S 1 is the coating layer area on substrate, and S 2 represents the melted area of
the substrate. The dilution rates are calculated to be 23.6% for the circular spot laser
prepared coating and 7.8% for the wide-band spot laser prepared coating.
Generally, when the powder feeding rate is the same, the scanning speed affects
the thickness of the coating, which can be evidenced by Fig. 3.3. The circular spot
laser prepared coating (0.86 mm) has smaller thickness than the wide-band laser
prepared one (1.27 mm), indicating that the higher the scanning speed, the thinner
the coating is, due to lower absolute powder feeding rate according to the following
equation
F
M= (3.2)
V
where M represents mass feeding rate, F stands for powder feeding rate, and V
is laser scanning speed. The absolute powder feeding rate of the wide-band spot
prepared coating is calculated to be about 2.3 times higher than that of the circular
spot prepared one. However, the two coatings have similar laser energy densities
(1.27 × 104 W/cm2 and 104 W/cm2 , respectively) according to the equation
P
E= (3.3)
S
where E represents laser energy densities, P stands for laser power, and S is the area
of laser spot. The circular spot laser has higher energy input due to lower absolute
powder feeding rate at the irradiated areas. In this case, a large part of the energy
goes to melting the substrate material, thus resulting in a relatively large dilution rate
compared with the wide-band spot laser prepared coating.
The molten volume penetration into the substrate is primarily driven by the temper-
ature gradients in the molten pool, which creates the viscous flows and buoyancy of
the material. The molten flow is caused by Marangoni convection force that typically
drives the molten material from the center of the molten pool to the edges and then
rises up from the bottom of the molten pool due to the effect of buoyancy flow. It is
also known as the effect of contra-flow and mass transfer, which makes the melted
substrate diffuse into the coating and change the chemical composition of the coating.
The dilution ratio of the coating is usually related to laser energy input and the speed
of powder delivery. Therefore, the coating produced by circular spot laser should
have larger dilution ratio.
3.2.3 Microstructure of Coating Specimens
The elemental content analysis and quantitative mapping of the microstructures of the
coating specimens in cross section were observed using an optical microscope and
SEM equipped with a Bruker Nano Xflash Detector 5010 EDS system. The phases
in the microstructures were identified with XRD. It can be seen in Fig. 3.4 that both
coatings are dense and have no obvious defects. In the two coatings, WC particles
are uniformly embedded in the eutectic. However, there is an evident transition layer
in the circular laser spot prepared coating, as seen in Fig. 3.4a, which has a structure
of coarse columnar dendrites. However, no such a layer is found in the wide-band
spot laser prepared coating (Fig. 3.4b), instead, there is a planar crystal layer at the
coating/substrate interface. Additionally, the WC particles in the former have larger
size than in the latter.
The SEM microstructures of the coatings are shown in Figs. 3.5 and 3.6. For
the coating produced by circular laser spot, the microstructure consists of uniformly
distributed block carbides, dendrite eutectic, and interdendritic eutectic carbides,
and different regions of the coating appear different microstructure characteristics.
At the bonding interface, there are coarse columnar dendrites, which were possibly
due to the transfer of iron (Fe) from the substrate, but the growth of the dendrite
was inhibited during the solidification process. In the molten pool, the pre-alloyed
WC particles may be partially dissolved, which caused a significant change in the
chemical composition of the molten pool. These particles have both primary cored
structure and noncore structure, as shown in Fig. 3.5a. The microstructure in the top
Fig. 3.4 Microstructure in

cross section of the coating
prepared via a circular laser
spot and b wide-band laser
spot [28]. Reprinted from
Yao et al. [28], Copyright
from Elsevier
region of the coating has the primary cored WC phase more uniformly distributed in
the eutectic matrix, and the growth of the noncore WC phase was inhibited during
the solidification process, as shown in Fig. 3.5b.
The different microstructure characteristics in the coating indicate that the solid-
ification of the coating was not uniform. This may be owing to the diffusion and
segregation of the solute atoms that caused by the temperature gradient and solidi-
fication rate. At the substrate/coating interface, the coarse columnar dendrites grew
along the interface where the temperature gradient was great. The dendrite structure
of γ -(Ni, Fe) began to grow with the increase of solidification rate. Once the bath
composition somewhere in the coating reached the eutectic point, the separated liquid
metal solute atoms such as W, Cr, and C were segregated into the lamellar eutectic
structure usually having an inside core. This may be owing to the incomplete dissolu-
tion of WC. The temperature in the top region of the cladding increased significantly
compared to the bottom region, resulting in an increase of the contents of W and C,
but the orderly growth of the lamellar eutectic structures was suppressed due to rapid
Fig. 3.5 SEM

microstructure of circular
laser spot prepared coating a
at interface and b at top [28].
cooling of this region. At the same time, the cored carbides with high melting point
separated out in the molten metal and embedded in the eutectic structure matrix.
The microstructure characteristics of the cladding layer produced by wide-band
laser spot are slightly different from that of the cladding layer produced by circular
laser spot. Generally, no cored WC phase is found in the cladding, but the primary WC
is also uniformly distributed in the eutectic matrix. In addition, the planar crystal at the
coating/substrate interface is a thin layer without obvious coarse columnar dendrites,
as shown in Fig. 3.6a. The top region of the cladding appears similar microstructural
characteristics (Fig. 3.6b) to the bottom region (close to the interface).
It is well known that when using a mixture of WC powder and Ni-based alloy
powder, WC particles tend to sink at the bottom of the coating layer during laser
cladding due to higher density than the nickel matrix. However, using pre-alloyed
WC-NiCrMo powder can solve this problem because the WC particles in the powder
were already evenly dispersed in the NiCrMo matrix before laser cladding, so it is
easier to achieve a uniform cladding.
Fig. 3.6 SEM

microstructure of wide-band
laser spot prepared coating a
at interface and b at top [28].
The XRD pattern of the coating is shown in Fig. 3.7. It can be seen that γ -(Ni, Fe)
is the main phase in the coating. There also exist WC, M23 C6 , Ni2.9 Cr0.7 Fe0.36 , and
Ni31 Si12 phases. Three areas in the microstructure of each coating were investigated
using SEM/EDS, as labeled in Fig. 3.8, and the element contents of the areas are
summarized in Table 3.2. For the coating produced by circular laser spot, the cored
phase (area 1) is mainly rich in W and Cr, and the content of C is high, which indicates
that the cored phase is composite carbides consisting of WC and M23 C6 . The two
lamellar eutectic structures have different chemical compositions, the contents of Cr,
Mo, and W in area 2 are much higher, and the content of Ni is much lower content
than area 3, indicating that the former is carbides (WC and M23 C6 ) with γ -(Ni, Fe)
matrix, while the latter is γ -(Ni, Fe) matrix. For the coating produced by wide-band
laser spot, since area 1 contains very high W content, and high Cr and C contents, it
should be major WC with minor M23 C6 , while area 2 contains very high Cr and C
contents with very low W content so that it might be M23 C6 . Area 3 with very high
Ni and Fe should be γ -(Ni, Fe) matrix.
Fig. 3.7 XRD pattern of

WC/NiCrMo coating [28].
Fig. 3.8 SEM

microstructure of a circular
laser spot prepared coating
and b wide-band laser spot
prepared coating with three
distinct areas indicated [28].
Table 3.2 EDS elemental contents (at.%) in different regions of WC/NiCrMo coatings [28]
Circular laser spot area C Si Cr Fe Ni Mo W
1 17.08 44.97 14.74 6.57 1.9 14.74
2 39.04 28.65 16.41 7.25 1.44 7.22
3 38.66 3.38 10.16 17.79 29.18 0.25 0.59
Wide-band laser spot area C Si Cr Fe Ni Mo W
1 25.42 32.68 7.95 8.89 0.87 24.18
2 32.79 1.72 37.44 9.11 18.07 0.12 0.76
3 17.23 7.45 7.27 15.21 52.67 0.03 0.14
When solidification begins, partially dissolved particles were first existed in the
molten pool and released Cr and W, while absorbing Ni and Fe. With the decrease
of temperature, the contents of Ni and Fe around the primary ceramic particles
increase, and Ni dendrites are formed owing to their low melting point. With the
further decrease of the molten pool temperature, the interdendritic eutectic carbides
nucleated and formed lamellar eutectic structures. According to the results of the
EDS and XRD analyses, the lamellar eutectic structure is composed of γ -(Ni, Fe)
and M23 C6 (M represents Cr and W), and the W came from the partially dissolved
WC particles.
3.2.4 Elemental Dilution
The results of microstructural analysis show that the microstructure and phase distri-
bution of the two coatings are different. This may be due to the different dilution
characteristics of Fe in the two claddings. Line scanning of Ni, Cr, W, and Fe elements
from the substrate to the coating surface was performed in the cross sections of the
two coating specimens using EDS. As seen in Fig. 3.9, there is a noticeable differ-
ence in dilution behavior between the two coatings at the coating/substrate interfaces
according to the element fraction distributions. For the coating produced by circular
laser spot, in the substrate region around the interface, the contents of Ni and Fe
elements vary largely, but these contents are almost constant in the region for the
wide-band laser spot prepared one. In addition, Fe concentration in the cladding layer
of the former is higher than that of the latter, and Ni concentration is the opposite.
These variations and differences in Ni and Fe contents suggest that Fe dilution was
greater in the coating produced by circular laser spot than the one produced by the
wide-band laser spot.
Fig. 3.9 Elemental

distributions from the
substrate to the coating
surface a circular laser spot
prepared coating and b
wide-band laser spot
prepared coating [28].

profiles of WC/NiCrMo
coatings in cross section
Elsevier
3.2.5 Coating Hardness
Hardness was measured for the coatings on surface using a Rockwell hardness tester
with a load capacity of 1471 N. The wide-band laser spot prepared coating has a
hardness valve about HRC62, which is much higher than the hardness (HRC50) of the
circular laser spot prepared coating. Microhardness of the claddings was measured on
cross section using a digital microhardness tester with a 300 load along the cladding
thickness (depth). The hardness distribution from the top of the coating to the interface
is shown in Fig. 3.10. Generally, the hardness is constant throughout the thickness
of the coating, but the hardness of the coating prepared by the broadband laser spot
is significantly higher than that of the coating prepared by the circular laser spot.
The hardness of the two substrates is the same as that of the original SS316L, which
indicates that the chemical composition and microstructure of the two substrates are
not affected by laser heat. The lower hardness of the coating prepared by the circular
laser point is attributed to Fe dilution. It is also shown that the hardness of both
coatings has a drop at the coating/substrate interface.
3.2.6 Coating Wear Performance
The wear resistance of the coatings was examined under ball-on-disc wear tests in dry
sliding mode at room temperature. The rotation speed of the specimen was 350 rpm,
and the normal load was 400 g. The ball was made from Si3 N4 with hardness 1300
HV0.2 . The test duration was 2 h, and a 6 mm diameter circular track was generated
in the surface as a result of wear. The same approach as described previously was
used to calculate the wear loss of each coating specimen. The cross-sectional profiles
of wear track of the two coatings are presented in Fig. 3.11a. It is obvious that the
maximum depth of the wear track of the coating produced by wide-band laser spot
Fig. 3.11 Dry sliding wear

test results of WC-NiCrMo
coatings: a cross-sectional
profile of wear track and b
average wear loss [28].
is much smaller than that of the coating produced by circular laser spot, indicating
that the former is more resistant to wear. The average wear losses of the two coatings
are shown in Fig. 3.11b, with the standard deviation bars attached for error analyses.
The results show that the average wear amount of the coating prepared by wide-band
laser spot is much lower than that of the coating prepared by circular laser spot,
which proves that the former has better wear resistance than the latter.
The worn surfaces of the coating specimens were evaluated using SEM to explore
the wear mechanisms. As seen in Figs. 3.12 and 3.13, consistent with the wear loss
results, the worn surface of the coating produced by circular laser spot (Fig. 3.12)
appears serious damage with significant cracking and fracture, bulk materials spalled
off the surface. On the contrary, the worn surface of the wide-band laser spot prepared
coating (Fig. 3.13) is very smooth and shows litter cracking and fracture. The wear
scars on this surface are shallow, and the wear debris is little.
Fig. 3.12 SEM worn

surface of circular laser spot
prepared coating: a at low
magnification [28].
3.3 Steel Composite Coating
3.3.1 Laser Cladding of TiC/H13 Composite
An effective way to enhance H13 steel surface can be laser cladding of a mixture
of TiC (20 wt%, average size 2 µm) and H13 steel (80 wt%, average size 70 µm)
powders on H13 steel substrate, thus to form a composite coating [19]. The chemical
composition (wt%) of H13 steel powder is 5.19% Cr, 1.64% Mo, 0.42% Mn, 0.42
%C, 0.99% Si, and 1.01% V (Bal. Fe). The laser cladding was prepared using a CO2
laser machining system, with the process parameters as laser power 2.5 kW, scanning
rate 500 mm/min, laser beam 4 mm diameter, and argon gas 25 L/min (purity 99.9%).
3.3 Steel Composite Coating 75
Fig. 3.13 SEM worn

surface of wide-band laser
spot prepared coating: a at
low magnification and b at
high magnification [28].
3.3.2 Microstructure of TiC/H13 Composite Coating
The microstructure of the cladding specimen was analyzed using a HitachiS-4700

scanning electron microscopy (SEM) equipped with Thermo Noran Vantage EIS
energy dispersive spectrometry (EDS) and X-ray diffraction with Cu Kα radiation.
The cross section can be identified in three regions, that is, cladding zone, dilution
zone, and heat-affected zone (HAZ), as shown in Fig. 3.14a. The SEM microstructure
in Fig. 3.14b shows a number of uniformly distributed particles (white) within the
solid solution matrix. The EDS analysis revealed that the dendrite particles are Ti–
rich. Further X-ray analysis indicated that the Ti–rich phase is TiC. This implied that
the TiC particles did not involve any reaction with other elements except minor Ti
oxidation during laser cladding. Additionally, Fe-rich carbides were detected in the
coating, which are embedded in the Fe–Cr solid solution matrix.
Fig. 3.14 a Morphology

and b SEM microstructure of
TiC/H13 steel coating cross
section [19]. Reprinted from Cladding zone
Kong et al. [19], Copyright
from IEEE
Dilution zone
HAZ HAZ
(a)
Cladding zone
Dilution zone
HAZ
(b)
3.3.3 Tribological Behavior of TiC/H13 Composite Coating
The wear resistance of the TiC/H13 steel composite coating was investigated on a
HT 600 pin on disc tribometer using a ceramic Si3 N4 ball under a 500 g load in dry
sliding wear mode at ambient temperature. The friction force was monitored during
the wear process, and the friction coefficient can then be recorded with time, as
illustrated in Fig. 3.15. Although fluctuation was observed, the friction coefficients
generally reached a constant with sliding time. The composite coating has a smaller
value of friction coefficient than H13 steel substrate. Accordingly, the weight loss
of the composite coating due to wear was measured to be only about a quarter of
that of H13 steel substrate. The SEM worn surface morphology of the H13 steel
substrate appears larger plastic deformation with obvious ‘warm-up’ and deeper
wear scars, compared with that of the composite coating, see Fig. 3.16. The latter
3.3 Steel Composite Coating 77
Fig. 3.15 Friction coefficient profiles of TiC/H13 steel coating and H13 steel substrate in dry
sliding wear tests [19]. Reprinted from Kong et al. [19], Copyright (2010), with permission from
IEEE
appears smoother and less deformed. The wear test results reveal that addition of
TiC to H13 steel can improve hardness and wear resistance significantly.
3.3.4 Thermal Stability of TiC/H13 Composite Coating
For the purpose of investigating the thermal stability of the TiC/H13 steel coating at
the operating temperature of hot-working die, the coating specimen experienced heat
treatments as follows: It was heated in a furnace to 600 °C, held at this temperature for
6 or 18 h, and then cooled down to room temperature in air. The microhardness of the
heat-treated coatings was measured in cross section from the coating surface to the
substrate, using an HXD-1000 microhardness tester, with an indentation load of 200 g
and dwelling time of 15 s. In general, hardness decreases along the coating depth,
indicating a nonuniform distribution of TiC within the coating depth, as illustrated
in Fig. 3.17. This is possible because TiC has lower density than H13 steel, and
thus, the TiC particles were prone to stay at the top of the melting pool during the
laser cladding process. Higher TiC concentration provides higher hardness in the top
layer of the coating. It is also shown that the heat treatments somewhat reduced the
hardness of the coating, but not very much. This may be a result of residual stress
release due to aging. It is interesting to notice that after the 6 h aging treatment, the
hardness of the HAZ increased. This may be attributed to secondary hardening at the
aging temperature during the holding time.
Fig. 3.16 SEM worn

surface morphology of a
H13 steel substrate and b
TiC/H13 steel coating [19].
Reprinted from Kong et al.
permission from IEEE
3.4 Summary of Composite Coating via Laser Cladding
The WC-NiCrMo composite coatings prepared by circular spot laser and wide-band
spot laser show different microstructures and wear properties, but both have a uniform
distribution of WC particles in the NiCrMo solution matrix. Compared with the
conventional method of preparing WC-NiCrMo composite coating using the mixed
powder of WC and NiCrMo alloy, pre-alloyed WC-NiCrMo powder where WC parti-
cles were previously dispersed in the NiCrMo matrix can obtain better microstructure
of WC-NiCrMo composite coating via laser cladding process. Regarding the differ-
ence in microstructure between the coating produced by circular laser spot and the
one produced by wide-band laser spot, wide-band (rectangular) laser spot usually has
a more uniform energy distribution and laser power density than circular laser spot; in
3.4 Summary of Composite Coating via Laser Cladding 79
Fig. 3.17 Hardness profiles in cross section of TiC/H13 steel coatings [19]. Reprinted from IEEE
Proceedings, Kong et al. [19], Copyright (2010), with permission from IEEE
other words, these two laser spot geometries can result in different temperature fields
during laser cladding process. It is worth noting that according to Fick’s diffusion
and Arrhenius law, the evolution characteristics of the microstructure are governed
by the concentration gradient of solute atoms and temperature field in the molten
pool [30]. In the coating produced by circular spot laser, reinforcement dissolution is
more significant due to the inherent feature of laser processing. Thus, a large number
of Fe atoms are transferred from the substrate to the coating, resulting in a lamellar
eutectic structure. The dilution Fe in the coating produced by circular laser caused
a decrease of hardness, compared with the coating produced by wide-band laser, as
shown in the microhardness tests.
The volume fraction of carbide particles (WC and M23 C6 ) in the composite coat-
ings were estimated using the SEM associated software. The results shown that the
coating produced by wide-band laser spot has a higher volume fraction (36 vol%) of
carbides than the coating produced by circular laser spot (20 vol%). This should be
the main reason why the former is harder and more wear-resistant than the latter. At
the same time, it was estimated that the volume fraction of WC particles in the two
coatings was almost the same, which means that the amounts of M23 C6 in the two
coatings are different. This difference may be caused by Fe dilution, because high
Fe content can affect and suppress the precipitation of M23 C6 [31]. Excessive Fe
concentration also has detrimental effect on the performance of γ -(Ni, Fe) matrix so
that Fe dilution is usually avoided as much as possible [32]. The wear mechanisms
of multi-phase composites are complex, which generally depend on several factors
such as the type, size, distribution, and volume fraction of the ceramic reinforce-
ments. In the WC-NiCrMo composite coatings, the hard ceramic reinforcements
have beneficial effect on resisting plastic deformation, while the soft and ductile
matrix experiences severe plastic deformation during the wear process. The coating
produced by wide-band laser spot has larger volume fraction of carbides thus harder
than that produced by circular laser spot, and therefore, the former is more resistant
to wear than the latter.
Adding 20 wt% TiC particles into H13 steel powder created a composite coating
on H13 steel substrate via laser cladding, which greatly improved the surface hard-
ness and wear resistance, but due to nonuniform distribution of TiC particles along
the coating depth, hardness appeared the maximum at the top surface of the coating
and decreases in the coating thickness. Aging treatments can affect the hardness of
the coating, but not significantly, which means that the TiC/H13 steel coating has
better thermal stability at elevated temperatures. Because of the temperature gradient
of the cladding layer during the laser process, the final microstructure of the clad
TiC/H13 coating exhibited variation from the surface layer to the substrate. Near
the coating surface, the TiC particles had partially molten, and thus, the microstruc-
ture showed a dendritic morphology, while within the coating, the microstructure
appeared irregular.
References
1. Lei TC, Ouyang JH, Pei YT, Zhou Y (1996) Microstructure and sliding wear properties of laser
clad TiN reinforced composite coating. Surf Eng 12(1):55–60
2. Kooi BJ, Pei YT, Th J, De Hosson M (2003) The evolution of microstructure in a laser clad
TiB-Ti composite coating. Acta Mater 51:831–845
3. Zhu BD, Zeng XY, Tao ZY, Yang SG, Cui K (1993) Coarse cemented WC particle ceramic-metal
composite coatings produced by laser cladding. Wear 170(2):161–166
4. Zhang WP, Liu S (2005) Research on the cracks of Ni-based metal-ceramic composite coating
by laser cladding. Fuhe Cailiao Xuebao 22(3):98–102
5. Du BS, Samant AN, Paital SR, Dahotre NB (2008) Pulsed laser synthesis of ceramic-metal
composite coating on steel. Appl Surf Sci 255(5–2):3188–3194
6. Guo C, Zhou J, Chen J, Zhao J, Yu Y, Zhou H (2011) High temperature wear resistance of laser
cladding NiCrBSi and NiCrBSi/WC-Ni composite coatings. Wear 270:492–498
7. Li Q, Song GM, Zhang YZ, Lei TC, Chen WZ (2003) Microstructure and dry sliding wear
behavior of laser clad Ni-based alloy coating with the addition of SiC. Wear 254:222–229
8. Janicki D (2017) Laser cladding of Inconel 625-based composite coatings reinforced by porous
chromium carbide particles. Opt Laser Technol 94:6–14
9. Farahmand P, Kovacevic R (2015) Corrosion and wear behavior of laser cladded Ni–WC
coatings. Surf Coat Technol 276:121–135
10. Ma QS, Li YJ, Wang J, Liu K (2015) Investigation on cored-eutectic structure in Ni60/WC
composite coatings fabricated by wide-band laser cladding. J Alloy Compd 645:151–157
11. Basso RIO, Candal RJ, Figueroa CA, Wisnivesky D, Alvarez F (2009) Influence of microstruc-
ture on the corrosion behavior of nitrocarburized AISI H13 tool steel obtained by pulsed DC
plasma. Surf Coat Tech 203:1293–1297
12. Yang J, Zhang T (2004) Tribological properties changes of H13 steel induced by MEVVA Ta
ion implantation. Appl Surf Sci 229(124):249–253
13. Saklakoglu N (2007) Characterization of surface mechanical properties of H13 steel implanted
by plasma immersion ion implantation. J Mater Proc Tech 189(123):367–373
14. Da Silva LLG, Ueda M, Nakazato RZ (2007) Enhanced corrosion resistance of AISI H13 steel
treated by nitrogen plasma immersion ion implantation. Surf Coat Tech 201(19–20):8291–8294
References 81
15. Jiméneza H, Deviaa DM, Benavidesa V, Deviaa A, Arangoa YC, Arangoa PJ, Velezb JM (2008)
Thermal protection of H13 steel by growth of (TiAl)N films by PAPVD pulsed arc technique.
Mater Charact 59:1070–1077
16. Tran VN, Yang S, Phung TA (2018) Microstructure and properties of Cu/TiB2 wear resistance
composite coating on H13 steel prepared by in-situ laser cladding. Opt Laser Technol 108:480–
486
17. Jiang WP, Molian P (2001) Nanocrystalline TiC powder alloying and glazing of H13 steel
using a CO2 laser for improved life of die-casting dies. Surf Coat Tech 135:139–149
18. Jiang WH, Kovacevic R (2007) Laser deposited TiC/H13 tool steel composite coatings and
their erosion resistance. J Mater Proc Tech 186:331–338
19. Kong FZ, Yao JH, Tang XD, Lou CH, Ding QM (2010) Study of microstructure and properties of
laser cladding TiC-H13 composite coating. In: Proceedings of the first international conference
on mechanic automation and control engineering (MACE), Wuhan, China, p 3611–3614
20. Acker KV, Vanhoyweghen D, Persoons R, Vangrunderbeek J (2005) Influence of tungsten
carbide particle size and distribution on the wear resistance of laser clad WC/Ni coatings. Wear
258:194–202
21. Shu D, Li ZG, Zhang K, Yao CW, Li DY, Dai ZB (2017) In situ synthesized high volume
fraction WC reinforced Ni-based coating by laser cladding. Mater Lett 195:178–181
22. Zhou SF, Huang YJ, Zeng XY (2008) A study of Ni-based WC composite coatings by laser
induction hybrid rapid cladding with elliptical spot. Appl Surf Sci 254:3110–3119
23. Liu H, Xu Q, Wang C, Zhang X (2015) Corrosion and wear behavior of Ni60CuMoW coatings
fabricated by combination of laser cladding and mechanical vibration processing. J Alloy
Compd 621:357–363
24. Wu DJ, Guo MH, Ma GY, Niu FY (2015) Dilution characteristics of ultrasonic assisted laser
clad yttria-stabilized zirconia coating. Mater Lett 141:207–209
25. Wang L, Yao JH, Hu Y, Zhang QL, Sun Z, Liu R (2017) Influence of electric-magnetic
compound field on the WC particles distribution in laser melt injection. Surf Coat Technol
315:32–43
26. Tobar MJ, Álvarez C, Amado JM, Rodríguez G, Yáñez A (2006) Morphology and character-
ization of laser clad composite NiCrBSi–WC coatings on stainless steel. Surf Coat Technol
200:6313–6317
27. Guo C, Chen JM, Zhou JS, Zhao JR, Wang LQ, Yu YJ, Zhou HD (2012) Effects of WC-Ni
content on microstructure and wear resistance of laser cladding Ni-based alloys coating. Surf
Coat Technol 206:2064–2071
28. Yao JH, Zhang J, Wu GL, Wang L, Zhang QL, Liu R (2018) Microstructure and wear resistance
of laser cladded composite coatings prepared from pre-alloyed WC-NiCrMo powder with
different laser spots. Opt Laser Technol 101:520–530
29. Lin CM, Li JC, Su CY, Chang YH, Kai WY, Chen CS (2017) Effects of water cooling on
microstructural evolution, hardness and anti-corrosion properties of Inconel 52 fusion-cladded
AISI 316L stainless steel. Surf Coat Technol 322:218–226
30. Gao T, Liu G, Liu X (2014) Compositions and morphologies of TiAlSi intermetallics in different
diffusion couples. Mater Charact 95:285–290
31. Feng K, Chen Y, Deng PS, Li YY, Zhao HX, Lu FG, Li RF, Huang J, Li ZG (2016) Improved
high-temperature hardness and wear resistance of Inconel 625 coatings fabricated by laser
cladding. J Mater Process Tech 243:82–91
32. He YM, Yang JG, Fu W, Wang L, Gao ZL (2016) An analysis of formation mechanism and
nano-scale hardness of the laser-induced coating on Ni–17Mo–7Cr based superalloy. J Alloy
Compd 673:8–16
Chapter 4
Laser Surface Hardening
Abstract Laser hardening is often used for hardening component segments that are
subject to severe wear. Using this method, segments irradiated by laser can locally
be hardened. Laser surface hardening treatment is applied on 17-4PH stainless steel
and infinite chilling medium NiCr cast iron. The microstructures of the laser-treated
surface layers are examined using scanning electron microscopy (SEM) or optical
microscopy. The mechanical properties of the laser-treated surface are determined
using nanoindentation test, and the cavitation-erosion behavior of 17-4PH stain-
less steel with the laser-treated surface is investigated in 3.5 wt% NaCl solution.
The eroded surfaces of 17-4PH stainless steel with and without laser treatment are
analyzed using SEM, and the depth data of the pits generated in the specimen surfaces
are fitted into the extreme value analysis (EVA) model to predict the maximum pit
depth that may occur in the material surface with a given service life. It is shown
that the laser surface hardening treatment improves significantly the mechanical and
cavitation-erosion performance of 17-4PH stainless steel. In the laser-treated infi-
nite chilling medium NiCr cast iron specimen, there are three distinct zones: melting
zone, transition zone and heat affected zone (HAZ). The size of the dendrite structure
in the melting zone is only 1/10 to 1/30 of that in the substrate. With the microstruc-
ture refinement, the hardness and wear resistance of infinite chilling medium NiCr
cast iron are improved remarkably. The field test on the surface-treated roller demon-
strates that the carrying capacity of the roller increases by 50% due to the laser surface
hardening, which results from the enhancement in hardness and wear resistance.
4.1 Surface Hardening of Steels
4.1.1 Methods of Surface Hardening
Surface hardening is often required for various mechanical parts such as cams,
ring gears, bearings, shafts, turbine, and automotive components to obtain a very
hard surface for wear resistance, while a tough interior can be kept to resist the
impact which occurs during operation. Most surface treatments result in compres-
sive residual stresses in the surface layer that reduce the probability of crack initiation

84 4 Laser Surface Hardening
and help arrest crack propagation at the case-core interface. Furthermore, the surface
hardening of steels can have an advantage over through hardening because less expen-
sive low-carbon and medium carbon steels can be surface hardened with minimal
distortion and cracking associated with the through hardening of thick sections.
Surface hardening can be implemented via diffusion methods which modify the
chemical composition of the surface with hardening species such as carbon, nitrogen,
boron, and so on. Selective surface-hardening methods are more attractive because
they allow localized hardening [1], and thus, other parts of the workpiece will not
be affected. Surface hardening by diffusion involves the chemical modification of a
surface. The mechanism of the basic process is thermochemical because certain heat
is needed to enhance the diffusion of hardening elements into the surface and subsur-
face regions of a part. The depth of diffusion is governed by processing time and
temperature. Surface hardening by diffusion includes several variations of hardening
elements such as carbon, nitrogen, and boron, handles and transports the hardening
elements to the surface of the part [2]. Selective hardening generally involves local
transformation of hardening elements, heating and quenching treatment in small
areas, but some selective hardening methods, for example, selective nitriding, ion
implantation, and ion beam mixing, are based solely on compositional modifica-
tion. Transformation hardening generally induces compressive residual stresses in
the surface layer, which are beneficial for fatigue strength. In selective hardening,
however, some residual tensile stresses may also exist in the interface region between
the hardened zone and the unhardened zone. Therefore, selective hardening by the
methods of flame or induction heating should be employed on the surfaces where
geometric stress concentrations are minimal [3].
4.1.2 Surface Hardening via Laser Process
Laser surface hardening is using laser as the heat source to complete the surface
treatment. It is one of the laser heat treatment methods widely used to harden local
areas of machine components which are made of steel and cast iron. This process
is sometimes referred to as laser transformation hardening in order to differentiate
it from laser surface melting process [4]. Laser transformation hardening does not
involve chemistry change of the treated surface, and the process, like induction
and flame hardening, provides an effective technique to harden ferrous materials
selectively. Other methods of laser surface treatments include surface melting and
surface alloying.
The mechanism of laser transformation hardening involves creating thin surface
zones that are heated by laser and cooled very rapidly owing to small treated area,
which results in very fine martensitic microstructures, even for the steels with rela-
tively low hardenability. With this technique, high hardness and good wear resis-
tance with less distortion of the treated part can be achieved. The laser treatment
method differs from induction and flame heating in that the laser can be applied
at some distance from the workpiece and the width of the heated spot or track can
4.1 Surface Hardening of Steels 85
be controlled because the laser light is reflected by mirrors to the focusing lens
[5]. During laser hardening, the energy from the laser beam is applied directly to
the component surface to heat the surface layer up to the hardening temperature
(>1000 °C) in a small area within a very short period of time. The main advantage of
using a laser heat source in surface treatment is low heat input required so that the heat
can be transmitted into the base material rapidly. Self-quenching of the surface layer
in air results in a martensitic structure formed, and the hardening layer is ‘cooled’.
Laser transformation hardening enables a very tough, fine-grained structure created
owing to the high heat-up rate during the surface treatment process. Moreover, self-
quenching can minimize the risk of cracks. The precisely focused energy ensures that
the treated component is subject to low heat impact, thus offering a great advantage
in minimum quench distortion [6].
4.2 Surface Hardening of 17-4PH Stainless Steel
4.2.1 Laser Hardening Process
Laser hardening is often applied on hardening steel component segments that are
subject to severe wear. Using this method, the segments irradiated by laser can
locally be hardened. For steel hardening, the material is heated above the austenitising
temperature by laser for a short time. With the further movement of the laser beam,
the hard metal structure is created which leads to the increase in hardness of the
target surface [7]. In the process of laser hardening, relatively low power densities
are used; the smaller the area for laser hardening and the required hardened depth,
the more efficient the process is.
There are strong demands from the hot rolling and steam turbine industries for
surface hardening of various parts which are subject to severe wear during service.
Accordingly, extensive studies of laser hardening have been conducted on cast irons
[8] and steels [9], which provide important guidance in surface enhancement of the
key components serving in these industries. As one of the popular materials for steam
turbine blades, precipitation hardened stainless steel 17-4PH stainless steel can be
laser solution-treated for improving cavitation-erosion resistance [10], which was
performed using a LDF400-2000 high power flexible fiber coupled diode laser and
the motion device of the IRB2400/16 six degree of freedom robot from Asea Brown
Boveri (ABB) Ltd, under shielding of argon gas with the process parameters: laser
energy density of 56.25 J/mm2 and feeding rate of 13 g/min. After laser hardening,
the 17-4PH steel specimen was aged in furnace at 460 °C for 3 h, cooled by water.
4.2.2 Microstructure of Hardened Surface
For microstructural analysis, the 17-4PH steel substrate and laser-treated 17-4PH
steel specimen were polished following the standard mechanical procedures and then
etched with a mixture of 5 g FeCl3 , 2 ml hydrochloric acid, and 99 ml absolute ethyl
alcohol. The morphologies and microstructures of the specimens were examined
using a Hitachi Model S-570 SEM with EDS. As shown in Fig. 4.1, 17-4PH steel
substrate has a typical lath martensite feature, while the laser-treated specimen has
additional precipitates of fcc ε-Cu besides lath martensite.
Fig. 4.1 SEM

microstructure of a 17-4PH
steel substrate and b
laser-treated 17-4PH steel
specimen [10]. Reprinted
Nature
(a)
Precipitate
(b)
4.2 Surface Hardening of 17-4PH Stainless Steel 87
Fig. 4.2 Hardness profiles

in cross section of the
substrate and laser-treated
specimen [10]. Reprinted
Nature
4.2.3 Hardness of Hardened Surface
Microhardness test was conducted on the cross sections of 17-4PH steel substrate
and laser-treated 17-4PH steel specimen using a HMV-2TADWXY Model Vivtorinox
hardness tester. The hardness variation from the specimen surface to a certain depth
was investigated at a constant interval distance of 0.8 mm under a 0.2 N indentation
load. The results are reported in Fig. 4.2. It is shown that hardness is nearly constant
along the depth of the 17-4PH steel substrate specimen, but the laser-treated spec-
imen shows decreasing of hardness in depth from the surface. Due to the hardening
treatment, the specimen has maximum hardness at the surface layer. It is evident
that the surface treatment improved the hardness by approximately 1.2 times and the
hardened layer is about 1 mm thick.
4.2.4 Mechanical Properties of Hardened Surface
The mechanical behavior of the treated surface of 17-4PH steel was investigated
under nanoindentation tests, in comparison with the 17-4PH steel substrate, using
a CSM nanohardness tester with a Berkovich indenter. The maximum normal load
applied on the specimen surface was 50 mN. A load–unloading curve can be gener-
ated from each indentation test in the form of load versus displacement. The schematic
diagram of loading–unloading curve for a metallic material in Fig. 4.3 is used to define
the parameters of interest. Segment OA represents loading process and segment AB
unloading process. The plastic strain energy stored in the material is represented
by the area of OAB. The area of BAC corresponds to the elastic work which can
be recovered during the unloading process. The parameters h max and Fmax are the
maximum displacement and load of the indenter, respectively. The parameter hr is
the depth of the residual impression. For a perfect plastic material, the unloading
Fig. 4.3 Schematic diagram

of indentation
load–displacement curve
[11]. Reprinted from Oliver
Springer Nature
curve of the material is a straight line AC, then hr = hmax , and area OAB is equal to
area OAC. However, most metallic materials are capable of working-hardening, and
thus, the ratio of area BAC to area OAC indicates the elastic deformation capacity of
the materials. The hardness and the Young’s modulus of the tested specimen surface
can be calculated from the loading/unloading curve using the Oliver–Pharr method
[11].
The load–displacement curves from the nanoindentation tests of the 17-4PH steel
specimens are presented in Fig. 4.4. To better depict the mechanical behavior of the
surfaces, the elastic deformation ratio, γ = AAOACBAC
, was calculated from the load–
displacement curve for each specimen, where ABAC is the elastic area (the integral
Fig. 4.4 Load versus

displacement of 17-4PH
steel specimens in
nanoindentation test [10].
Nature

Specimen The Young’s Hardness Elastic
nanoindentation results for
modulus Hv capability
17-4PH steel specimens [10]
GPa γ
17-4PH 194.03 479.28 0.1942
substrate
Laser-treated 223.3 556.89 0.2283
17-4PH
of unloading line), and AOAC is the total area (the integral of unloading line), as
illustrated in Fig. 4.3. This parameter represents the elastic capability of the tested
material. The larger the γ value, the better the elastic recovery of the material is. On
the other hand, the larger the elastic recovery, the less the plastic deformation remains.
The obtained mechanical properties of the specimen surfaces, such as hardness, the
Young’s modulus, and the elastic capacity γ , are reported in Table 4.1. It is evident that
the laser treatment enhanced the surface of 17-4PH steel with improved hardness and
the Young’s modulus. In regard of the elastic capacity γ , the treatment also increased
the elastic deformation of 17-4PH steel surface; on the contrary, it reduced the plastic
deformation.
4.2.5 Cavitation-Erosion Resistance of Hardened Surface
The cavitation-erosion performance of 17-4PH steel substrate and laser-treated 17-

4PH steel was evaluated in 3.5 wt% sodium chloride (NaCl) aqueous solution using a
XOQS-2500 Cavitation Machine. This testing system consists of a booster, ultrasonic
generator, cavitation stand with piezoelectric converter, sonotrode with the testing
specimen, and cooling water bath. The cavitation-erosion test used a vibrating disk
which was the specimen of 8 mm in thickness and 16 mm in diameter, screwed into
an amplifying horn of the oscillator. In the test, the specimen was immersed into 3.5
wt% NaCl solution which was maintained at room temperature by using a cooling
water bath. The test parameters were set to ultrasonic power of 1000 W, vibrational
frequency of 20 kHz, and peak-to-peak amplitude of 50 µm. The test was stopped
at every hour, and then, the specimen was cleaned with acetone and alcohol, dried
with a drying oven, and finally weighed using an electronic weighing scale with the
accuracy of 0.01 mg. The total test time of each specimen was 40 h. The weight loss
was measured at every 10 min in the first hour and then at each hour until the test
was ended. The eroded surfaces were examined using SEM or/and EDS, and the pit
depths in the surface of the specimens were measured using a 2D scanning profiler.
The cavitation-erosion resistance of the specimens was evaluated by measuring
weight loss in the test, as depicted in Fig. 4.5. The weight losses of the 17-4PH steel
specimens due to the cavitation erosion are plotted as a function of exposure time.
Fig. 4.5 Weight loss versus

exposure time of 17-4PH
steel specimens under 3.5
wt% NaCl solution
cavitation erosion [10].
Nature
It is evident that for both specimens, the cumulative mass loss increases with time.
The laser-treated 17-4PH steel performed much better than 17-4PH steel substrate
in terms of cavitation-erosion resistance. This indicates that the surface treatments
greatly improved the erosion resistance of 17-4PH steel.
The erosion loss at 10 min interval for the first hour of the cavitation-erosion test
is further plotted with exposure time for the 17-4PH steel specimens in Fig. 4.6.
The main concern on this plot is the incubation time where erosion loss started to
occur. It characterizes the typical accumulation process of internal stresses and plastic
deformation beneath the specimen surface, which is the precursor of significant
material loss. As summarized in Table 4.2, the cavitation-erosion test results reveal
Fig. 4.6 Weight loss versus

exposure time of 17-4PH
steel specimens in the first
hour of 3.5 wt% NaCl
solution cavitation-erosion
test [10]. Reprinted from

Material Incubation Cumulative Erosion rate
cavitation-erosion test results
time (min) mass loss (mg/hr)
[10]
(mg)
17-4PH steel 10 512 12.8
substrate
Laser-treated 25 315 7.87
17-4PH steel
that between the specimens, the laser-treated specimen has much less cumulative
mass loss but longer incubation time than 17-4PH steel substrate.
Analyzing the eroded surfaces of the specimens using SEM can favor the under-
standing of the cavitation-erosion mechanism of the 17-4PH stainless steel substrate
and the laser-treated surfaces in 3.5 wt% NaCl solution. It is found that the surfaces
of the specimens tested for 1 h are smooth and no obvious deformation and pits are
observed. However, the surfaces of the specimens tested for 40 h are rugged and
show obvious deformation, also have many pits in different shapes and sizes, as seen
in Fig. 4.7. Moreover, the pits in the laser-treated specimen surface are relatively
small and shallow, compared with that in the 17-4PH substrate specimen.
To highlight the comparison of the cavitation erosion in 3.5 wt% NaCl solution
between the 17-4PH substrate and laser-treated surface, top twenty maximum pits
in each eroded surface of the specimens were selected to measure the depths. The
average depth of the pits was then calculated and obtained for each specimen. The
average depths of the pits are reported using histogram in Fig. 4.8, along with the
standard deviations representing the measuring errors attached. In consistency with
the cavitation-erosion loss results, the 17-4PH substrate specimen is worse than
the laser-treated specimen in cavitation-erosion resistance because of larger average
depths of the pits in the former. In principle, the deterioration of a surface due
to cavitation erosion starts in a sudden surge of bubbles, which finally results in
deformation and eventually damage of the protective oxide film. Surging of bubbles
would expedite corrosion, leading to pitting, and therefore, the number and depth of
pits generated in the surface can characterize the erosion performance of the surface
under cavitation.
4.2.6 Extreme Value Analysis (EVA) Model
A statistics analysis tool, known as the extreme value analysis (EVA) model, was
utilized in the study of the cavitation-erosion performance of the 17-4PH specimens
in 3.5 wt% NaCl solution. This model was derived based on the Gumbel statistics
theory [12] and can be used to predict the extreme value (maximum pit depth) of
a material due to cavitation erosion for a given service life, in terms of the pits
Fig. 4.7 Morphology of

eroded surface of a 17-4PH
substrate and b laser-treated
17-4PH after 40 h test in 3.5
wt% NaCl solution [10].
Nature
generated in the material surface [13]. The model is fitted with the measured data of
maximum pit depth in the 17-4PH specimen surface after the cavitation-erosion test.
The maximum pit depths in the specimens were measured using a 2D profiler. To
create a formula that can predict the lifetime of a material subjected to pitting failure,
the predicted maximum pit depth Dpre in the surface layer and the time parameter t
are incorporated in the following formula:

Dpre = K α + K β × [− ln(− ln P)] × t (4.1)
where P is a constant with the 0.5% risk of accepting Dpre as the maximum pene-
tration of the surface, which is equal to the ratio of the rank r of the pit depth data
Fig. 4.8 Average pit depths

of the 17-4PH steel
specimens tested for 40 h
Springer Nature
to the total number n of the pit depth data plus one, that is, P = n+1 r
. The parameter
α is the slope, and β is the x-axis intercept of the plot, − ln(− ln P) versus the pit
depth, respectively. The terms K α and K β are the slopes of the plot α and β versus t,
respectively. For a practical application, when the industry accepts a certain material
with the 0.5% risk in its total 10 years lifetime, the maximum pit depth Dpre of the
material can be predicted for a given cavitation-erosion condition using this formula.
To implement the EVA model, top twenty pits in each specimen surface were
selected to measure the depths. The data were then ranked in the order from small
to large value, as shown in Tables 4.3 and 4.4 for the test duration of 6 h and 40 h,
respectively. The cumulative extreme value distribution P was calculated from P =
r
n+1
, and the data of Tables 4.3 and 4.4 were then fitted to the model in terms of Gumbel
theory [32] by plotting − ln(− ln P) against maximum pit depth, as illustrated in
Fig. 4.9. It gives the slope α and the x-axis intercept β when − ln(− ln P) = 0.
Additionally, α and β against time t were plotted, respectively (Fig. 4.10). It shows
the time-dependence of the Gumbel distribution parameters, α line and β line, and
then, the slopes of them, K α and K β can be obtained.
To demonstrate the EVA model used for this research, it is assumed that the total
service lifetime of the specimens is 10 years, the specimen user would tolerate the
0.5% risk chance of material failure. Thus, with the K α and K β values obtained for
the specimens, as summarized in Table 4.5, the predicted maximum pit depth Dpre
was calculated for each specimen. The laser-treated specimen has smaller pit depth
for a given service life, which means that this specimen has better cavitation-erosion
resistance in 3.5 wt% NaCl solution. The results from the EVA model predictions
agree well with the weight loss data.
Table 4.3 Maximum pit

Rank r 17-4PH substrate Laser-treated 17-4PH
depths (mm) of the 17-4PH
steel specimens tested for 6 h 1 0.01809 0.00908
[10] 2 0.01901 0.00916
3 0.01924 0.00939
4 0.01938 0.00941
5 0.01966 0.00974
6 0.02188 0.00977
7 0.02247 0.00983
8 0.02263 0.00986
9 0.02278 0.00987
10 0.02325 0.00993
11 0.02337 0.00998
12 0.0236 0.01016
13 0.02374 0.01021
14 0.02375 0.01024
15 0.02484 0.01059
16 0.02603 0.01072
17 0.02812 0.01141
18 0.02869 0.01142
19 0.03523 0.01251
20 0.03844 0.01337
4.3 Surface Hardening of Cast Iron
4.3.1 Laser Surface Remelting
In hot rolling work, the rollers are exposed to elevated temperature, cyclic
stress/strain, corrosion, and wear conditions [14]. The roller life can become the
limiting factor for efficient long-run slab operation. Infinite chilling bainite spherical
graphite cast iron with medium or high NiCr is often used to combat this severe
operating environment, at the fine rolling stage or the medium thickness slab rolling
stage. However, it has been found that after a long-time service, the roller surface
was seriously damaged due to deficient hardness. To this end, laser surface remelting
treatment has been applied on infinite chilling bainite spherical graphite cast iron to
modify surface properties [15]. This material has a chemical composition (wt%) of
1.1% Cr, 1.2% Ni, 0.5% Mo, 0.8% Mn, 0.9% Si, and 3% C, Bal. Fe. The specimen
was finished by rolling before laser hardening, coated with an absorbing material.
4.3 Surface Hardening of Cast Iron 95
Table 4.4 Maximum pit

Rank r 17-4PH substrate Laser-treated 17-4PH
depths (mm) of the 17-4PH
steel specimens tested for 1 0.35368 0.22088
40 h [10] 2 0.36481 0.22291
3 0.36799 0.22609
4 0.38103 0.22905
5 0.39417 0.23129
6 0.39902 0.23181
7 0.41269 0.23258
8 0.41617 0.23343
9 0.41849 0.25081
10 0.42325 0.26486
11 0.42952 0.27277
12 0.43285 0.27415
13 0.43979 0.28018
14 0.44989 0.28169
15 0.45271 0.28462
16 0.45706 0.28631
17 0.46613 0.30539
18 0.49015 0.31182
19 0.49346 0.32089
20 0.52635 0.32274
The absorbance coefficient of the coating to laser with the wavelength of 10.6 µm
was 95%. The surface remelting was performed using a continuous wave CO2 laser
beam (7 kW power) under argon gas shielding.
4.3.2 Microstructure of Hardened Layer
The microstructure of the hardened layer from optical microscopy shows three zones:
melting zone, semi-molten zone and HAZ (Fig. 4.11). In the melting zone, both
orderly dendrite and cellular structures are observed (Fig. 4.12a). The semi-molten
zone is narrow and also considered as transition zone (Fig. 4.12b). The molten area
solidified to fine dendrite and the unmolten area was overheated to form austenite,
then transferred to needle-shape martensite and bainite, along with residual austenite.
Secondary cementite and ledeburite are also found in this area, but they have much
smaller size than the matrix. The HAZ appears having partial phase transformation
(Fig. 4.12c). The austenitizing area transferred to martensite and sorbate. The original
Fig. 4.9 Extreme value

fitting of the 17-4PH steel
specimens tested for a 6 h
and b 40 h [10]. Reprinted
Nature
cementite mostly remained, and the perlite partially transferred to martensite or

sorbate.
The thickness of the melting zone was determined by the energy input of laser,
including power density and scanning rate. The higher the energy input, the thicker the
melting zone is. During the laser hardening process, high energy heated the substrate
to liquid state rapidly, which caused perlite, ledeburite and secondary cementite
austenitizing quickly, and the remaining perlite was to dissolve into the austenite.
Simultaneously, the carbon and other alloys elements in the substrate can diffuse into
the austenite. When the laser power moved away, the melting zone quickly solidified
at the surface, forming epitaxial planar crystal. With cooling rate increasing, dendrite
crystal nucleated, forming cellular dendrite structure and growing along the direction
of the heat flow. In addition, it is noticed that the grain size in the HAZ is larger than
Fig. 4.10 Time-dependence

of the Gumbel distribution
parameters a α and b β [10].
Nature
Table 4.5 Summary of EVA

Material Kα Kβ Dpre
model results [10]
(mm/hour) (mm/hour) (mm)
17-4PH substrate 1.13E−02 1.09E−03 1497.7
Laser-treated 17-4PH 6.98E−03 9.34E−04 611.45
Fig. 4.11 Microstructure of

the laser hardened layer
under optical microscopy
with permission from 14th
Congress of International
Federation for Heat
Treatment and Surface
Engineering
that in the other two. This is because the HAZ was overheated during the laser
hardening process while it was cooled relatively slow compared to the top surface,
which allowed the grains to grow.
4.3.3 Hardness and Wear Resistance of Hardened Layer
The hardness of the hardened layer was evaluated under Vickers indentation test at
a load of 200 g. The laser hardening experiments demonstrated that the substrate
material started to melt when the laser power density reached 104 w/cm2 . Then, the
energy input of per unit area (Es) determined the temperature field of the melting pool.
Low speed of laser scanning resulted in high laser power acting on the melting pool,
leading to large HAZ. As seen in Fig. 4.13, the surface hardness of the hardened layer
prepared with lower Es is higher than that prepared with higher Es. Due to limited
energy input, only a thin layer can be molten rapidly and then was cooled quickly.
In this case, there was no sufficient time for the alloying elements to diffuse, thus
forming an amorphous thin layer with higher hardness at the substrate surface. The
hardness decreases gradually from the surface to the substrate. The hardened layer
is ~ 0.3 mm for both low and high energy input Es. In general, higher Es can result
in higher hardness of the hardened layer except at the surface layer. Higher Es can
melt thicker layer but with lower cooling rate, thus allowing more dendrite formation
and phase transformation as well as diffusion of elements, which can strengthen the
layer.
To simulate the real application condition of the infinite chilling medium NiCr
cast iron roller, the laser hardened layer on the roller was tested for wear resistance
in the industry workshop. The wear resistance of the hardened layer was evaluated
by determining the reduction fraction in diameter of the roller for rolling per ton of
steel. It was reported that the amount of steel that could be rolled within the roller life
was increased greatly (about 50%) by the laser hardening treatment. Furthermore,

a melting zone, b
semi-molten zone and c heat
affected zone under optical
microscopy [15]. Reprinted
from Yao et al. [15],
permission from 14th
Federation for Heat
Engineering

profiles of the laser hardened
layers [15]. Reprinted from
Yao et al. [15], Copyright
from 14th Congress of
International Federation for
Heat Treatment and Surface
Engineering
Fig. 4.14 Comparison in

wear resistance between the
rollers with and without laser
hardening treatment [15].
permission from 14th
Federation for Heat
Engineering
as illustrated in Fig. 4.14, with the same wear loss (reduction fraction of the roller
diameter), the roller with the laser hardened layer has a much higher rolling capacity
(amount of steel rolled).
4.4 Summary of Laser Surface Hardening
The mechanical performance and cavitation-erosion behavior in 3.5 wt% NaCl solu-
tion of 17-4PH stainless steel surface treated via laser process were investigated,
compared with that of untreated 17-4PH stainless steel. It was found that the heat
treatment improved the hardness, the Young’s modulus, the resistance to plastic
deformation, as well as the cavitation-erosion resistance of the steel surface. The
erosion loss, eroded surface observation, the EVA model, and nanoindentation test
all agreed well toward consistent conclusions.
4.4 Summary of Laser Surface Hardening 101
The failure mechanisms of cavitation-erosion are very complex. This type of

failure mode differs from single wear and corrosion, instead it is the synergetic
effect of these two at least [16]. Due to the generation of gas pockets or vapor
inside the flow of liquid, the cavitation-erosion behavior is considered the process of
deterioration and material loss of specimen surface [17]. These pockets are formed
because of low pressure well below the saturation vapor pressure of the liquid and
erosion caused by the bombardment of vapor bubbles on the specimen surface [18].
Therefore, two factors can be deemed to influence the cavitation-erosion resistance
of a material predominantly. One is the ability of forming and retaining a dense oxide
film on its surface, which can protect the corrosion of the substrate material [19]. The
other is the hardness and resistance to plastic deformation of the surface, because
these properties directly relate to the material removal from the surface subject to
bombardment of vapor bubbles [20].
During the cavitation process, the surface deformation and the break of the protec-
tive oxide film on the surface due to the cyclic intense shock wave from imploding
of voids in the liquid can increase the electrochemical potential of the material in the
medium, thus expediting corrosion. The erosion loss values, eroded surfaces, and
EVA model predictions all demonstrate better cavitation-erosion resistance of the
laser-treated specimen. From the viewpoint of oxide film, 17-4PH stainless steel is
able to form an oxide film on its surfaces owing to the high Cr content so that the
specimens can have a protective film during cavitation. However, with the cavitation
proceeding, the intense shock wave impacted repeatedly on the specimen surface,
broke the oxide film thus resulting in pits, as observed in the eroded surfaces. There-
fore, the behavior of the oxide film on the specimen surface plays an important role
in the cavitation-erosion resistance of the specimen. If the film can be retained better
on the specimen surface, the substrate material could be less corroded by 3.5 wt%
NaCl solution during the cavitation process.
In concern of the surface treatment effect on 17-4PH stainless steel, it is evident
that the cavitation-erosion resistance has been significantly improved by the heat
treatment because the specimen has less erosion loss, less and shallow pits, and
smaller value of predicted maximum pit depth Dpre from the EVA model than the as-
received specimen. The nanoindentation test results show higher value of the Young’s
and the elastic capacity γ of the heat-treated specimen than the as-received specimen,
which can explain the observations in the cavitation-erosion test. In addition, the
surface treatments apparently improved the hardness of 17-4PH stainless steel, from
both microhardness and nanoindentation tests.
The grain size of infinite chilling medium NiCr cast iron can be refined by laser
treatment. Due to formation of fine dendrites and phase transformation, the surface
of infinite chilling medium NiCr cast iron can be hardened by laser heat treatment,
which improves the wear resistance of the infinite chilling medium NiCr cast iron
roller significantly. The industry test demonstrated that the rolling capacity of the
roller with the laser hardened layer increased greatly compared to that of the roller
without laser heat treatment. Pairs of infinite chilling medium NiCr cast iron roller
with laser surface remelting treatment were field-tested. The amount of steel that
could be rolled within the roller life increased for the roller with surface laser-treated,
doubled compared with the roller without surface treatment.
References
1. Lee MK, Kim GH, Kim KH, Kim WW (2004) Control of surface hardness, hardening depths,
and residual stresses of low carbon 12Cr steel by flame hardening. Surf Coat Technol 184(2–
3):239–246
2. Cho KT, Song K, Oh SH, Lee YK, Lee WB (2013) Surface hardening of shot peened H13 steel
by enhanced nitrogen diffusion. Surf Coat Technol 232:912–919
3. Kimura T, Miyazaki T (1989) Surface hardening of carbon steel produced by small diameter
nozzle plasma arc. J Japan Soc Preci Eng 55:1450–1455
4. La Rocca AV, Ramous E, Cantello M (1987) Laser surface hardening of thin steel slabs. J Mater
Sci 22(5):1737–1742
5. Li RF, Jin YJ, Li ZG, Qi K (2014) A comparative study of high-power diode laser and CO2
laser surface hardening of AISI 1045 steel. J Mater Eng Perform 23(9):3085–3091
6. Sarkar S, Gopinath M, Chakraborty SS, Syed B, Nath AK (2016) Analysis of temperature
and surface hardening of low carbon thin steel sheets using Yb-fiber laser. Surf Coat Technol
302:344–358
7. Martinez S, Lamikiz A, Ukar E, Calleja A, Arrizubieta JA, Lopez de lacalle LN (2017) Analysis
of the regimes in the scanner-based laser hardening process. Opt Laser Eng 90:72–80
8. Nemecek S (2013) Surface of cast iron after laser hardening. Adv Mater Res 685:92–96
9. Yao JH, Zhang QL, Kong FZ, Ding QM (2010) Laser hardening techniques on steam turbine
blade and application. Phys Procedia 5:399–406
10. Yao JH, Ding YP, Liu R, Wang L, Zhang QL, Sheng JJ, Xue CG (2020) Mechanical and
cavitation-erosion performance of 17–4PH stainless steel surface treated with laser-based
process. J Mater Eng Perform 29(4):2687–2696
11. Oliver WC, Pharr GM (1992) An improved technique for determining hardness and elastic
modulus using load and displacement sensing indentation experiments. J Mater Res 7:1564–
1583
12. Gumbel EJ (1954) Statistical theory of extreme values and some practical applications. NBS
Appl Math Ser 33:1–51
13. Aziz PM (1956) Application of the statistical theory of extreme values to the analysis of
maximum pit depth data for aluminum. Corrosion 12:35–46
14. Wen ED, Song RB, Xiong WM, Zhang X, Wang ZH, Guo K, Hu JF (2015) Hot deformation
behavior of NM550 wear-resistant steel. In: Proceedings of the 7th international conference
on high strength low alloy steels, HSLA steels, Hangzhou, China, pp 873–879
15. Yao JH, Zhang QL, Xie SJ (2004) Laser surface remelting of medium Ni-Cr infinite chilling
cast iron roll. Trans Mater Heat Treat 25(5):1009–1012
16. Abouel-Kasem A, Ahmed SM (2008) Cavitation erosion mechanism based on analysis of
erosion particles. J Tribo 130(3):1–6
17. Zhang XB, Chang X, Wei T, Liu CS (2011) Microstructure and cavitation-erosion mechanism of
laser cladding NiCrSiB coating on CrNiMo stainless steel. Adv Mater Res 154–155:1788–1791
18. Hattori S, Mikami N (2009) Cavitation erosion resistance of stellite alloy weld overlays. Wear
267(11):1954–1960
19. Liu FB, Zeng QY, Jiang H, Cui Y, Cao LG, Yang Y (2016) Generation mechanism of Fe-base
nanostructures induced by cavitation erosion. Mocaxue Xuebao Tribology 36(6):749–754
20. Lo KH, Cheng FT, Man HC (2003) Cavitation erosion mechanism of S31600 stainless steel
laser surface-modified with unclad WC. Mater Sci Eng A 357(1–2):168–180
Chapter 5
Laser-Processed Coatings Involving
Nanoparticles
Abstract Metal matrix composites reinforced by nanoparticles are very promising

materials, suitable for a large number of applications. The nanoparticles can improve
the base material in terms of wear resistance, damping properties, and mechanical
strength. Formation of brittle Laves phase is always a problem in laser cladding of
nickel-based Inconel 718 alloy. To solve the Laves phase problem, carbon nanotubes
(CNTs) are incorporated into the laser cladding of Inconel 718 alloy, while they also
provide additional strength to the cladded alloy. Owing to many superior features of
ceramic materials such as high temperature and chemical stability, excellent corro-
sion, oxidation, and wear resistance, ceramic nanoparticles have been deposited by
laser to create coatings for many applications. Nanostructural Al2 O3 is used for
preparing wear- and oxidation-resistant coatings with fine grains by co-depositing
Al2 O3 with Ni–P together via electroless composite plating and then applying laser
treatment on the Ni–P–Al2 O3 plating. Due to the brittleness of Al2 O3 , the laser
process of nano-Al2 O3 coating inevitably causes cracks in the cladding layer. To
minimize the cracking, the influence of laser process paraments and coating overlap
on the cracking behavior of the cladding layer using Ni-coated nano-Al2 O3 particles
with the mass percentages of Al2 O3 in the Ni-coated nano-Al2 O3 powder being 20%,
50%, and 85%, respectively, is studied.
5.1 Laser Process of Nanomaterials
5.1.1 Application of Nanoparticles in Material Development
The properties of nanoparticles often differ markedly from those of larger particles of
the same substance. Since the typical diameter of an atom is between 0.15 and 0.6 nm,
a large fraction of the nanoparticles material lies within a few atomic diameters from
its surface. Therefore, the properties of that surface layer may dominate over those
of the bulk material. This effect is particularly strong for nanoparticles dispersed in
a medium of different composition since the interactions between the two materials
at their interface also becomes significant [1].

104 5 Laser-Processed Coatings Involving Nanoparticles
Nanotechnology offers potential opportunities to create better materials with

enhanced properties for use in various application areas. The atoms within nanopar-
ticles are impeccably ordered; therefore, when the dimensions of a material are
condensed from macrosize to microsize (nanosize), substantial changes occur in
the properties of the material [2]. The microdimensions of nanoparticles have led
to a revolution of nanotechnology that has had a radical impact on the cosmetics,
construction, electronics, manufacturing, and medical industries [3]. The distinctive
physical and chemical properties of nanoparticles allow the design of systems with
high sensitivity, large surface areas, special surface effects, high functional density,
and high strain resistance [4].
Metal matrix composites (MMCs) reinforced with nanoparticles, also called metal
matrix nanocomposites (MMNCs), are being investigated worldwide in recent years,
owing to their promising properties suitable for a large number of functional and
structural applications. The reduced size of the reinforcement phase down to the
nanoscale is such that interaction of particles with dislocations becomes of signifi-
cant importance and, when added to other strengthening effects typically found in
conventional MMCs, results in a remarkable improvement of mechanical properties
[5].
There are various methods developed to produce MMNCs, but the main issue to be
faced in the production of MMNCs is the low wettability of ceramic nanoparticles
with the molten metal matrix, which do not allow the production of MMNCs by
conventional casting processes. Small powder aggregates are in fact prone to form
clusters, losing their capability to be homogeneously dispersed throughout the matrix
for an optimal exploitation of the strengthening potential [6]. For this reason, several
alternative methods have been proposed to overcome this problem. The production
methods can be categorized into two major groups: ex situ and in situ. The first
synthesis route consists of adding nanoreinforcements to the liquid or powdered
metal, while in situ processes refer to those methods leading to the generation of
ceramic nanocompounds by reaction during processing [7]. Several methods have
been developed for ex situ synthesis of MMNCs. In particular, different powder
metallurgy techniques were successfully employed. Moreover, ultrasound-assisted
casting plays a particularly promising role for its high potential productivity. Laser
cladding is also one of the most popular methods for synthesis of MMNCs [8].
5.1.2 Laser Process of Nanoparticle-Containing Materials
Laser cladding technology has been applied in preparing metal matrix nanocomposite
coatings with excellent properties to make up the poor metallic substrate with no
limit of matrix metal material [9]. The combination of laser cladding and nanometer
technology certainly will obtain surface coatings with outstanding performance to
prolong the life of components and advance the production quality because of a series
of excellent characteristics, such as a finer microstructure, a thicker coating with low
dilution, and a higher bonding strength interface [10].
5.1 Laser Process of Nanomaterials 105
It was reported that nano-TiCN particles were generally used as a strengthening

phase in the fabrication of wear-resistant coatings via laser cladding. Titanium-
based ceramic coatings on Ti6Al4V alloy substrates were prepared via laser cladding
process using a TiCN plus SiO2 mixed powder as the pre-placed starting materials
with 3 wt% CeO2 nanoparticles additive [11]. The influence of the CeO2 nanoparticle
additive on the microstructure and wear performance of the laser cladding coatings
were investigated. The experimental observations showed that the main composi-
tions of the cladding coating were TiCN and TiN phases. Compared to the coatings
without CeO2 , the coatings modified with CeO2 nanoparticles led to more excellent
mechanical properties. The average microhardness of the coatings modified with
CeO2 nanoparticles was approximately 1230 HV0.2, and the wear volume loss of
the coatings modified with CeO2 nanoparticles was approximately 14% less than
that of the coatings without CeO2 under a simulated body fluid lubrication environ-
ment. Laser cladding was also applied to deposit nanoparticle TiC on Ti6Al4V alloy
substrate to create coating [12]. The effects of the laser process parameters such
as laser power, scanning speed, pre-placed powder thickness, laser spot diameter,
and multi-track overlapping ratio on the quality characteristics of the coating were
studied. The experimental and analytical results showed that the powder thickness
and spot diameter were important process parameters for each characteristic.
Nano-TiCp -reinforced Inconel 625 composite coating was fabricated
by laser cladding of an Inconel 625 plus 5 wt% TiC powder mixture, particle size of
the raw powders both in micrometer range [13]. By controlling the specific energy
input, the micro-TiCp partially dissolved into nanometer scale. The influence of
specific energy input on particle size, morphology and the microstructure, phase
constitution, and mechanical properties of the composite coating was investi-
gated by scanning electron microscopy (SEM), X-ray diffraction, transmission
electron microscopy (TEM), and nano-indentation test. This composite coating
has potential in applications such as for turbine blades and engine components
with improved performance. Laser cladding was applied on the surface of Cr12
mold steel with Ni-coated nano-Al2 O3 particles powder as coating material [14].
Compact cladding layer without crack, gas hole, and other defects was obtained,
consisting of three phases: Fe–Ni solid solution, Fe–Cr solid solution, and nano-
Al2 O3 particle. The presence of nano-Al2 O3 particles enhanced the inhomogeneous
nucleation of Fe-based alloy, refined the crystal grains, and strengthened the
mechanical properties of cladding layer. The composite coating consisting of
NiFeBSi alloy and 10 wt% nano-SiC particle was prepared by laser cladding on
carbon steel [15]. It was found that the microstructure of the coating has FeNi3 +
a-Fe eutectoid structure, and four kinds of carbides were also formed between γ
(Fe, Ni) dendrites due to decomposition of SiC particles. The hardness and wear
resistance of NiFeBSi alloy were obviously improved due to the enhancement of
multi-carbide and refinement of FeNi3 + α-Fe eutectoid structure.
5.2 Carbon Nanotubes Containing Superalloy Coating
5.2.1 Strengthening of Inconel 718 Alloy
Nickel-based Inconel 718 superalloy is widely used for the components operating at
the high temperature up to 650–700 °C, in particular, in the modern aero-engines,
due to outstanding mechanical strength in the high temperature, excellent forma-
bility, and relatively low cost [16]. Laser cladding is highly desirable in the repair
of the high-valued Inconel 718 alloy components such as turbine blades, vanes,
blisks. However, during the rapid solidification of laser cladding, the reaction time
is too short to precipitate the γ or γ ’ phases; instead, large amounts of Laves phase
are formed by the Laves/γ eutectic reaction owing to high degree of interdendritic
element segregation in the last stage of solidification [17]. The Laves phase is a brittle
intermetallic compound, which is normally expressed by the formula of (Ni, Cr, Fe)2
(Nb, Mo, Ti) [18]. The formation of Laves phase not only depletes the valuable
alloying elements like Nb and Mo, but also promotes the initiation and propagation
of liquation cracking in the cladded layer [19].
To solve the Laves phase problem, it was proposed to incorporate carbon
nanotubes (CNTs) into the laser cladding of Inconel 718 alloy, while they also provide
additional strength of the cladded alloy [20]. CNTs are widely accepted as one of
the promising quasi-one-dimensional nanoreinforcements due to their low density,
large aspect ratio, and extremely high mechanical strength [21]. However, thermal
destruction is always a key issue of CNTs in laser cladding due to high-power heat
[22]. Therefore, a pre-treatment is usually applied on CNTs to coat them with a
protective layer. As reported, CNTs were embedded in Al powders via ball milling
or spray drying the surface treatment [23]. As a result, an Al coating was formed on
the surfaces of the CNTs, which can act as a thermal shield protecting the CNTs from
the thermal destruction during the plasma spraying. Also, to incorporate CNTs into
the laser cladding of Inconel 718, NiP protective coating was made on the surfaces
of the CNTs [20]. The results showed that with the addition of NiP-coated CNTs,
the liquation cracking resistance and the tensile strength of the cladded Inconel 718
alloy were all improved. Further investigation of the effect of CNTs additive in the
laser cladding of Inconel 718 was made using Ni-coated CNTs [24]. The coating
was deposited on the CNTs with an electroless plating method.
5.2.2 Preparation of Coated Carbon Nanotubes (CNTs)
The reinforcement material used in the laser cladding of Inconel 718 was commer-
cial multi-walled carbon nanotubes (MWCNTs) having the diameter in a range of
30–50 nm and length between 10 and 20 μm. To apply a protective coating on the
MWCNTs, the raw MWCNTs were treated by the electroless plating. As shown
in Fig. 5.1, the as-received MWCNTs were firstly immersed into the concentrated
5.2 Carbon Nanotubes Containing Superalloy Coating 107
Fig. 5.1 Electroless plating flowchart of Ni-coated CNTs [24]. Reprinted from Chen et al. [24],
Copyright (2019), with permission from Elsevier
nitric acid and hydrofluoric acid in turn for 48 h and 24 h, respectively. After filtered
and washed with the de-ionized water, the purified MWCNTs were sensitized in
an aqueous solution of 0.1 M SnCl2 /0.1 M HCl at the room temperature for 24 h.
After washed again, the MWCNTs were activated in an aqueous solution containing
0.0014 M PdCl2 /0.25 M HCl. The MWCNTs were immersed into the plating solu-
tion for the electroless plating of Ni after washed again. The chemical composition
and bath conditions used for this electroless plating were detailed in Table 5.1. At
the beginning of the plating process, the plating solution was in dark blue color. With
the reaction of the plating, lots of bubbles were generated and the blue color of the
plating solution was faded gradually. When the plating solution was changed to the
transparent feature with no more bubbles generated, it was identified as the termina-
tion of the plating. To achieve a thicker coating, the plating solution was replaced by
a new fresh plating solution. The plating reaction was then restarted. This process
was repeated for three and six times, respectively, which corresponded to 0.5 wt%
Table 5.1 Chemical

Chemical Concentration
compositions and bath
conditions used for NiCl2 ·6H2 O 30 (g/L)
electroless plating of Na3 C6 H5 O7 ·2H2 O 40 (g/L)
Ni-coated CNTs [24]
NaOH 10 (g/L)
N2 H4 ·H2 O (80 vol. %) 45–50 (mL/L)
PH 12
Bath temperature 60 °C
Reprinted from Chen et al. [24], Copyright (2019), with permission
from Elsevier
and 1 wt% of MWCNTs in the Ni-coated MWCNTs powder, with the cladding spec-
imen named Ni0.5CNTs/Inconel 718 and Ni1CNTs/Inconel 718 accordingly. After
the electroless plating treatment, the NiCNTs powders were dried in an air-blast
drying closet at 80 °C for 6 h and a vacuum drying oven at 120 °C for 3 h. In order
to achieve good flowability, the Ni-coated CNTs powder was ground into a particle
size about 100 mesh.
5.2.3 Laser Cladding Experiment
The depositing powder used was gas-atomized spherical Inconel 718 superalloy
powder with a particle size of 100–150 μm. The Ni-coated CNTs powder was added
to the Inconel 718 superalloy powder in 10 wt%. The substrate material was solution-
treated Inconel 718 with a dimension of 120 × 10 × 6 mm.
The laser cladding experiment was performed using a laser system consisting
of a coaxial powder-feeding nozzle and a 2 kW high-power diode laser unit (Lase-
line LDF400-2000). The diameter of the focused laser beam was about 4 mm. The
powder-feeding system was equipped with double powder-feeding cylinders. The
powders could be mixed inside the feeding tubes simultaneously during the powder
delivery process. The feeding rate of the powders in each of the cylinders could
be adjusted individually so that the content of each powder in the cladding spec-
imen could be controlled. For comparison and better investigation of the effects of
MWCNTs addition on the microstructure evolution, element segregation, and Laves
phase formation in the cladded Inconel 718 alloy, various single-track cladding spec-
imens were prepared such as pure Inconel 718 alloy, Inconel 718 alloy with 10 wt%
Ni additive, Inconel 718 alloy with addition of Ni1CNTs and Ni0.5CNTs, respec-
tively. The main laser process parameters used were as follows: laser power of 600 W,
laser scanning speed of 2 mm/s, and powder-feeding rate of 6 g/min.
5.2.4 Morphology of Ni-Coated MWCNTs Powder
The morphology of Ni-coated NiCNTs powder was examined with scanning electron
microscopy (SEM), and the images are shown in Fig. 5.2. The powder appears porous,
which should be attributed to the Ni coating, as seen in Fig. 5.2a. After mechanically
ground, the powder particles have a size of around 20–100 μm (Fig. 5.2b). In the
image of high magnification (Fig. 5.2c), tubular-like morphology of the MWCNTs
can still be observed, although they had been coated with Ni. The diameter of
the MWCNTs was increased from original 30–50 nm to about 300 nm when they
were electrolessly plated with Ni for three repeated times. However, the tubular-like
morphology disappeared when the MWCNTs were electrolessly plated with Ni for
six repeated times, due to the thicker Ni layer formed, as shown in Fig. 5.2d.
Fig. 5.2 SEM morphology of electrolessly plated NiCNTs powder: a before grinding, b after
grinding, c Ni1CNTs powder at high magnification, and d Ni0.5CNTs powder at high magnification
[24]. Reprinted from Chen et al. [24], Copyright (2019), with permission from Elsevier
The Ni-coated MWCNTs powder was also studied using energy-dispersive X-ray
spectroscopy (EDS). Figure 5.3 presents the EDS analysis results, which show high
Ni content in the coating layer. Since the MWCNTs have been coated with Ni, carbon
is hardly detected on the surface of the MWCNTs, which also indicates a good Ni
coating formed on the MWCNTs from the electrolessly plating. A small O peak is
also detected, which should be attributed to the oxidation groups such as −OH, −
CO, −COOH generated in the concentrated nitric acid and hydrofluoric acid during
the purification process.
Fig. 5.3 EDS analysis results of Ni1CNTs powder: a SEM morphology and b EDS spectrum [24].
Reprinted from Chen et al. [24], Copyright (2019), with permission from Elsevier
Fig. 5.4 XRD patterns of

MWCNTs powder and
Ni-coated MWCNTs powder
[24]. Reprinted from Chen
Elsevier
Bare MWCNTs powder and Ni-coated MWCNTs powder were further analyzed
with X-ray diffractomery (XRD); the XRD patterns are presented in Fig. 5.4. It is
evident that for bare MWCNTs, the diffraction peak of crystal plane (002), which
represents the tubular carbon, is very strong. This indicates high purification of the
MWCNTs. After electroless plating, the typical C peaks disappeared, because of the
presence of the Ni coating. Accordingly, pure Ni phase shows strong peaks. This
also means that the MWCNTs were well coated with Ni.
5.2.5 Microstructure of Cladded Specimens
The cladding specimens were transversely sectioned from the center of the spec-
imens. The cut samples were then mounted, polished, and chemically etched in a
solution of 100 ml C2 H5 OH + 100 ml HCl + 5 g CuCl2 . The preparation of the trans-
mission electron microscopy (TEM) samples involved pre-thinning of the sampes
down to 50–60 μm and then electropolishing with a twin-jet system in a 10 vol%
perchloric acid alcohol at a voltage of 30 V and temperature −20 °C. The microstruc-
tures of the cladding specimens were studied using SEM, EDS, XRD with a Cu Kα
radiation at a scanning speed of 5°/min and TEM operating at an accelerating voltage
of 200 kV.
Figure 5.5 shows the microstructure of the cladded Ni1CNTs/Inconel 718 spec-
imen, which has a dendritic structure (Fig. 5.5a). Similar to the microstructure of pure
Inconel 718 alloy, a large amount of Laves phase is found in the interdendritic regions
of the cladded specimen. However, the Laves phase particles formed in the cladded
Ni1CNTs/Inconel 718 specimen are more discrete, finer, and less, compared with
the Laves phase in the cladded pure Inconel 718 specimen. This may be attributed
to the Ni dilution in Inconel 718 alloy due to high Ni concentration in Ni1CNTs,
Fig. 5.5 SEM

microstructure of cladded
Ni1CNTs/Inconel 718
specimen: a at low
magnification [24].
Reprinted from Chen et al.
which resulted in the relative reduction of the Laves phase formation elements such
as Nb, Mo, Ti. Moreover, as shown in Fig. 5.5b, addition of Ni1CNTs induced the
transformation of a large amount of black film-like phase in the interdendritic region
of the cladded Ni1CNTs/Inconel 718 specimen. In the previous study, this phase was
typically named as carbon nanoribbons (CNRs). They were transformed through
the microstructural evolution of MWCNTs [20]. On the other hand, the formation
of Laves phase was greatly suppressed by the transformed CNRs during the rapid
solidification of laser cladding.
To confirm the phase identifications, EDS analysis was conducted on the cladded
Ni1CNTs/Inconel 718 specimen, and the results are presented in Fig. 5.6. High C
concentration appears in the region of CNRs (indicated by black arrows in Fig. 5.6a).
This is also demonstrated by the elemental mapping shown in Fig. 5.6b. Within the
selected area marked in Fig. 5.6a, the light region has no Ni but very high Nb and
Mo concentrations, as seen in the mapping images in Fig. 5.6c–e. This confirms
the Laves phase of the light particles. The other regions are rich in Ni, as shown in
Fig. 5.6c.
(a)
Fig. 5.6 EDS analyses of cladded Ni1CNTs/Inconel 718 specimen: a SEM microstructure, b
mapping of C element, c mapping of Ni element, d mapping of Nb element, and e mapping of
Mo element [24]. Reprinted from Chen et al. [24], Copyright (2019), with permission from Elsevier
Figure 5.7 shows the microstructure of the Ni0.5CNTs/Inconel 718 specimen.

Different from the microstructure of Ni1CNTs/Inconel 718 specimen, the Laves
phase particles in the Ni0.5CNTs/Inconel 718 specimen are hardly observed, but
lots of pores in the size of several microns approximately in a rhombic shape are
present in the interdendritic regions, as seen in Fig. 5.7a. Also, the transformed
film-like graphene nanosheet (GNS) is found in this specimen, along with CNRs

Ni0.5CNTs/Inconel 718
specimen: a at low
magnification, b GNS and
CNR, c dendrite growth, and
d collapsed MWCNTs [24].
Reprinted from Chen et al.
(Fig. 5.7b). Furthermore, inside some of the pores, there are the film-like GNS, which
are detached from the metal matrix, as shown in Fig. 5.7b. During the melting process
of the laser cladding, GNSs and CNRs were formed in the molten pool, around which
partial liquid is trapped, forming liquid droplets. Because of poor wetting property
between the GNSs/CNRs and metal liquid, the liquid droplets can easily be pushed
to the remaining liquid in the interdendritic regions during the dendritic growth in the
solidification process. Once the droplets were trapped by the solid, the liquid cannot
get into the droplets owing to the surrounding of the GNSs/CNRs. With the decrease
of temperature, the droplets shrunk in the solidified coating. As the volume reduction
of the droplets exceeded a critical size, the droplets were detached from the metal
matrix, leading to the formation of interdendritic pores and small particles inside
them. The rhombic shape of the pores may be attributed to the typical feature of the
dendrite growth. The dendrites grew in rhombic columns on microscopic scale, as
demonstrated in Fig. 5.7c. The detailed microstructure of the collapsed MWCNTs
is shown in Fig. 5.7d, along with the transformed CNRs in the growth tips of the
dendrites. With the addition of MWCNTs, the diffusion path of the elements in the
Inconel 718 could be somewhat blocked; thus, the element segregation and Laves
phase formation were depressed.
The initial Ni-coated MWCNTs content in the Ni1CNTs/Inconel 718 mixed
powder was double of that in the Ni0.5CNTs/Inconel 718 mixed powder. However, it
is evident that the carbon nanoproducts, that is, collapsed Ni-coated MWCNTs, trans-
formed GNSs and CNRs in the metal matrix, were more in the Ni0.5CNTs/Inconel
718 laser cladded specimen. This was due to low MWCNTs retention in the
Ni1CNTs/Inconel 718 specimen during the laser cladding process, since MWCNTs
were easier burn out by the high energy of the laser beam and high-temperature
heat of the molten pool. As indicated previously, the Ni coating on Ni0.5CNTs was
thicker than that on Ni1CNTs (Fig. 5.2c and Future Fig. 5.2d); thus, the MWCNTs
in Ni0.5CNTs/Inconel 718 powder can be better protected because of more effective
shield to reduce the direct irradiation of the laser beam and thermal destruction of
the molten pool, which led to more carbon nanoproducts in the Ni0.5CNTs/Inconel
718 laser cladded specimen.
Figure 5.8 shows the dendritic microstructure of the Ni0.5CNTs/Inconel 718
specimen and associated EDS elemental mapping. It is shown that the Laves phase
size in this specimen was reduced to about 100 nm, which confirmed the fact that
owing to better retention of MWCNTs thus more carbon nanoproducts formed, more
effective depression effect was made on the element segregation and Laves phase
formation. In the EDS analyses presented in Fig. 5.8, the Laves phase shows high
Nb and Mo contents (Fig. 5.8d and e).
5.2.6 Laves Phase Formation
Further studies on the carbon nanoproducts in the cladded Ni0.5CNTs/Inconel 718

specimen were made with TEM. Figure 5.9a shows the typical microstructure of
Fig. 5.8 EDS analyses of cladded Ni0.5CNTs/Inconel 718 specimen: a SEM microstructure, b
mapping of C element, c mapping of Ni element, d mapping of Nb element, and e mapping of Mo
element [24]. Reprinted from Chen et al. [24], Copyright (2019), with permission from Elsevier
the CNRs transformed in the Ni1CNTs/Inconel 718 specimen, revealing that the
porous CNRs consist of interbonded graphene fragments. As reported by Bang et al.
[25], under the laser beam irradiation, the tubular walls of the MWCNTs in the
ethanol can be unzipped due to great stresses induced in the walls of the MWCNTs,
resulting in the formation of GNSs. This typical transformation behavior from the
MWCNTs to GNSs was also observed in the research of Chen et al. [20]. However,
Fig. 5.9 TEM analyses of carbon nanoproducts in cladded Ni0.5CNTs/Inconel 718 specimen: a
porous CNR, b tubular-like structure of MWCNTs in CNR, c large area with GNSs, and d very
thin GNSs [24]. Reprinted from Chen et al. [24], Copyright (2019), with permission from Elsevier
differently, during the laser cladding process of Ni0.5CNTs/Inconel 718 powder on

solution-treated Inconel 718 substrate, the Ni-coated MWCNTs were dispersed in
the high-temperature molten pool but not in ethanol; thus, the transformed GNSs can
further be destructed into graphene fragments. During the rapid cooling process of the
laser cladding, these graphene fragments could be interbonded with the neighboring
ones, resulting in porous CNRs formation eventually. In Fig. 5.9b, some of tubular-
like structures of MWCNTs can still be observed in the transformed CNRs. This
was due to the fact that the thicker Ni coating on the MWCNTs reduced the CNR
transformation. In addition to CNRs, large amounts of GNSs were also identified
in the cladded Ni0.5CNTs/Inconel 718 specimen, as shown in Fig. 5.9c. This was
also considered to be attributed to the protective effect of the thicker Ni coating
on the MWCNTs during the laser cladding process, which gave the condition to
form graphene fragments. Nevertheless, some of the GNSs were very thin, as shown
in Fig. 5.9d. The presence of CNRs and GNSs provided large surface areas inside
the laser deposited layer, which inhibited the atom movement in the solidification.
Consequently, the element segregation and Laves phase formation in the cladded
Ni0.5CNTs/Inconel 718 layer were suppressed.
In order to better understand the effect of MWCNTs addition on the element
segregation and Laves phase formation in Inconel 718 superalloy during the rapid
solidification of laser cladding, the microstructures of laser cladded pure Inconel 718,
Inconel 718 with 10 wt% Ni additive, Ni0.5CNTs/Inconel 718, and Ni1CNTs/Inconel
718 were compared. The amount and distribution of Laves phase in the pure Inconel
718 and Inconel 718 with 10 wt% Ni specimens were similar, as shown in Fig. 5.10a,
b. However, with addition of 10 wt% Ni1CNTs, the amount of Laves phase formed in
the Inconel 718 cladding was greatly reduced, as seen in Fig. 5.10c. Moreover, addi-
tion of 10 wt% Ni0.5CNTs further reduced the Laves phase amount in the Inconel
718 cladding, as shown in Fig. 5.10d. For more details, the volume fractions of Laves
phase in these four cladded layers were estimated via the binarized quantitative metal-
lography image process; the results were reported to be 13.3%, 12.6%, 8.8%, and
7.4% for pure Inconel 718, Inconel 718 with 10 wt% Ni additive, Ni0.5CNTs/Inconel
718, and Ni1CNTs/Inconel 718, respectively. This further proved the depression
effect of the addition of MWCNTs on the Laves phase formation and thicker Ni
coating on the MWCNTs can better retain the carbon nanoproducts transformed from
the MWCNTs, thus provided more profound depression effect on the Laves phase
formation, because of larger surface area of the net-like or film-like morphology of
the GNSs, CNRs, and collapsed MWCNTs.
5.3 Coating Prepared Using Nano-Al2 O3
5.3.1 Preparation of Coating with Fine Grains
Owing to high strength, excellent wear and abrasion resistance, good thermal fatigue
and high-temperature oxidation performance, as well as low cost, nano-Al2 O3
powder has been popularly used for preparing wear- and oxidation-resistant coat-
ings with fine grains. There are various methods developed to prepare such coatings
using nano-Al2 O3 powder. One of them is to co-deposit Al2 O3 with Ni–P together
via electroless composite plating and then apply laser treatment on the Ni–P-Al2 O3
plating [25]. This approach enables applying a Ni coating on nano-Al2 O3 particles,
which can reduce burning of the nanoparticles during laser treatment.
An attempt was made to create fine-grain coating on 45 steel (Table 5.2) using
nano-Al2 O3 powder. The 45 steel substrate had experienced a heat treatment to
achieve the hardness of HV0.2 180. The main coating material, Al2 O3 powder, had
an average grain size of 20 nm, used as the insoluble component in the composite
electroless suspension, which was chemically pre-treated for de-oiling with lye and
cleaning with cold water. The pre-treated nano-Al2 O3 powder was then added into the
Ni–P electroless bath and stirred by ultrasonic treatment for above an hour to achieve

laves phase in laser cladded
specimens: a Inconel 718, b
Ni/Inconel 718, c
Ni0.5CNTs/Inconel 718, and
d Ni1CNTs/Inconel 718
[24]. Reprinted from Chen
Elsevier
5.3 Coating Prepared Using Nano-Al2 O3 119
Table 5.2 Chemical composition of 45 steel (wt%)

C Si Mn P S Fe
0.43 0.23 0.66 0.002 0.014 Bal
homogeneous suspension. Form this process, the compound electroless plating with
a depth of 0.02 mm can be achieved on the nano-Al2 O3 particles.
The deposition of nano-Al2 O3 powder plated with Ni–P on 45 steel substrate
was completed utilizing a pulse wave Nd:YAG laser system with a rated power of
300 W in a low-order mode. The laser beam had a diameter of 3 mm, and the lens
had a focal length of 75 mm. Argon was used as shielding gas to protect the nano-
particles from burning lost. The laser beam power and scanning speed were adjusted
during the experiment to achieve the cladding layer under different process parameter
conditions. The optimal process parameters obtained for preparing the coating by
laser heating the nano-Ni–P–Al2 O3 plating were the current of 250 A, the pulse width
of 2.5 ms, the pulse frequency of 20 Hz, and the overlapping ratio between adjacent
tracks of 66%.
5.3.2 Microstructures of Ni–P–Al2 O3 Plating and Coating
The coating specimens from the laser process were cut in transverse section, and
the section surfaces were mechanically polished and then etched with ethanol solu-
tion of 4% HNO3 for microstructural analysis. The phase identification of the Ni–
P–Al2 O3 plating and coating was performed with X-ray diffraction (Thermoarl-
SCINTAGX’TRAX). The element distributions were investigated with EDS (Hitachi
S-4700).
The surface morphology of the Ni–P–Al2 O3 electroless plating layer before
laser processing, together with the XRD patter for phase identification, is shown
in Fig. 5.11. It can be seen that cellular cells with size of 10 μm are populated over
the surface of electroless plating (Fig. 5.11a). After adding nano-Al2 O3 particles into
the plating bath, the cellular structure of the plated layer is formed in the mode of
heterogeneous nucleation and grew during deposition. The random distribution of
the cellular cells resulted in the smooth composite layer with high density.
The hardness of the plated layer was measured to be approximately HV0.2 350.
According to the previous research [26], when the phosphorus composition was more
than 8% in Ni–P electroless plating, the structure of plated surface was amorphous
rather than crystalline. In the Ni–P–Al2 O3 electroless deposit layer, the content of
phosphorus was 9.3% determined with EDS analysis. The XRD pattern of the Ni–P–
Al2 O3 plated layer (Fig. 5.11b) shows a wide peak at 2θ = 45°, representing typical
diffraction peak of amorphous material.
When pulse laser was applied on the Ni–P–Al2 O3 plating, the material surface
experienced four stages: heating, melting, crystallizing, and solidifying. The surface

Ni–P–Al2 O3 plating: a SEM
morphology and b XRD
pattern [25]. Reprinted from
Zhang et al. [25], Copyright
from Elsevier
(a)
(b)
morphology of the coating formed on 45 steel from the laser treatment is shown in
Fig. 5.12a. Compared with the morphology of the plating player (Fig. 5.11a), the
cellular cells disappear and the surface is smoother with thinner grains. This indicates
that the plating layer is smelted and solidified under the irradiation by laser beam.
Figure 5.12b shows the top region of the coating in cross-section. The high cooling
rate at the coating surface resulted in microcrystalline structure within 18 μm depth.
As shown in Fig. 5.12c, the microcrystalline structure mainly consists of tiny and
stagger quadric dendrites, and the tiny cellular structures with the size of 1–3 μm are
caused by intersecting of the quadric dendrites. Additionally, some white particles
are observed in the coating (Fig. 5.12d), with the size about 300 nm in diameter,
present both on grain boundary and in crystal grain. The elemental composition of
the white particles was examined with EDS, and the results are reported in Fig. 5.13
Fig. 5.12 SEM microstructure of laser-processed coating: a coating surface morphology, b top
and middle regions of coating in cross-section, c dendrite structure of top region of coating, and d
particles in dendrite region [25]. Reprinted from Zhang et al. [25], Copyright (2010), with permission
from Elsevier
Fig. 5.13 EDS spectrum of white particles [25]. Reprinted from Zhang et al. [25], Copyright (2010),
with permission from Elsevier
Table 5.3 Element concentrations in white particles [25]

Elements Al Fe Ni Pt
at.% 0.19 82.57 8.78 8.46
Reprinted from Zhang et al. [25], Copyright (2010), with permission from Elsevier
Fig. 5.14 XRD pattern of

laser-processed coating [25].
Reprinted from Zhang et al.
and Table 5.3. It is shown that the particles contain Al, Fe, Ni, and Pt elements.
Element Pt was involved in the coating layer by spraying it on the coating surface
for increasing conductivity. The white particles can prevent the growth of grains and
promote the transformation of fine grains. In the meanwhile, as the heterogeneous
nucleation, the white particles can contribute to the promotion of melting nucleation
rate.
The phases in the coating were identified via XRD analysis, as shown in Fig. 5.14;
they include Al5 FeNi, FeNi, and Fe0.64 Ni0.36 . At the high temperature of the laser
irradiation, nano-Al2 O3 particles would decompose; thus, the element Al from the
Al2 O3 particles may react with Fe and Ni elements to form Al5 FeNi.
In the middle region of the coating depth, the microstructure is composed of
cellular grains and dendrites, as shown in Fig. 5.15a. The grains in this region are
obviously larger than that in the top region, which was caused by a lower solidification
rate. In the bottom region of the coating layer close to the substrate, the plating layer
and fusion zone are observed (Fig. 5.15b). The columnar crystals are along the
vertical direction of the laser scanning, and cellular dendrites appear in the bottom
region of the plating layer.
5.3.3 Microhardness of Plating and Coating
The Vickers hardness of the Ni–P–Al2 O3 plating and laser-processed coating was
measured along the depth using a microhardness tester (HXD-1000 hardness instru-
ment) under an indentation load of 200 g with a dwelling time of 15 s. The hardness

laser-processed coating in
cross-section: a in the
middle region and b in the
bottom region [25].
(a)
10μm
(b)
profiles of the plating and coating are presented in Fig. 5.16. It is shown that the hard-
ness of the plating and coating varies in depth. At the plating surface, the hardness
has a value of HV0.2 490, but after the laser treatment, the hardness of the coating
surface can reach HV0.2 587. For the former in about 20 μm depth, hardness decreases
below HV0.2 200, which is the hardness of the substrate material. However, for the
latter at 25 μm below the surface, hardness decreases to about HV0.2 520 and then
rises up to a maximum value of HV0.2 840 occurring at the depth of about 80 μm,
where the fusion zone is located and the hardness is 1.7 times as high as that of the
plating and 4.5 times the substrate. After reaching the maximum, the hardness of the
laser-processed coating decreases gradually along the depth till the substrate.
Fig. 5.16 Microhardness profiles along the depth of Ni–P–Al2 O3 plating and coating [25].
Reprinted from Zhang et al. [25], Copyright (2010), with permission from Elsevier
The hardness decreases at the sublayer (25 μm below surface) of the laser-
processed coating due to two reasons. One is that the grains at the surface layer
are finer (Fig. 5.12b), which contribute to the higher hardness. The other may be the
formation of hard phases such as Al5 FeNi, FeNi, and Fe0.64 Ni0.36 , which are concen-
trated at the surface layer. However, the highest hardness of HV0.2 840 occurs in the
fusion zone (about 80 μm below the surface), which resulted from the diffusion
of Ni and P elements from the Ni–P–Al2 O3 electroless plating into the substrate.
The formed phosphides were found uniformly distributed in the fusion zone, which
enhanced the hardness. On the other hand, because of the short pulse width and
high cooling rate of the pulsed Nd:YAG laser, the diffusion was limited. As a result,
the thickness of fusion zone is only 15–18 μm. Below the fusion zone is the heat-
affected zone consisting of needle martensite, which was attributed to high degree
of supercooling. The thin martensite resulted in phase transformation hardening and
fine-grain hardening.
5.4 Coatings Prepared with Different Laser Powers
5.4.1 Coating Preparation Processes
Nano-Al2 O3 particles have a small volume and low specific weight so that the attrac-
tive force between particles is high, which leads to aggregation and growth of the
nanometer particles. This would deteriorate the favorable properties of the nanometer
5.4 Coatings Prepared with Different Laser Powers 125
material such as high microhardness and toughness. With the unique feature of
extremely high heating and cooling rate, laser coating deposition technique can effec-
tively control the size of nanometer particles by optimizing the process parameters.
The influence of laser power on the microstructure, hardness, and wear resistance
of the coating obtained by laser heating Ni–P nano-Al2 O3 plating on stainless steel
3Cr13 substrate was studied [27].
The substrate stainless steel 3Cr13 plate with the dimension of 70 × 40 × 3 mm
had experienced quenching and tempering treatments. The γ -Al2 O3 powder used
has a melting point of 2050 °C with an average grain size of 20 nm. The substrate
specimen was polished, cleaned, and dried before deposition of the coating. The
nano-Al2 O3 powder was pre-treated by chemically de-oiling with lye and cleaning
with cold water. The nano-Al2 O3 powder was added into the Ni–P electroless bath
and stirred by ultrasonic for about an hour to achieve homogeneous suspension. This
process would achieve a compound electroless plating with a thickness of 0.02 mm
on nano-Al2 O3 particles.
The Ni–P nano-Al2 O3 plating was heated using a continuous wave CO2 transverse
flow laser with a maximum power of 6 kW. Argon gas was used to protect the
nanoparticles from burning lost. The laser beam power and scanning speed were
adjusted for each specimen to obtain the cladding layers under different parameter
conditions.
5.4.2 Coatings Prepared with Low Laser Power
The main process parameters that govern the final properties of the coating from
laser heating the Ni–P nano-Al2 O3 plating can be laser power density and scanning
velocity. When laser power density was fixed, the scanning velocity of the laser beam
became the key factor determining the property of the cladding layer. The size of
the laser beam was 10 × 2 mm, the laser power varied from 600 to 900 W, and the
scanning velocity varied from 1 to 2.5 m/min.
The cross-sections of the coating specimens were prepared by a common
metallographic technique. Phase identification and crystallinity measurement were
performed on the specimens with XRD (Thermoarl-SCINTAGX’ TRAX). The
element distributions in the coatings were analyzed using EDS (Hitachi S-4700).
Figure 5.17 shows the XRD pattern of the Ni–P nano-Al2 O3 electroless plating. A
strong peak at 2θ = 45° is identified, which represents the typical diffraction peak
of amorphous materials. This indicates that adding nano-Al2 O3 particles into Ni–P
electroless solution did not change the amorphous nature of Ni–P electroless solu-
tion, but some small peaks are also present, which imply that the amorphous level
was reduced to some extent by mixing Al2 O3 powder.
Figure 5.18 shows the XRD pattern of the laser-processed coating. Differently,
part of the amorphous phase is transformed to crystalline phases including Ni3 P,
α-Fe, and Ni5 P2 . Since the laser power density was low (600–900 W) and the action
time of laser was short, most of P element was remained, which made the coating
Fig. 5.17 XRD pattern of Ni–P nano-Al2 O3 electroless plating [27]. Reprinted from Zhang et al.
[27], Copyright (2010), with permission from Elsevier
mainly consist of Ni–P alloy. Because of high heating and cooling rates of laser
treatment, Ni3 P and Ni5 P2 remained fine, which contributed to the hardness.
5.4.3 Coatings Prepared with High Laser Power
When the laser power density was increased (900 W), the deposition layer can be
melted. To control the growth of the nanometer particles during laser re-melting
process, high scanning velocity (14 m/min) of laser beam was adopted. The laser
power was chosen to be 4 kW, and the size of laser spot was 2 × 2 mm. The
crystallinity and phases of the laser-processed coating were analyzed by XRD. It was
shown that the crystallinity of the coating was about 81.26%, and the average grain
size was 21.8 nm. The main phases in the coating were Ni3 P and Ni with minor Al-Ni
compound, as demonstrated by the XRD diffraction pattern in Fig. 5.19. Because
of the high laser power density used, there was no unstable phase present in the
coating. The XRD analysis results revealed that most of the amorphous phase in the
Ni–P nano-Al2 O3 electroless plating was transformed to crystalline phases with fine
grains.
The element distributions in the coating processed with high laser power were
analyzed via EDS. As revealed by the EDS spectrum in Fig. 5.20 and the element
contents (wt%) reported in Table 5.4, about 7.64% Al was present in the coating and
Fig. 5.18 XRD pattern of laser-processed coating under low laser power [27]. Reprinted from
Zhang et al. [27], Copyright (2010), with permission from Elsevier
Fig. 5.19 XRD pattern of laser-processed coating under high laser power [27]. Reprinted from
Fig. 5.20 EDS spectrum of laser-processed coating under high laser power [27]. Reprinted from
Table 5.4 Element

Al Fe Ni P
concentrations (wt%) in the
coating processed with high 7.64 3.03 47.07 42.26
laser power [27] Reprinted from Zhang et al. [27], Copyright (2010), with permis-
sion from Elsevier
no O element was identified. This was caused by the decomposition of the nano-
Al2 O3 particles under high-energy laser beam. The Al element is diffused into the
microzone after the decomposition. This happened because the Al atoms are mostly
deviated from normal crystal array after electroless plated, and there existed defects
such as foreign atoms and molecule group, which promoted the Al diffusion, and
then formed the Al-Ni compound. However, due to the extremely short reaction time
of laser heat, the Al diffusion was limited to a short time, resulting in fine grains of
Al-Ni compound, which strengthened the coating.
5.4.4 Microhardness and Wear Resistance of Coatings
The Vickers hardness of the coatings processed under different laser heating condi-
tions was measured using a HXD-1000 hardness instrument under a load of 200 g
Fig. 5.21 Hardness of coatings prepared under different laser-heating conditions [27]. Reprinted
from Zhang et al. [27], Copyright (2010), with permission from Elsevier
with a dwelling time of 15 s. Figure 5.21 illustrates the influences of both laser scan-
ning velocity and laser power on the hardness of the coating. The coating prepared
with laser power of 700 W exhibited the highest hardness within the laser powers
selected. The hardness increased with the scanning rate and reached HV0.2 1280 at
the scanning rate of 2.5 m/min. However, the hardness decreased when the scanning
velocity was raised. This was because the input laser power was not enough to create
the temperature gradient needed for crystallization of the coating. When the laser
power was increased to 900 W, the coating hardness remarkably descended with a
lower scanning rate. The reason for this was that the long action time of the laser
beam on the coating surface caused slow cooling and crystallization thus rapid grain
growth.
Hardness was also compared between the 3Cr13 steel substrate, Ni–P nano-Al2 O3
electroless plating and laser-processed coating. As in Fig. 5.22, the laser-processed
coating has the highest hardness (HV0.2 865) and the substrate has the lowest
(HV0.2 243). Compared with the Ni–P nano-Al2 O3 electroless plating (HV0.2 525),
laser heat treatment did improve the plating hardness significantly. The application
of the coating enhanced stainless steel 3Cr13 surface remarkably.
The wear resistance of the laser-processed coating was evaluated on a pin-on-disk
MPX-2000 friction abrasion machine in dry-sliding mode at room temperature. The
test was performed under a normal load of 900 N at a rotational speed of 1100 rpm.
The wear mass loss versus sliding time is illustrated in Fig. 5.23, along with the
Fig. 5.22 Comparison of hardness among substrate, plating, and coating [27]. Reprinted from
Fig. 5.23 Comparison of wear loss between substrate and coating [27]. Reprinted from Zhang et al.
[27], Copyright (2010), with permission from Elsevier
Table 5.5 Chemical composition of stainless steel 3Cr13

Element C Si Mn P S Cr Fe
Content 0.31 0.96 0.6 0.03 0.03 13 Bal
(wt%)
curve for the 3Cr13 substrate for comparison. It is evident that the coating played
an important role in enhancing the wear resistance of the 3Cr13 substrate. Also,
the coating showed slightly increasing of wear loss with sliding proceeding, but the
3Cr13 substrate exhibited nearly linear ascending.
5.5 Cracking of Nano-Al2 O3 Coatings
5.5.1 Nano-Al2 O3 Coating Preparation
It has been found that nano-Al2 O3 coating is prone to crack during laser cladding
because of its brittleness and poor match with base metal in thermal expansion.
Nickel is often used as a kind of transition material to improve the bonding with
brittle ceramic phase and tough metal substrate. The improvement in cracking of
the laser-clad nano-Al2 O3 coating was attempted by using Ni-coated nano-Al2 O3
particles [28]. Stainless steel 3Cr13, with the chemical composition in Table 5.5, was
used as the substrate material, which had experienced a heat treatment to achieve
the hardness of HV0.2 270. The dimension of the substrate specimen was 50 × 50 ×
3 mm. The Ni-coated nano-Al2 O3 powder was made by chemical vapor deposition.
The diameter of the Al2 O3 particles was about 50 nm and increased to 200 nm after
vapor deposition with Ni, as shown in Fig. 5.24. The mass percentages of Al2 O3 in
the Ni-coated nano-Al2 O3 powder were 20%, 50%, and 85%, respectively.
Prior to laser cladding, the 3Cr13 specimens were polished and cleaned with
acetone. A slurry of Ni-coated nano-Al2 O3 was coated on the surface of the 3Cr13
substrate then air dried, forming a pre-deposition coating with the thickness of 0.7–
0.8 mm. The cladding process was performed using a pulsed wave Nd:YAG laser
beam with a power capacity of 300 W. The beam spot size was 3 mm in diameter
and had a lens with a focal length of 75 mm. Argon was used as shielding gas.
5.5.2 Crack Examination
The cladding specimens were cut at cross-section, mechanical polished, and etched
with FeCl3 solution for microstructural characterization under optical microscope
and SEM (Hitachi S-4700). As shown in Fig. 5.25, there are four distinct regions
that can be clearly identified in the cross-section of the cladding specimen, which are
Fig. 5.24 SEM morphology of Ni-coated nano-Al2 O3 powder [28]. Reprinted from Zhang et al.
[28], Copyright (2008), with permission from American Institute of Physics
Cladding layer
Transion layer
Hea reatment zone layer
Matrix
Fig. 5.25 SEM microstructure in cross-section of Ni-coated nano-Al2 O3 cladding specimen [28].
Reprinted from Zhang et al. [28], Copyright (2008), with permission from American Institute of
Physics
5.5 Cracking of Nano-Al2 O3 Coatings 133
cladding layer, transition layer, heat treatment zone, and matrix. Cracks are found in
the cladding layer starting from the coating surface and terminating at the transition
layer. Since the profile of the cladding layer is a crescent, the cracks were concentrated
in the central area of the cladding layer. As a ceramic material, Al2 O3 has different
thermal expansion coefficients from the metal matrix. When Al2 O3 was coated on
3Cr13 substrate, high temperature gradient was generated in the melting pool, which
induced large thermal stresses, resulting in cracks within the cladding layer. Nickel
was added in the coating to moderate the difference of thermal properties between the
cladding layer and the matrix. However, due to the very high heating and cooling rates
by the pulsed YAG laser, cracks inevitably occurred in the Ni-coated nano-Al2 O3
coating. Therefore, the crack sensibility in the coating depended on the coating
composition and the laser cladding process condition as well.
5.5.3 Laser Process Parameters
The main parameters that govern the cladding process using the pulsed wave Nd:YAG
laser include pulse length, pulse frequency, scanning velocity, laser power, among
which the first three were investigated for the Ni-coated nano-Al2 O3 cladding layer,
focusing on the influence of these process parameters on the cracking behavior of
the coating. The width and length of the cladding layer for each coating specimen
were measured, and the number of cracks was examined under an optical micro-
scope. These data for all the specimens which were prepared with different process
parameters are summarized in Table 5.6.
It can be seen that higher frequency led to higher laser power, thus resulted in a
larger cladding layer in both depth and width. Meanwhile, higher frequency created
more overlaps between two adjacent beams, which caused less thermal gradient of
the cladding layer. Therefore, when the pulse frequency was increased from 10 to
40 Hz, the cracking of the coating was mitigated. However, severe cracking was
observed in the cladding layer when the pulse frequency was raised to 50 Hz. This
was due to the increased heat gradient of the melting pool.
Peak power and pulse width exhibit an inversely proportional relationship, as
follows:
E
Pp = (5.1)
τ
where Pp is the peak power (W ), E is the energy per pulse (J), and τ is the pulse
width (mm). Thus, larger pulse width results in higher peak power, then induces
higher temperature of melting pool and higher thermal gradient. Therefore, cracking
increases with pulse width.
With the increase in scanning velocity, the interaction time of laser on the coating
material was reduced, which resulted in less heat input and thus caused smaller width
of the cladding layer. Meanwhile, the cooling rate increased, thus leading to a higher
Table 5.6 Summary of cladding layer geometry and associated laser process parameters [28]
Sample Current/A Pulse Pulse Scanning Depth of Width of Crack
width/ms frequency/Hz velocity/mm·min−1 cladding cladding
layer/mm layer/mm
1–1 150 2 50 400 0.45 2.21 Severe
1–2 150 2 40 400 0.38 2.12 No
1–3 150 2 30 400 0.35 2.08 Slight
1–4 150 2 20 400 0.21 2.04 Medium
1–5 150 2 10 400 0.1 1.85 Severe
2–1 100 1 30 400 0.07 1.53 No
2–2 100 2 30 400 0.14 2 No
2–3 100 3 30 400 0.17 2.04 No
2–4 100 4 30 400 0.24 2.16 Slight
2–5 100 5 30 400 1 2.25 Slight
3–1 150 2 30 100 0.2 2.35 No
3–2 150 2 30 300 0.2 2.3 Slight
3–3 150 2 30 600 0.19 2.25 Medium
3–4 150 2 30 1000 0.18 2.2 Severe
3–5 150 2 30 1200 0.16 2.12 Severe
Reprinted from Zhang et al. [28], Copyright (2008), with permission from American Institute of Physics
temperature gradient of the melting poor and more cracks. However, these three
parameters are correlated rather than independent. For example, scanning velocity
contributes to the overlap between two adjacent beams. Low peak power and small
pulse width can lead to low hardness of the cladding layer. Therefore, the process
parameters must be considered together with respect to the properties of the cladding
layer and crack sensibility.
5.5.4 Ratio of Nano-Al2 O3 Particle
To investigate the influence of nano-Al2 O3 content in the Ni-coated Al2 O3 powder on

the cracking behavior of the coating, the coating specimens were prepared by using
Ni-coated Al2 O3 powder with 20%, 50%, and 85% (in weight) nano-Al2 O3 content,
respectively. The laser process parameters were chosen as the scanning velocity of
400 mm/min, the current of 200 A, the pulse width of 2 ms, the pulse frequency of
30 Hz.
The microstructures of the nano-Al2 O3 cladding layers with different Al2 O3 ratios
are presented in Fig. 5.26. No cracks are observed in the coating with 20% Al2 O3 ,
but the grains are coarser (Fig. 5.26a). For the coating with 50% Al2 O3 , cracks are
observed obviously, but the grains are finer (Fig. 5.26b). Large and deep cracks are
observed in the coating with 85% Al2 O3 , and the grains of this coating are tiny

nano-Al2 O3 coating with a
20% Al2 O3 , b 50% Al2 O3 ,
and c 85% Al2 O3 [28].
permission from American
Institute of Physics
(a)
(b)
(c)
(Fig. 5.26c). Therefore, it can be concluded that with the increase in Al2 O3 content,
the possibility of cracking increased in the coating.
Figure 5.27 shows the SEM microstructures of different parts of the cladding layer
with 85% Al2 O3 . From the coating surface to the transition region, the microstruc-
ture changes from fine cellular structure, equiaxed crystal to dendrite structure. The
grain size gradually increases from the top to the interior of the coating. These obser-
vations can be explained with respect to the heat gradient and freezing rate. At the
beginning of solidification, the temperature gradient of the melt pool was the highest,
while freezing rate was the smallest, which resulted in planar grains. With the solid-
ification proceeding, the temperature gradient decreased and freezing rate raised,
which led to fine dendrite structure formed in the middle region of the cladding layer
(Fig. 5.27b). In the transition region (Fig. 5.27c), it is a gradient of structure showing
good metallurgical bonding between the cladding layer and substrate.
The element concentrations of the nano-Al2 O3 coatings were determined with
EDS, and the results are reported in Table 5.7. It was found that the cladding layers
contain elements Al, Fe, Cr, O, C, and Si. Apparently, Fe, Cr, C, and Si came from the
3Cr13 substrate, and Al and O were from Al2 O3 particles. Nickel was not detected
in the coatings. The possible reason for this may be the segregation of Ni under
strong stirring of the melting pool during the action of the high-pulse laser. Further
research for this mechanism is needed. The presence of Al, Fe, Cr, O, C, and Si
determined the coatings consisting of (Fe, Cr) solid solution, M23 C6 carbide, and
α-Al2 O3 . Thus when more Al2 O3 was added to the coating, other oxides can form
due to the decomposition of Al2 O3 . The nano-α-Al2 O3 resulted in the fine cellular
structure in the top layer of the coatings.
Between the adjacent grains is the bright grain boundary in the coating, which
is composed of (Fe, Cr) solid solution and M23 C6 carbide. Due to the dimensional
effect of nano-Al2 O3 , more addition of nano-Al2 O3 to the coating created more
nucleation sites, thus formed finer grains. This explained why the coating with 85%
Al2 O3 formed finer structures than that of 20% Al2 O3 . However, the more the content
of Al2 O3 , the more brittle the grains are. The thermal stresses induced in the laser
process were more likely to generate cracks in brittle structures. Cracks were initiated
at the grain boundaries of the coating surface and then extended along the depth of
coating. Moreover, more Al2 O3 may result in the decomposition of Al2 O3 , such that
oxygen was brought to the melting pool and formed other oxides, which deteriorated
the densification of the coating thus promoted more cracks formed.
5.5.5 Overlapping of Coating
From the analyses above, it can be concluded that it was the high cooling rate of
the laser process that resulted in the formation of cracks in the coatings. To reduce
the solidification velocity, multiple-track overlapping was used to create the nano-
Al2 O3 coating. Multiple-track scanning is necessary when the area of laser treatment
is large. When the coating is prepared by multiple tracks, subsequent track overlaps
(a)
(b)
(c)
Fig. 5.27 Microstructure of nano-Al2 O3 coating with 85% Al2 O3 : a top region, b middle region,
and c transition region [28]. Reprinted from Zhang et al. [28], Copyright (2008), with permission
from American Institute of Physics
Table 5.7 Element concentrations of nano-Al2 O3 coatings [28]

Element Al C Cr Fe Si O
20% Al2 O3 0.23 2.58 13.12 82.79 0.7 0.58
50% Al2 O3 0.34 4.44 13.72 79.53 0.71 1.26
85% Al2 O3 3.44 4.33 12.1 73.66 0.69 5.78
Reprinted from Zhang et al. [28], Copyright (2008), with permission from American Institute of
Physics
part of the former track, so as to reduce the cooling rate and heat gradient. However,
the microstructure of the overlapped part would experience tempering, which may
decrease the hardness of the region. Therefore, the overlap ratio is an important
parameter determining the softened region of the coating.
Three overlap increments between two tracks of 1.5 mm, 2 mm, and 2.5 mm
were used to create nano-Al2 O3 coatings, which corresponded to the overlap ratios
of 50%, 67%, and 83%, respectively. For comparison, single scanning and multiple-
track scanning were performed with the same process parameters. The morphologies
of the coatings with single-track scanning and multiple-track scanning are shown in
Fig. 5.28. As cracks were observed in the single-track coating (Fig. 5.28a), no cracks
were found in the coating with four-track scanning (Fig. 5.28b), which proved that
overlapping did improve cracking of nano-Al2 O3 coatings.
Fig. 5.28 Morphology of

nano-Al2 O3 coating: a single
track and b multiple tracks
[28]. Reprinted from Zhang
American Institute of
Physics
1 mm
(a)
1 mm
(b)
overlap ratio=50%
overlap ratio=67%
overlap ratio=83%
750
700
Microhardness /HV0.2
650
600
550
500
0.0 0.1 0.2 0.3 0.4 0.5 0.6

Transverse distance /mm
Fig. 5.29 Hardness profiles in cross-section of the coatings with overlapping [28]. Reprinted from
Zhang et al. [28], Copyright (2008), with permission from American Institute of Physics
To investigate the influence of overlap ratio on softening of the cladding layer,

the hardness in cross-section at the sublayer 0.2 mm below the coating surface was
measured for each coating specimen with overlap using a HXD-1000 hardness tester
under a load of 200 g with a dwelling time of 15 s. The distance between two
indentations is 0.05 mm in the transverse direction. The hardness data are illustrated
in Fig. 5.29. It is evident that hardness varies along the transverse direction at the
sublayer. It was estimated that the hardness decrements in the overlap region were
17%, 6.7%, and 8.4% for the overlap ratio of 50%, 67%, and 83%, respectively.
When the overlap was increased between two tracks, the region of multiple scanning
became large, then the whole heat input rose, which allowed grain growth, thus
decreasing the hardness. However, if the overlap was small, the heat gradient of the
cladding would be high, which may induce crack formation. Based on the analyses
above, the overlap of 2 mm (overlap ratio of 67%) is the best for the nano-Al2 O3
coating, with respect to cracking.
5.6 Summary of Laser Cladding of Nanomaterials
Electroless plating of Ni on the surfaces of multi-walled carbon nanotubes

(MWCNTs) with two thicknesses of plating was achieved. The two Ni-coated
MWCNTs were designated as Ni1CNTs and Ni0.5CNTs. The Ni-coated MWCNTs
powder was added to Inconel 718 superalloy powder in 10 wt%, and the composite
powder was deposited on solution-treated Inconel 718 substrate via laser cladding.
The microstructures of the cladded Ni0.5CNTs/Inconel 718 and Ni1CNTs/Inconel
718 layers were analyzed using SEM/EDS. It was revealed that due to the pres-
ence of the protective Ni coating, the MWCNTs could be partially retained from
the laser cladding process, but most of the nanotubes were unzipped into graphene
nanosheets (GNSs) and graphene fragments, which were further interbonded with
the neighboring ones, forming large porous carbon nanoribbons (CNRs) in the laser
cladded layer. The Ni coating played a protective role on the MWCNTs surfaces to
avoid their burning out in the molten pool during the laser process. The Ni1CNTs and
Ni0.5CNTs composite powders provided profound suppression effect on the element
segregation and Laves phase formation of IN718 superalloy, which was considered
to be attributed mostly to the large surface areas of the transformed GNSs and CNRs.
Owing to the thicker Ni coating, the depression effect provided by the Ni0.5CNTs
powder on the element segregation and Laves phase formation of IN718 superalloy
was greater than that provided by the Ni1CNTs powder.
Nanostructural alumina with high surface area, thermal stability, conductivity,
mechanical strength, stiffness, inertness to most acids and alkalis, adsorption
capacity, wear resistance, oxidation, electrical insulation, and nontoxic has potential
applications in industrial fields. Nano-Al2 O3 powder had been popularly used for
preparing wear- and oxidation-resistant coatings with fine grains by co-depositing
Al2 O3 with Ni–P together via electroless composite plating and then applying laser
treatment on the Ni–P–Al2 O3 plating. This approach enabled applying a Ni coating
on nano-Al2 O3 particles, which can reduce burning of the nanoparticles during laser
treatment. An attempt was made to create fine-grain coating on 45 steel using nano-
Al2 O3 powder. The nano-Al2 O3 powder was chemically pre-treated for de-oiling
with lye and cleaning with cold water and then added into the Ni–P electroless
bath and stirred by ultrasonic treatment to achieve homogeneous suspension. The
compound electroless plating with a depth of 0.02 mm can be achieved on the nano-
Al2 O3 particles from this process. Pulsed Nd:YAG laser treatment was conducted
on the Ni–P-nano-Al2 O3 electroless plating to create a coating on 45 steel substrate.
The XRD analysis revealed that the Ni–P nano-Al2 O3 electroless plating was amor-
phous, but after the laser irradiation, the coating exhibited microcrystalline struc-
ture. The microcrystalline structure mainly consisted of tiny and stagger quadric
dendrites, and the tiny cellular structure was caused by intersecting of the quadric
dendrites. The phases in the coating included Al5 FeNi, FeNi, and Fe0.64 Ni0.36 , which
contributed to the hardening of the coating through fine-grain strengthening and
dispersion strengthening.
Furthermore, the influence of laser power on the microstructure, hardness, and
wear resistance of the coating obtained by laser-heating Ni–P nano-Al2 O3 plating on
stainless steel 3Cr13 substrate was investigated. The laser treatment was performed
on Ni–P nano-Al2 O3 plating with low laser power or high laser power. The
crystallinity, phases, and element distribution of the coating were analyzed with
SEM/XRD/EDS. It was revealed that the coating processed with low laser power
(less than 900 W) resulted in the partial transformation from amorphous to crystal
structure with main phases of Ni3 P, α-Fe, and Ni5 P2 , but when treated with high laser
5.6 Summary of Laser Cladding of Nanomaterials 141
power (4 kW), the coating had most of amorphous phase transformed to fine crys-
talline structure containing Ni3 P and Ni with minor Al-Ni compound. The coating
from laser treating Ni–P nano-Al2 O3 plating played an important role in enhancing
the hardness and wear resistance of 3Cr13 substrate.
In the laser process of nano-Al2 O3 coating, cracks inevitably occurred in the
cladding layer due to brittleness and poor match with base metal in thermal expan-
sion of ceramic Al2 O3 . Nickel is often used as a kind of transition material to improve
the bonding with brittle ceramic phase and tough metal substrate. The improvement
in cracking of nano-Al2 O3 coating deposited 3Cr13 stainless steel via laser cladding
using a pulsed Nd:YAG laser was attempted by using Ni-coated nano-Al2 O3 parti-
cles with the mass percentages of Al2 O3 in the Ni-coated nano-Al2 O3 powder being
20%, 50%, and 85%, respectively. The influence of laser process paraments and
coating overlap on the cracking of the cladding layer was studied. It was demon-
strated that lower pulse frequency, larger pulse width, and higher scanning velocity
more likely caused cracks in the cladding layer. Therefore, these parameters must
be considered simultaneously to minimize the crack sensibility. For the ratio of
Al2 O3 in the Ni-coated nano-Al2 O3 powder, the higher the ratio, the more likely the
cracking occurred, but the grains of the coating became finer with more nano-Al2 O3
present. Multiple-track scanning can reduce the crack sensibility to a certain degree.
However, the overlap can cause local softening of the cladding. The compromise
between cracking and softening suggested the optimal overlap ratio of 67%.
References
1. Dieringa H (2011) Properties of magnesium alloys reinforced with nanoparticles and carbon
nanotubes: a review. J Mater Sci 46:289–306
2. Gupta M, Wong M (2015) Magnesium-based nanocomposites: light weight materials of the
future. Mater Charact 105:30–46
3. Tjong SC (2013) Recent progress in the development and properties of novel metal matrix
nanocomposites reinforced with carbon nanotubes and graphene nanosheets. Mater Sci Eng R
Rep 74:281–350
4. Sajjadi SA, Ezatpour H, Beygi H (2011) Microstructure and mechanical properties of Al–Al2 O3
micro and nano composites fabricated by stir casting. Mater Sci Eng A 528:8765–8771
5. Hamedan AD, Shahmiri M (2012) Production of A356–1 wt% SiC nanocomposite by the
modified stir casting method. Mater Sci Eng A 556:921–926
6. Bang JH, Suslick KS (2010) Applications of ultrasound to the synthesis of nanostructured
materials. Adv Mater 22:1039–1059
7. Hu ZC, Dong S, Xue QF, Xu RG, Yip HL, Huang F, Cao Y (2015) In-situ synthesis of metal
nanoparticle-polymer composites and their application as efficient interfacial materials for both
polymer and planar heterojunction perovskite solar cells. Orga Electro 27:46–52
8. Casati R, Vedani M (2014) Metal matrix composites reinforced by nanoparticles—a review.
Metals 4:65–83
9. Li JN, Chen CZ, Zhang CF (2013) Effect of nano-CeO2 on microstructure properties of TiC/TiN
+ nTi(CN) reinforced composite coating. Mater Sci B 36:541–546
10. Li MX, Zhang SH, Li HS, He YZ, Yoon JH, Cho TY (2008) Effect of nano-CeO2 on cobalt-
based alloy laser coatings. J Mater Process Technol 202:107–111
11. Wang HJ, Chen T, Cong WL, Liu DF (2019) Laser cladding of Ti-based ceramic coatings
on Ti6Al4V alloy: effects of CeO2 nanoparticles additive on wear performance. Coatings
9(2):109–127
12. Chen T, Wu WN, Li WP, Liu DF (2019) Laser cladding of nanoparticle TiC ceramic powder:
effects of process parameters on the quality characteristics of the coatings and its prediction
model. Opt Laser Technol 116:345–355
13. Jiang DF, Hong C, Zhong ML, Alkhayat M, Weisheit A, Gasser A, Zhang HJ, Kelbassa I,
Poprawe R (2014) Fabrication of nano-TiCp reinforced Inconel 625 composite coatings by
partial dissolution of micro-TiCp through laser cladding energy input control. Surf Coat Technol
249:125–131
14. Zhang W (2015) Experimental study of nano-Al2 O3 particles reinforced Fe-based composite
coating made by laser cladding. Adv Mater Res 1120–1121:698–701
15. Li YZ, Wang CS, Li T, Yao B (2010) Influence of nano-SiC particle on microstructure and
properties of laser clad NiFeBSi alloy coating. Chin J Laser 37(5):1356–1360
16. Tian Y, McAllister D, Colijn H, Mills M, Farson D, Nordin M, Babu S (2014) Rationaliza-
tion of microstructure heterogeneity in Inconel 718 builds made by the direct Laser additive
manufacturing process. Metall Mater Trans A 45:4470–4483
17. Choi JP, Shin GH, Yang S, Yang DY, Lee JS, Brochu M, Yu JH (2017) Densification and
microstructural investigation of Inconel 718 parts fabricated by selective laser melting. Powd
Technol 310:60–66
18. Loria EA, Eiselstein HL (1989) Superalloy 718: metallurgy and application. International
symposium on the metallurgy and applications of superalloy 718, The Minerals. Metals &
Materials Society, Warrendale, pp 229–240
19. Chen Y, Zhang K, Huang J, Hosseini SRE, Li ZG (2016) Characterization of heat affected zone
liquation cracking in laser additive manufacturing of Inconel 718. Mater Des 90:586–594
20. Chen Y, Lu FG, Zhang K, Nie PL (2016) Laser powder deposition of carbon nanotube reinforced
nickel-based superalloy Inconel 718. Carbon 107:361–370
21. Laha T, Agarwal A, McKechnie T, Seal S (2004) Synthesis and characterization of plasma spray
formed carbon nanotube reinforced aluminum composite. Mater Sci Eng A 381:249–258
22. Bakshi SR, Singh V, Seal S, Agarwal A (2009) Aluminum composite reinforced with multi-
walled carbon nanotubes from plasma spraying of spray dried powders. Surf Coat Technol
203:1544–1554
23. Peng T, Chang I (2014) Mechanical alloying of multi-walled carbon nanotubes reinforced
aluminum composite powder. Powd Technol 266:7–15
24. Chen Y, Zhang Q, Chen ZJ, Wang L, Yao JH, Kovalenko V (2019) Study on the element
segregation and Laves phase formation in the carbon nanotubers reinforced IN718 superalloy
by laser cladding. Powd Technol 355:163–171
25. Zhang QL, Yao JH, Pan Y (2010) Pulse laser assisted composite electroless deposit to prepare
ceramic coating. Phys Proce 5:327–332
26. Guo Z, Keong KG, Sha W (2003) Crystallisation and phase transformation behaviour of elec-
troless nickel phosphorus platings during continuous heating. J Alloy Comp 358(1–2):112–119
27. Zhang QL, Yao JH, Pan Y (2010) Study of nanometer of Al2 O3 composite electroless deposit
strengthened by different laser power. Mater Des 31:1695–1699
28. Zhang QL, Yao JH, Pan Y (2008) Crack controlling of composite coating with nanometer
Ni–Al2 O3 by pulsed Nd:YAG laser cladding. In: Proceedings of 3rd Pacific International
Conference on Application of Lasers and Optics, pp 998–1003

Laser Applications in Surface Modification: Jianhua Yao Qunli Zhang Rong Liu Guolong Wu

Uploaded by

Copyright:

Available Formats

You might also like

Laser Applications in Surface Modification: Jianhua Yao Qunli Zhang Rong Liu Guolong Wu

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Laser Applications in Surface Modification: Jianhua Yao Qunli Zhang Rong Liu Guolong Wu

Uploaded by

Copyright:

Available Formats

Advanced Topics in Science

and Technology in China 65

More information about this series at https://link.springer.com/bookseries/7887

Laser Applications in Surface

Rong Liu Guolong Wu

ISSN 1995-6819 ISSN 1995-6827 (electronic)

Jointly published with Zhejiang University Press, China

© Zhejiang University Press 2022

Hangzhou, China Jianhua Yao

2.3.5 Electrochemical Corrosion Behavior . . . . . . . . . . . . . . . . . . . . 40

5 Laser-Processed Coatings Involving Nanoparticles . . . . . . . . . . . . . . . . 103

1.1 Hardfacing via Laser Cladding

1.1.1 Materials for Hardfacing

Hardfacing is a metalworking process to apply harder or tougher materials to a base

1.1.2 Stellite Alloys

Stellite alloys are a group of cobalt-based alloys, mainly in two composition

a low-carbon Stellite alloy generated some new phases—intermetallic compounds

1.1.3 Hardfacing Process

Hardfacing can be applied on a surface by a number of different welding processes.

1.1.4 Hardfacing from Laser Process

Laser cladding or hardfacing is a welding-related technique which is mainly utilized

1.2 Surface Hardening by Laser

1.2.1 Features and Advantages

Laser hardening is considered as a heat treatment process or surface hardening

on irregular, three-dimensional workpieces. Laser hardening can improve the hard-

1.2.2 Applications on Steel and Cast Iron

1.3 Laser Treatment of Nanomaterials

1.3.1 Characteristics of Nanomaterials

materials are immense, including promising extraordinary physical, chemical, and

1.3.2 Beneficial Effects of Nanoparticles

1.3.3 Nanoparticles in Surface Coatings

Abstract Metal components often operate in a corrosion and wear combined

2.1 Stellite Alloy Hardfacing for Control Valves

2.1.1 Sealing Surface Enhancement

© Zhejiang University Press 2022 11

2.1.2 Improvement of Stellite Alloy Hardfacings

2.2 Stellite 6 Hardfacing

2.2.1 Problems in Amine Environment

As mentioned above, Stellite 6 is usually overlay-welded on valve seats as a hard-

2.2.2 Fabrication of Hardfacings

Table 2.1 Chemical compositions of Stellite 6 materials (wt%, Co in balance)

Fig. 2.1 SEM microscopic

Fig. 2.2 Schematic diagram

Fig. 2.3 Energy distribution

2.2.3 Microstructure and Carbide Ratio

Fig. 2.4 SEM

Fig. 2.5 SEM

2.2.4 Hardness and Wear Properties

2.2.5 Corrosion Behavior Under Polarization Test

Electrochemical tests such as potentiodynamic polarization and cyclic polarization

Fig. 2.6 Comparison of 4

Wear track depth (μm)

200 400 600 800 1000 1200

Fig. 2.7 Comparison of 4

Wear Volume loss (mm3)

Fig. 2.10 Potentiodynamic

Current density I (A/cm2)

Table 2.4 Polarization parameters of Stellite 6 specimens in morpholine solution [25]