CMP v7 PDF

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COMPREHENSIVE MATERIALS
PROCESSING
EDITOR-IN-CHIEF
Saleem Hashmi
Dublin City University, Dublin, Ireland
ASSOCIATE EDITORS-IN-CHIEF
Gilmar Ferreira Batalha

University of São Paulo, São Paulo, Brazil
Chester J. Van Tyne
Colorado School of Mines, Golden, CO, USA
Bekir Yilbas
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
VOLUME 7
NANO- AND MICROSCALE PROCESSING – MODELING

VOLUME EDITOR
Bekir Yilbas
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
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EDITOR-IN-CHIEF
Saleem Hashmi graduated from East Pakistan University of Engineering and Technology in 1967,
and in 1972 he completed his master’s and PhD degrees from the University of Manchester. He
was appointed as a postdoctoral fellow with UMIST, Manchester, in January 1973, and in October
1973, he joined Sheffield Hallam University as a lecturer. In 1976, he was promoted to senior
lecturer, then to principal lecturer in 1977, and to reader in 1984.
In January 1987, Professor Hashmi founded the School of Mechanical & Manufacturing Engi-
neering at Dublin City University. While in the process of establishing this school, he attracted
substantial external research funding to set up the Material Processing Research Centre (MPRC),
a research center of excellence in the field of material processing. To this day, he continues his
affiliation with Dublin City University as an emeritus professor in the school he founded 27 years ago.
In 1990, Professor Hashmi established Advances in Materials and Processing Technologies
(AMPT), a much needed international conference in materials processing. He continues to be the
Chairperson of the Steering Committee for this series of conferences. In 1998, he was appointed
as editor-in-chief of Elsevier Journal of Material Processing Technology and continued in this role
until 2008.
In 1995, Professor Hashmi was awarded the higher doctorate degree of DSc, by the University of
Manchester, the highest academic degree any university in the United Kingdom can award.
Professor Hashmi has supervised or co-supervised 110 PhD and 55 MEng research students to successful completion. Over the years,
he has also acted as an external examiner and expert assessor for PhD candidates and engineering departments with universities in Ireland,
the United Kingdom, India, Pakistan, Bangladesh, Hong Kong, Canada, Australia, and Malaysia. He is a Chartered Engineer (CEng), a Fellow
of the Institution of Mechanical Engineers, UK (FIMechE) and also a Fellow of the Institution of Engineers of Ireland (FIEI). He has
published over 430 papers and 12 books and is still publishing.
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EDITORIAL BOARD
Chester J. Van Tyne is the FIERF (Forging Industry Education and Research Foundation) professor
at Colorado School of Mines (CSM) in Golden, Colorado. He received his undergraduate and
graduate degrees from Lehigh University and worked for Bethlehem Steel as a research engineer for
a short period before joining Lafayette College in the Metallurgical Engineering Department as
a professor in 1980. In 1988, he joined the Metallurgical and Materials Engineering Department at
CSM. He is actively engaged in the research operations of the Advanced Steel Processing and
Products Research Center at CSM. His research interests are in metal deformation processes
especially forging, sheet stamping, and friction during metalworking operations.
Gilmar F. Batalha graduated as a mechanical engineer from the University of Brasilia in 1982. He
completed his MSc in Mechanical Engineering at the Federal University of Santa Catarina (1987),
his PhD in Mechanical Engineering (1995) and habilitation/livre-docencia in manufacturing
processes (2010) at the Department of Mechatronics and Mechanical Systems, Polytechnic School
of Engineering, University of Sao Paulo, where he has been a tenured professor since 1989. He has
had postdoctoral research experience at the Friedrich Alexander University Erlangen–Nuremberg,
Germany (1997–98). He was a visiting professor at Ecole Centrale de Lille, France (2004–06), and
at the Faculty of Mechanical Engineering of the Silesian University of Technology, Gliwice, Poland
(2012–13). He served as an adjunct professor at the Faculty of Engineering, UDESC, Joinville, Brazil
(1984–89). He has been an advisor on several PhD theses and master’s dissertations, coordinator
of the Laboratory of Manufacturing Engineering of the EPUSP, and is responsible for several
international and national cooperation agreements for exchange of students and researchers as well
as for consultancy with the industry. He is the volume editor for the Materials Modeling and
Characterization volume in Elsevier’s Comprehensive Materials Processing series.
Sergio T. Button received his PhD in Mechanical Engineering from School of Mechanical Engi-
neering, University of Campinas, Brazil, in 1990. He is currently full professor of Manufacturing
Processes at the University of Campinas. His main research fields include metal forming and
numerical simulation. Currently, his research is focused on cross wedge rolling and hot stamping.
He is the coauthor of 2 books and more than 100 papers in international journals and conferences.
He is the editor and reviewer of many international journals, and participates in the organization of
three national and international scientific conferences.
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viii Editorial Board
David Cameron is currently scientific advisor to Miktech Oy, Finland, and adjunct professor in
Dublin City University, Ireland. From 2003 to 2013, he was professor of Material Technology in
Lappeenranta University of Technology, Finland, where he established the Advanced Surface
Technology Research Laboratory (ASTRaL). He obtained his doctorate from the University of
Glasgow in 1980 and has spent his research career working on thin-film technology. He was
a senior research fellow at the Royal Signals and Radar Establishment in the United Kingdom until
1982 when he joined the School of Electronic Engineering at Dublin City University, becoming
associate professor. His research focus is on atomic layer deposition and its industrialization.
Joseph A. McGeough is an honorary professorial fellow in the School of Engineering at the

University of Edinburgh. He is a graduate from the universities of Glasgow (BSc and PhD) and
Aberdeen (DSc). He held research appointments at the universities of Leicester, Queensland, and
Strathclyde. As a student he gained numerous county, university, and national championship
athletic awards. His industrial training began as an undergraduate vacation apprentice for a firm of
electrical contractors based at ICI ltd Nobel Division, and he subsequently undertook postgraduate
experience at International Research and Development, Newcastle upon Tyne, before returning to
university service. He was successively a lecturer, senior lecturer, and reader in Engineering at
Aberdeen University, and then moved to Edinburgh University to take up its Regius Chair of
Engineering. His research work has dealt mainly with manufacturing processes for which he has
been awarded Institution of Mechanical Engineers and the Society for Underwater Technology
prizes. He has been the recipient of a Royal Society/SERC (Science and Engineering (now Engi-
neering and Physical Sciences) Research Council) Industrial Fellowship in order to transfer the
results of his research to industry. His publications include Principles of Electrochemical Machining,
Advanced Methods of Machining, and Micromachining of Engineering Materials (editor). His latest book
is The Engineering of Human Joint Replacements (2013), which contains details of the materials and
manufacturing processes used in this field. He is a fellow of the Institution of Mechanical Engi-
neers, International Academy for Production Engineering, Royal Society of Edinburgh, and Royal
Academy of Engineering.
Emin Bayraktar is a full university professor and research director at Supmeca/Paris, School of
Mechanical and Manufacturing Engineering, Paris, France. He was awarded a PhD degree in
Mechanical Engineering by IST/OSU and a second PhD degree in Materials Science and Engi-
neering in Paris. Subsequently, Professor Bayraktar was awarded a higher doctorate degree of
habilitation (DSc) in Mechanics of Materials in recognition of his research contributions at
Paris 6, University Marie-Curie. His teaching and research expertise lies on the processing and
manufacturing of the composite materials and damage analysis. Recently he has been appointed
as an adjunct professor in UNICAMP-Campinas, Brazil, on the new design of composites for the
application in aeronautical engineering. He is on the editorial board of a number of scientific
journals. He is also a member of the Steering Committee for the International Conference Series
on Advances in Materials and Processing Technologies (AMPT).
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Editorial Board ix
Bekir S. Yilbas received his PhD degree in Mechanical Engineering from Birmingham University.
He was awarded the Doctor of Engineering degree in 2005 by Birmingham University due to his
significant contribution to his field of study. He has published 375 journal papers in reputable
international journals and presented over 60 papers at international conferences. He has served
as an editorial board member of international journals, including International Journal of Machine
Tool and Manufacture Design, Research and Application, International Journal of Subsurface Sensing
Technologies and Applications, Journal of Materials Processing Technology, Journal of Achievements in
Materials and Manufacturing Engineering, International Journal of Nanomanufacturing, and Archives of
Materials Science and Engineering. He has received numerous awards in recognition of his research
work.
Nabil Bassim was born and raised in Cairo, Egypt. Dr. Bassim received a BSc in Chemical Engi-
neering from Cairo University in 1965. He went to the University of Virginia, United States, where
he received his MSc in Chemical Engineering (Nuclear Engineering option), and a PhD in Materials
Science in 1973. He moved to Canada where he is now professor of Materials Science and Engi-
neering at the University of Manitoba. He served for years as associate dean of research at the
Faculty of Engineering and was director of International Programs for the faculty. His areas of
research interest include mechanisms and mechanics of plastic deformation, dislocation theory,
fracture and fatigue, and nondestructive evaluations. He has patents on the use of acoustic emission
for monitoring of structures. He also has an interest in studying the behavior of materials at high
strain rates and large strains as they affect processes such as metal forming and machining. He has
published over 120 papers and supervised numerous MSc and PhD theses.
Syed H. Masood is professor of Mechanical and Manufacturing Engineering at Swinburne

University of Technology in Melbourne, Australia, where he is also the program coordinator of the
master’s program in advanced manufacturing technology. He obtained his PhD from the University
of Queensland, Australia; MEng from the University of New Brunswick, Canada; PG Dip from IIT
Delhi; and BSc Eng Hons from Aligarh Muslim University, India. Professor Masood has worked
previously at Central Queensland University, Rockhampton, and PNG University of Technology,
Papua New Guinea. He has published over 275 technical articles in international journals, books,
and conferences in different areas of advanced manufacturing. His current research interests include
additive manufacturing technologies, especially fused deposition modeling and direct metal
deposition, plastics manufacturing processes, material development, and material characterization.
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x Editorial Board
Mustafizur Rahman is currently a professor at the Department of Mechanical Engineering at

National University of Singapore (NUS), and has been with NUS since 1982. He obtained his BSc
in Engineering from Bangladesh University of Engineering and Technology (BUET), MEng and PhD
from Tokyo Institute of Technology, Japan. His research interests include micro-/nanomachining,
design and development of miniature machine tools and devices for micro-/nanomachining, and
high-speed machining of difficult-to-machine materials. He has received Outstanding Achievement
Awards from the Singapore Institute of Engineers and the Japan Society of Mechanical Engineers in
2003 and 2005, respectively.
George Krauss is currently university emeritus professor at the Colorado School of Mines and
a metallurgical consultant specializing in steel microstructural systems. Dr. Krauss received the BSc
in Metallurgical Engineering from Lehigh University in 1955 and the MSc and ScD degrees in
Metallurgy from the Massachusetts Institute of Technology in 1958 and 1961, respectively, after
working at the Superior Tube Company as a development engineer in 1956. In 1962–63, he was an
NSF postdoctoral fellow at the Max Planck Institut für Eisenforschung in Düsseldorf, Germany. He
served at Lehigh University as assistant professor, associate professor, and professor of Metallurgy
and Materials Science from 1963 to 1975, and in 1975 joined the faculty of the Colorado School of
Mines as the AMAX Foundation professor in Physical Metallurgy. He was the John Henry Moore
professor of Metallurgical and Materials Engineering at the time of his retirement from the Colo-
rado School of Mines in 1997.
In 1984, Dr. Krauss was a principal in the establishment of the Advanced Steel Processing and
Products Research Center, an NSF Industry-University cooperative research center at the Colorado
School of Mines, and served as its first director until 1993. He has authored the book Steels: Pro-
cessing, Structure, and Performance, (ASM International, 2005), coauthored the book Tool Steels, fifth
edition, (ASM International, 1998), and edited or coedited conference volumes on tempering of
steel, carburizing, zinc-based coatings on steel, and microalloyed forging steels. He has published
over 330 papers and lectured widely in technical conferences, universities, corporations, and ASM
International chapters, presenting a number of keynote, invited, and honorary lectures. He presented the Edward DeMille Campbell
Memorial Lecture of ASM International in 2000, the Howe Memorial Lecture of ISS in 2003, and the Adolf Martens Memorial Steel Lecture of
AIST in 2010.
Dr. Krauss has served as the president of the International Federation of Heat Treatment and Surface Engineering (IFHTSE), 1989–91,
and as President of ASM International, 1996–97. He is a fellow of ASM International, TMS, and IFHTSE. He has been awarded the Adolf
Martens Medal of the German Society for Heat Treatment and Materials, the Charles S. Barrett Silver Medal of the Rocky Mountain Chapter
of ASM, the George Brown Gold Medal of the Colorado School of Mines, and several other professional and teaching awards, including the
ASM Albert Easton White Distinguished Teacher Award in 1999. He is an honorary member of the Iron and Steel Institute of Japan,
a distinguished member of the Iron and Steel Society, an honorary member of ASM International, and an honorary member of the Japan
Institute of Metals.
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CONTRIBUTORS TO VOLUME 7
D. Abliz S.B. Mansour

Xi’an Jiaotong University, Xi’an, China and Clausthal King Fahd University of Petroleum and Minerals,
University of Technology, Clausthal-Zellerfed, Germany Dhahran, Saudi Arabia
A.Y. Al-Dweik M.M. Morshed
King Fahd University of Petroleum and Minerals, Dublin City University, Dublin, Ireland
Dhahran, Saudi Arabia
A.J.T. Naik
M.M. Alam University College London, London, UK
Islamic University, Kushtia, Bangladesh
L.-M. Romero-Nunez
N. Ali Queen Mary University of London, London, UK
Nanosmat Ltd., Manchester, United Kingdom
M.E.A. Warwick
M. Aliofkhazraei University College London, London, UK and UCL
Tarbiat Modares University, Tehran, Iran Energy Institute, London, UK
R. Binions L. Xie
Queen Mary University of London, London, UK Xi’an Jiaotong University, Xi’an, China and ABB
Corporate Research Switzerland, Dättwil, Switzerland
D. Li
Xi’an Jiaotong University, Xi’an, China B.S. Yilbas
King Fahd University of Petroleum and Minerals,
M. Maniruzzaman
Dhahran, Saudi Arabia
Islamic University, Kushtia, Bangladesh
xi
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CONTENTS OF VOLUME 7
Editor-in-Chief v
Editorial Board vii
Contributors to Volume 7 xi
Preface xv
7.01 Introduction to Nano- and Microscale Processing e Modeling 1

B S Yilbas
7.02 Micro/Nano Scale Energy Transport in Metallic Films and Stress Analysis: Analytical Approaches 3
B S Yilbas, A Y Al-Dweik and S B Mansour
7.03 Thermal Stresses in Micro- and Nanostructures 21
B S Yilbas
7.04 PVD Technology in Fabrication of Micro- and Nanostructured Coatings 49
M Aliofkhazraei and N Ali
7.05 Fabrication of Micro/Nanostructured Coatings by CVD Techniques 85
7.06 Fabrication and Properties of Micro- and Nanostructured Coatings Using Electrochemical
Depositions 119
7.07 Thin Film Coating for Polymeric Micro Parts 157
L Xie, D Abliz and D Li
7.08 Electric FieldeAssisted Chemical Vapor Deposition for Nanostructured Thin Films 171
M E A Warwick, L-M Romero-Nunez, A J T Naik and R Binions
7.09 AFM Applications in Micro/Nanostructured Coatings 191
7.10 Application and Advances in Microprocessing of Natural Fiber (Jute)eBased Composites 243
M M Alam, M Maniruzzaman and M M Morshed
xiii
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PREFACE
In recent years considerable advances have taken place in materials and their processing technologies, the pace
of which is progressing at an accelerated rate. It is therefore vitally important that researchers, academics, design
engineers, and manufacturing technologists be up to date with these new developments. Such developments
open up excellent opportunities to improve effective utilization of material resources, improve efficiency,
reliability, durability, and cost effectiveness of the products. This comprehensive series will serve researchers all
over the world in keeping them fully abreast of such new developments.
Comprehensive Materials Processing is a one-stop resource consolidating and enhancing the literature of the
materials processing and manufacturing universe. The work addresses recent progress in materials technologies
and science as well as covering recent developments in specific manufacturing processes involved with materials
for applications in engineering, biomedical, environmental protection, health and safety, and sensor materials
and technologies. The authoritative analysis of these processes will assist scientists and engineers in the selec-
tion, design, and usage of materials, whether required in the lab or in action across industry.
As the editor-in-chief of this comprehensive series, a truly collaborative work, I am greatly indebted to the
volume editors, internationally renowned experts in their fields, for guiding and selecting the topics for their
respective volumes, commissioning authors, and reviewing the content so meticulously. Their true dedication to
the scientific community is reflected in the time and energy they have given to this project. My sincere thanks are
also due to all of the authorseresearchers and materials practitioners who have contributed extensive coverage
of literature review as well as recent works of research to this huge project. Their insight and specialist knowledge
in their respective fields is reflected in the high quality of this work.
Myself, the three associate editors-in-chief, and all of the volume editors are greatly appreciative of all the
hard work undertaken to turn this idea into a publishable work. Our special thanks go to Gemma Tomalin, the
project manager, along with Joanne Williams, and the rest of the team at Elsevier who served successively to
keep the project on track through friendly nudges in order to ensure timely completion. We are also hugely
grateful to Mohamed Imrankhan for his dutiful coordination of the proofs.
The extensive academic discussion of core theories and applications, supplemented by applied case studies
and advanced multimedia features has drawn together numerous areas of research and I sincerely hope that this
work will prove to be of great help to both the young and experienced members of the international research
community, academics, and industrial practitioners for many years to come.
Saleem Hashmi
Editor-in-Chief
xv
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7.01 Introduction to Nano- and Microscale Processing – Modeling
BS Yilbas, King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
2014 Elsevier Ltd. All rights reserved.
7.01.1 Chapters in This Volume 2

7.01.2 Concluding Remarks 2
Acknowledgment 2
Nano- and microscale processing of materials find wide applications in industry because of the recent advancements in processing
technologies. The nano- and microscale processes are involved with multiphysics and require precision of operation. The process
can cover many technologies including sensors, machine tools, superalloys, ceramics, etc. The main focus in this volume is
concentrated on development of current and new processes, and extension of the practical applications in various areas. Although
nano- and microscale processes are relatively new, various processing techniques are well established in industries such as the
production of thin films in energy sector, soil ecology, biomedical applications, and the development of nanocrystalline materials
for space applications.
In the energy systems, the efficiency of the device, such as fuel cells, depends on the parameters defining the device characteristics
such as catalytic reaction activities. Charge transport and reactions taking place in porous electrodes of fuel cells also depend on the
configuration of the small scale and complex structure of the porous elements. In order to capture the physical process at small scale,
transport incorporating at micro-/nanoscale should be considered. This requires modification of governing equations from equi-
librium to nonequilibrium form. Although the development of the computational power in recent years enables reduction of the
computational cost and efforts, the physical problem associated with the micro-/nanoscale require further improvements in
computational capabilities. Otherwise, the current computational capacity provides only limited insight into the process and
obscures the detailed physical aspects associated with micro-/nanolevel processing. Most of the processes are highly coupled, such
as the catalytic reactions and are involved with charges (proton/ions and electrons); therefore, experimentation of the physical
process becomes unavoidable, despite the fact that the experiments are costly and involve engagement of well-trained technical
personnel. Recently, several microscopic models have been developed and purposed from atomistic to nanoscales involving
molecular dynamics and pseudoparticle methods to capture the material properties and transport processes in complex porous
structures, such as porous electrodes, catalyst layers thin films, etc. The limitations in number of atoms incorporated in the
molecular dynamics simulations limit the accuracy of the findings. On the other hand, in pseudoparticle models, such as lattice-
based Boltzmann modeling and dissipative particle dynamics, the particle–particle interactions are much milder than those in
the molecular dynamics model. This requires larger particle sizes and time steps to investigate the material structures and hydro-
dynamics while lacking the details of the actual process such as catalytic reactions, boundary resistances, and scattering effects.
Nevertheless, progress has been made toward achieving unified and comprehensive modeling of material behavior and energy
transport at micro-/nanolevels in complex structures.
The research into thermal stability of the materials has led to development of the nanocrystalline materials for high temperature
applications. The main strategy adopted for achieving thermal stability is to control grain growth and stabilize the grain size using
thermodynamics aspects, such as Gibbs adsorption for grain boundary segregation. However, grain boundary energy cannot be
considered as constant for the grain growth in nanosized alloys with a large fraction of interfacial volume. The effect of the grain
boundary energy on the grain size evolution is important for the physical understanding of grain boundary segregation; therefore,
thermodynamics aspects of the growth process should be accompanied with the process kinetics. Unfortunately, from the ther-
modynamics aspects, a sound and complete physical description of the process incorporating the evolution of the grain growth is
not yet established. Research studies are still in progress in this area.
The recent developments in nanocomposites make the polymer processing at micro-/nanolevels one of the focused research
areas. A major difference between a conventional polymer composite and polymer nanocomposite lies in the size of fillers.
Because of the differences in sizes, polymer nanocomposites have different properties from the conventional composites. The
intercalation of polymer chain inside montmorillonite galleries is an important step in nanocomposite compounding. Therefore,
the dynamics of polymers confined in spaces comparable with their dimensions become drastically different than in their
equivalent bulk. Consequently, improvement of the properties enables the nanocomposite polymers to be used in many
industries including aerospace applications to energy sector.
One of the techniques for nanofabrication is the gas cluster ion beam processing. Due to the unique interactions between the
cluster ions and surface atoms, modification of the surface becomes possible for surface smoothing applications at micro-/nano-
levels. The recent technological developments enable control of energy and size of the clusters, which makes the gas cluster ion
beam processing a favorable tool in surface engineering. The reactive cluster ion beams can be effectively used in etching of photonic
crystals. The smoothing effect by the cluster is derived from the horizontal moment of many surface atoms via impacts. Although
significant progress has been made toward the development of this technology, research into the extension of its application to
various areas is still in progress.
The information technology and computation are highly dependent on progresses made in micro-/nanoelectronics. The
semiconductor industry is on the path of ultimate scaling of its classical planar complementary metal oxide semiconductor (CMOS)
Comprehensive Materials Processing, Volume 7 http://dx.doi.org/10.1016/B978-0-08-096532-1.00700-7 1

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2 Introduction to Nano- and Microscale Processing – Modeling
devices. Scaling provides a direct benefit of achieving higher drive current, which directly results in the reduction of inverter delay.
However, smaller devices are leaky enough to increase undesired power consumption resulting in hotter device surface and reduced
battery lifetime. This brings the challenges to balance between the device size and heat generation due to excessive current flow in
microelectronic devices. Although considerable advancements have been made toward reducing the device size, improvement in
thermal and electrical efficiencies of such devices requires further investigations at micro-/nanolevel processing.
7.01.1 Chapters in This Volume
This volume has 10 chapters in addition to the Introduction chapter. These are as follows:
7.01. Introduction to Nano- and Microscale Processing – Modeling
7.02. Micro/Nano Scale Energy Transport in Metallic Films and Stress Analysis: Analytical Approaches
7.03. Thermal Stresses in Micro- and Nanostructures
7.04. PVD Technology in Fabrication of Micro- and Nanostructured Coatings
7.05. Fabrication of Micro/Nanostructured Coatings by CVD Techniques
7.06. Fabrication and Properties of Micro- and Nanostructured Coatings Using Electrochemical Depositions
7.07. Thin Film Coating for Polymeric Micro Parts
7.08. Electric Field–Assisted Chemical Vapor Deposition for Nanostructured Thin Films
7.09. AFM Applications in Micro/Nanostructured Coatings
7.10. Application and Advances in Microprocessing of Natural Fiber (Jute)–Based Composites
The materials presented in all the chapters in this volume are self-sufficient to explain different aspects of micro-/nanoprocessing
and their applications in practice. Two chapters deal with the thermal stress development at micro-/nanolevel processing under
high-energy beams and model study incorporating the nonequilibrium transport. The four chapters are related to different tech-
niques for surface engineering applications at micro-/nanolevels. The main emphases are given toward the development of the
nano-/microcoating technologies. The remaining chapters give insight into the various processing technologies and the measure-
ment techniques at micro-/nanolevels.
7.01.2 Concluding Remarks
This volume covers the processing technologies and model studies at micro-/nanolevels. The model studies focus on the
nonequilibrium transport during high-energy beam processing such as heat transport and microlevel stress developments. The
surface coating technologies associated with micro-/nanolevel processing are also given in detail. The current research trends and
expected future developments are also included, which forms the guidance for researchers and engineers in the field. The chapters
presented in this volume are self-contained in terms of the description of the physical processes taking place at micro-/nanolevels
and their practical applications in various industries. The readers should find this volume a great source for pertinent information
and relevant literature.
Acknowledgment
The editor expresses his deep appreciation to all the authors and coauthors of the chapters contained in this volume for all their hard
work that have been devoted in preparing their individual chapters. The editor greatly acknowledges the support provided by
Deanship of Scientific Research of KFUPM through projects IN101039 and IN101040.
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7.02 Micro/Nano Scale Energy Transport in Metallic Films and Stress
Analysis: Analytical Approaches
BS Yilbas, AY Al-Dweik, and SB Mansour, King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
7.02.1 Introduction 3
7.02.2 Micro/Nano Scale Energy Transport Model for Thin Films 3
7.02.3 Analytical Solution of Nano-Scale Lattice Transport Model and Thermal Stress Equation for Metallic Film 8
7.02.4 Micro/Nano Scale Transport Model in the Lattice Subsystem in Relation to the Boltzmann Equation 11
7.02.5 Findings and Discussions 15
7.02.5.1 Micro/Nano Scale Energy Transport and Stress Fields after Incorporating the Electron Kinetic Theory Approach15
7.02.5.2 Temperature Field due to the Solution of Radiative Phonon Transport 16
7.02.6.1 Electron Kinetic Theory Approach 18
7.02.6.2 Radiative Phonon Transport 18
Acknowledgments 18
References 19
7.02.1 Introduction
Micro/nano scale energy transport becomes important when the device size is small and the transition time is comparable to the
thermalization time of the substrate material. In this case, the classical approach for energy transport overestimates the properties of
the resulting states, such as temperature increase across the thin films. Depending on the metallic and nonmetallic substrates, energy
carries change from electrons to phonons at the microscopic level. In this case, electrons act as energy carriers in metals while
phonons are the primary energy carriers in dielectric materials. Therefore, care must be taken when modeling the energy transport at
micro/nano scale. In addition, material response to a thermal field results in thermal expansion and, consequently, thermal stress
development in the micro/nano size thin films. The closed form solution for energy transport at micro/nano scale provides useful
information on the dependent variables such as temperature and the independent variables such as energy input in time and space.
Although considerable research studies were carried out to explain the physical process taking place at micro/nano scale, most of the
work carried out has focused on the thermal response while neglecting the stress field (1–10).
In the case of metals, when the external energy is applied in the form of heat, thermal separation between electron and lattice
subsystems takes place. The thermal communication of these subsystems results in nonequilibrium energy transfer across the thin
film and the Fourier heating law fails to predict correct temperature increase in the film because of the assumption of infinite
thermal wave speed in the Fourier analysis. Consequently, care must be taken to formulate the physical aspects of the thermal
process to predict the correct temperature rise. Although two main approaches were introduced in the past, such as two-equation
model (11) and electron kinetic theory approach (12), both approaches become identical for the time shorter than the thermali-
zation time of the substrate material and the length scale comparable to the mean free path of the carriers. However, the two-
equation model uses the phenomenological equations while electron kinetic theory approach has a fundamental base formulating
the energy transfer process. Therefore, it has an advantage to use it in the analysis. Moreover, one of the fundamental equations
incorporating the nonequilibrium effects of the energy transport is the Boltzmann transport equation. This is because the
temperature difference across thin films results in nonequilibrium energy transport in the films and the energy transfer does not
follow the classical description. Therefore, phonon transport predominantly takes place in the thin films and phonons suffer from
the thermal resistance due to scattering and dispersion in the film. However, the simplification of the Boltzmann equation is
possible to minimize the efforts; in which case, consideration of the gray body assumption of the substrate material having the
average mean free path reduces the Boltzmann equation into the equation for the radiative phonon transport (13). Moreover, the
equation for the phonon transport can be further reduced to the hyperbolic differential equation after useful mathematical
arrangements.
In the present study, energy transfer in metallic and dielectric thin films is considered and mathematical arrangements for the
differential form of the energy equation due to external heating of the films are provided. In addition, the analytical solutions of
resulting equations are included and individually presented for metallic and dielectric thin films.
7.02.2 Micro/Nano Scale Energy Transport Model for Thin Films
The carriers, such as electrons, play a major role in energy transport in a metallic film. In this case, electrons receive the
energy from the external field and transfer their excess energy to the lattice site through the collision process. The thermal

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4 Micro/Nano Scale Energy Transport in Metallic Films and Stress Analysis: Analytical Approaches
relaxation of phonons, through the thermal transport, defines the thermal conductivity of the metallic substrates. Since the
distance between the two closely spaced planes is not zero and the energy distribution within this space depends on the
electron energy distribution in the confined space, temperature gradient may not linearly vary across the closely spaced
planes. Consequently, assumption made in the classical Fourier theory for the constant temperature gradient across these
planes fails to predict correct temperature rise in the confined space. Therefore, a new model based on the probabilistic
distribution of electron energy and the electron-lattice site collisions becomes necessary to introduce and to govern the
micro/nano scale energy transport in nano-scale devices. Although the electron kinetic theory approach for nano/micro scale
heating was introduced in previous studies (12–15), some basic formulations are provided for improved understanding of
the transport phenomena in metallic thin films.
Considering the electron motion in the surface region of the metals because of the thermal radiation at the surface, electrons can
travel from surface to solid bulk as well as bulk to solid field, which can be schematically shown in Figure 1.
However, electrons reaching the surface can escape once their energy exceeds the surface potential barrier. Consequently,
electrons with some fraction (j) reaching the surface can manage to escape. In order to account for the reflected electrons from the

N
surface, a mirror image at the surface is considered (14). Now, if we consider the location A in Figure 1, the net flow of Nsx w
6
number of electrons toward the surface occurs and j fraction of these electrons may escape from the surface. The situation, which
occurs at location A in Figure 1 is an exact mirror image of that corresponding to point B, i.e., (1j)Nsx is the number electrons still
N
flowing toward the surface from location B, i.e., (1j)Nsx electrons flow to the right and to the left at location B, Figure 1. In the
6
case of location A approaching location B, the number of electrons Nsx that flow from ‘x’ to ‘s’ discontinuously changes at s ¼ 0 and at
s ¼ x. However, at all locations, there is a balance between electrons that are reflected from the surface and escaped from the surface,
which leads to
N
Nsx þ Nxs ¼ ð2 jÞ [1]
6
where Nxs is the number of electrons, which flow from ‘x’ to ‘s’.
The electron energy, which is characterized by temperature Te(s,t), is augmented from the initial Te(s,t) by an amount equal to
that absorbed in traveling from s to x. The total number of electrons that travel from ds to dx in this time is
f 0 ðxÞ
I0 dx [2]
ðNsx þ Nxs ÞV
where I0 and f 0 ðxÞ are the pulse peak power intensity and the intensity distribution function in the absorption depth of the solid
material and V is the electron mean velocity, since all the beam energy is absorbed in the x-axis.
However, electrons receive energy from the irradiated field and make collisions among themselves as well as lattice site ions and
they transfer some fraction of their excess energy through the collision process, i.e., electrons scatter after the first collision and make
further collisions with less energetic electrons and lattice site ions. The energy exchange between energetic electrons, due to
absorption of the irradiated field, and other species can be formulated after considering the collision probability of energetic
electrons.
Considering the probability of electrons traveling a distance ‘x’ without making a collision it gives (12)
x
exp [3]
l
Figure 1 Electron movement in the surface region (x ¼ 0 is the free surface). Reproduced from Yilbas, B. S. Improved Formulation of Electron Kinetic
Theory Approach for Laser Short-Pulse Heating. Int. J. Heat Mass Tran. 2006, 49 (13–14), 2227–2238.
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Micro/Nano Scale Energy Transport in Metallic Films and Stress Analysis: Analytical Approaches 5
where x < 2l and l is the mean free path of the electrons. Consider Figure 1, the probability of electrons, which make a collision in
B, can be written as (12)
dx
w [4]
l
provided that x < 2l. The probability of electrons that last collided in B now colliding in A is

ds jx sj dx
exp [5]
l l l
However, the number of electrons (Nsx) leaving the location A in Figure 1, area A in time dt is Nsx AVdt, where Nsx is the number
density of electrons that transfer energy from dx to ds, and V is the mean electron velocity. The number of these electrons that just
collided in location A is

ds dx jx sj
Nsx AVdt exp [6]
l l l

ds dx jx sj
where exp is the probability of electrons that just collided in location A.
l l l
If the temperature of lattice site in dx is Tl(x, t) and the temperature of the electrons when they arrive at dx is Te(s, t) (allowing for
absorption on the way), then the energy transfer to the lattice site in dx from collisions with electrons in which the electrons give up
a fraction ‘f’ of their excess energy is

ds dx jx sj
Nsx AVdt exp f ðEe El Þ [7]
l l l
where Ee and El are the energy of electron and lattice ion, respectively. The analysis related to f is given below.
The fraction of electron excess energy transfer during the time comparable or slightly greater than the electron–
phonon collision time (sp) can be written in terms of the energy balance across the section dx in the substrate mate-
rial, i.e.,
ðElectron energyÞin ðElectron energyÞout ðTe Þin ðTe Þout

f ¼ or f ¼ [8]
ðElectron energyÞin ðPhonon energyÞ ðTe Þin Tl
where (Te)in is the temperature of an electron entering the section, (Te)out is the temperature of the electron leaving the section, and
Tl is the phonon temperature. f takes the values 0 f 1.
Integrating the contributions from all such infinitely small strips as to the energy in location B in Figure 1 gives
ZN
ds dx jx sj
Nsx AVdt exp f ðEe El Þds [9]
l l l
N
In this case, energy transfer during Dt (Dt sp, where sp is the electron–phonon collision time) due to absorption of an irradiated
field and the collision process can be written after incorporating the electron distribution function (14).
ZN Yð2s xÞ jx sj

DEtrans Vf kB
¼ Nsx 1 j exp Te s; t ds
AdxDt l2 2x l
N
ZN Yð2s xÞ jx sj
Vf kB
Nsx 1 j exp Tl x; t ds [10]
l2 2x l
N
ZN Zs
I0 f Nsx jx sj
þ exp f 0 ðxÞdxds
l2 Nsx þ Nxs l
N x
where
Yð2s xÞ
1j
Nsx x
¼ [11]
Nsx þ Nxs 2j
The first term on the left-hand side of eqn [10] is energy gain by the substrate material through the collision process, first and
second terms on the right-hand side represent electron and lattice energies, and the third term on the right-hand side is the energy
gain of the electrons due to the irradiated field.
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The final temperature of the electrons in dx after the collision process can be readily found from the conservation of energy, i.e.,
Total electron energy change after collision ¼ Total electron energy during dt – Change of lattice site energy.
Total electron energy after collision is
ZN Yð2s xÞ jx sj

VkB
Nsx 1 j exp ðTe ðs; tÞ f Tl ðx; tÞÞds [12]
l2 2x l
N
Total electron energy carried into dx during dt is
ZN Yð2s xÞ jx sj

VkB ð1 f Þ
N sx 1 j exp Te ðs; tÞds
l2 2x l
N
Yð2s xÞ [13]
ZN 1j Zs
I0 ð1 f Þ 2x jx sj
l2 2j l
N x
Therefore, the conservation of energy yields
ZN Yð2s xÞ jx sj

VkB
2 Nsx 1 j 2x
exp
l
ðTe ðs; tÞ fTl ðx; tÞÞds
l
N
ZN Yð2s xÞ jx sj

VkB ð1 f Þ
¼ Nsx 1 j exp Te ðs; tÞds [14]
l2 2x l
N
Yð2s xÞ
ZN 1j Zs
I0 ð1 f Þ 2x jx sj
l2 2j l
N x
Equations [10] and [14] can be rewritten after considering the electron distributions for the lattice element dx apart and for
electrons passing an area A, i.e.,
ZN ZN
DEtrans fk jx sj fk jx sj
¼ exp Te ðs; tÞds exp Tl ðx; tÞds
AdxDt l3 l l3 l
N N
Zjxj Zjxj
fk jx sj fk jx sj
þ j 3 exp Tl ðx; tÞds j 3 exp Te ðs; tÞds
l l l l
0 0
[15]
ZN Zs
I0 f 1 jx sj
l2 ð2 jÞ l
N x
ZN Zs
I0 f j jx sj
exp f 0 ðxÞdxds
l2 ð2 jÞ l
N x
and
ZN Zjxj
k jx sj jk jx sj
exp ðTe ðs; tÞ f T l ðx; tÞÞds exp ðTe ðs; tÞ f Tl ðx; tÞÞds
l2 l l2 l
N 0
ZN Zjxj
kð1 f Þ jx sj kð1 f Þ jx sj
¼ exp Te ðs; tÞds exp Te ðs; tÞds [16]
l2 l l2 l
N 0
ZN Zs Zjxj Zs
I0 ð1 f Þ jx sj 0 I0 ð1 f Þ jx sj
þ exp f ðxÞdxds exp f 0 ðxÞdxds
l2 ð2 jÞ l l2 ð2 jÞ l
N x 0 x
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where k is the thermal conductivity, which makes use of the simple kinetic theory result for the electron thermal conductivity (12)
NVkB l
k¼ [17]
3
The energy content of the small lattice site element dx apart can be written as
DE ¼ AdxCl Tl ðx; tÞ [18]
DE DE
where Cl ¼ rCp. The energy gain of the small lattice element during the small time interval dt is . The expansion of yields
dt dt
" #
DE 1 ðdtÞ2 00
¼ E t þ dtE0 t þ E t þ.E t [19]
dt dt 2!
or
DE ðdtÞ 00
¼ E0 t þ E t þ. [20]
dt 2!
Combining eqns [18] and [20] yields

DE v ðdtÞ v2
¼ Adx Cl ½Tl ðx; tÞ þ Cl 2
½Tl ðx; tÞ þ . [21]
dt vt 2! vt
When the time increment approaches the thermal relaxation time (dt / ss), eqn [21] reduces to

ve DE v v
¼ xCl Tl ðx; tÞ þ ss ðTl ðx; tÞÞ [22]
vt dtAdx vt vt
where e is the volumetric energy content of the lattice site. The energy gain of the small lattice element through collisional energy
transport can also be written as

DE 1 DEtrans v DEtrans
¼ þ ss [23]
AdxDt Adx Dt vt Dt
Substituting eqn [23] into eqn [15] yields the change of the lattice site energy, which is
0 1
ZN ZN
fk jx sj fk jx sj
B Tl ðx; tÞds C
B 3 exp Te ðs; tÞds exp C
B N l l l3 l C
B N C
B C
B C
B Zjxj Zjxj C
B jx sj jx sj C
B fk fk C
B þ j 3 exp Tl ðx; tÞds j 3 exp Te ðs; tÞds C
B l l l l C
B 0 C
DE B 0 C
¼B C
AdxDt B Zs
C
B ZN C
B I0 f 1 jx sj 0 C
B þ exp f ðxÞdxds C
B l2 ð2 jÞ l C
B C
B N x C
B C
B C
B ZN Z s C
B I f j jx sj C
@
0
exp f 0
ðxÞdxds A
l2 ð2 jÞ l
N x
0 1 [24]
ZN ZN
fk jx sj fk jx sj
B exp T ðs; tÞds exp Tl ðx; tÞds C
B l3 l
e
l3 l C
B N C
B N C
B C
B C
B Zjxj Zjxj C
B jx sj jx sj C
B fk fk C
B þ j 3 exp Tl ðx; tÞds j 3 exp Te ðs; tÞds C
B l l l l C
vB B 0 0 C
C
þ ss B C
vt B Zs
C
B ZN C
B I0 f 1 jx sj 0 C
B þ exp f ðxÞdxds C
B l 2 ð2 jÞ l C
B C
B N x C
B C
B C
B ZN Zs C
B I f j jx sj C
@
0
exp f 0
ðxÞdxds A
2 ð2 jÞ l
l
N x
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Equations [16] and [24] are the energy transport equations of interest for short pulse heating process at micro/nano level.
However, for small rise of electron temperature during the low-intensity heating pulse prevents electron escape from the surface.
Consequently, the term j in eqns [16] and [24] becomes zero.
Equations [16] and [24] can be transformed into differential equations. The method of solution to be used in the following
analysis is the transformation of the simultaneous differential – integral eqns [16] and [24] using the Fourier integral trans-
formation, with respect to x (15). This is due to the fact that the resultant ordinary differential equations may then be handled much
more conveniently.
Hence, the Fourier transformation of eqns [16] and [24] and eliminating the electron temperature among them results as
follows:

v l2 v2 vTl v2 Tl v v2 Tl v
1 þ ss C ¼ k þ sp þ I0 df expðdjxjÞ þ sp ½I0 df expðdjxjÞ [25]
vt f vx2 l vt dx2 vt dx2 vt
Equation [25] is similar to that obtained from the quasi-ballistic approach (16).
7.02.3 Analytical Solution of Nano-Scale Lattice Transport Model and Thermal Stress Equation for Metallic Film
Equation [25] represents the temperature field in the lattice subsystem. The analysis is presented in line with the previous study (15)
and the one-dimensional form of eqn [25] can be written as
2
v l2 v2 vTl v2 T l v v Tl

1 þ ss
C ¼ k þ s p
k
2 þ ðf dIðt Þexpðdjx jÞÞ [26]
vt f vx
2 l vt
vx
2 vt vx
where ss is the electron–phonon characteristic time (ss ¼ Ce/G), G is the electron–phonon coupling factor, l is the mean free path of
electrons, f is the fraction of excess energy change, Cl and Ce are the lattice and electron heat capacities, respectively, k is the thermal
conductivity, sp is the electron mean free time between electron coupling and phonon coupling, I(t*) ¼ I0exp(dt*), where I0 is the
pulse peak power intensity, exp(dt*) is the temporal distribution function of the pulse, d is the absorption coefficient. x* is the
distance along the x-axis and t* is the time variable. Tl and Te are the lattice site and electron temperatures, respectively. Introducing
the following equalities and dimensionless variables
fk Ce
l2 ¼ ; ss ¼
G G
[27]
Te Tl t
kd2 Ce
qe ¼ ; ql ¼ ; x ¼ x
d; t¼ ; a¼ ; ε¼
T0 T0 Ce =G G Cl
to eqn [26] finally yields
v3 ql v2 q v2 q vq
að1 þ mÞ þ εa 2l 2l l b expðxÞexpðgtÞ ¼ 0 [28]
vx2 vt vx vt vt
sp G fI0 dðmg εÞ dCe
where m ¼ ; b¼ ; g¼ :
Cl T0 G G
This model provides the improved energy transport equation including ballistic effects with volumetric source in dimensionless
form. Once the lattice site temperature is determined, the electron temperature can be found from
vql
¼ Gðqe ql Þ [29]
vt
Equations [28] and [29] describe temperature distribution in the lattice and electron subsystems. Moreover, the coefficients of
eqn [28] are considered to be independent of temperature. Hence,
v3 ql v2 ql v2 ql vql
að1 þ mÞ þ εa 2 bexpðxÞexpðgtÞ ¼ 0;
vx2 vt vx2 vt vt
[30]
vql
¼ εðqe ql Þ
vt
In the absence of the volumetric source, one can see that b ¼ 0. So, the system (eqn [30]) reduces to the following
system:
v3 ql v2 q v2 q vq
að1 þ mÞ 2
þ εa 2l 2l l ¼ 0;
vx vt vx vt vt
[31]
vql
¼ εðqe ql Þ
vt
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Since the absorption depth of the substrate material is significantly smaller than the thickness of the substrate material, the
assumption of a semi-infinite solid heated by a time decaying source from the surface can be justifiable. The boundary conditions
for the problem can be written as follows:
vqe vqe
ð0; tÞ ¼ I0 ek1 t ; ðN; tÞ ¼ 0
vx vx [32]
qe ðx; NÞ ¼ q0 ; ql ðx; NÞ ¼ q0
I0
The dimensionless source amplitude, I0 , is related to the dimensional one, I0, through the relation I0 ¼ , and the dimen-
kdT0
dCe
sionless power, k1, is related to the dimensional one d, through the relation k1 ¼ ¼ g.
G
Recently, Yilbas et al. (17) constructed the closed form solutions for temperature distribution with surface heat sources. The
surface heat source corresponds to the short duration contact of the gold film with a heat source at the surface. The solution of the
boundary value problem can be given, when

ε ε
k1 > 1 & k1 < or k1 < 1 & k1 > [33]
1þm 1þm
as follows:
εI0
ql ðx; tÞ ¼ q0 expð k1 ðt þ uxÞÞ
uk1 ðk1 εÞ
[34]
I0
qe ðx; tÞ ¼ q0 þ expð k1 ðt þ uxÞÞ
uk1
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1 k1
where u ¼ :
ak1 ðk1 ð1 þ mÞ εÞ

ε
It should be noted that the solution for ql(x,t) and qe(x,t) in eqn [34] is only valid for k1 > 1 & k1 < or
1þm

ε
k1 < 1 & k 1 > . In which case, ε is of the order 102 for metals and k1 < 1 for short pulse heating situation.
1þm
The equation governing the momentum in a one-dimensional solid for a linear elastic case can be written as (18)
v2 sx
1 v2 sx
v2 T

2
2
2 ¼ c2
2l [35]
vx c1 vt vt
where c1 is the wave speed in the solid.

rffiffiffi
E 1þn
c1 ¼ and c2 ¼ raTl
r 1n
where n is Poisson’s ratio, r is the density of the solid, and aTl is the thermal expansion coefficient of the solid.
The solution of eqn [34] provides temperature distribution ql with surface heat sources. So, by using the dimensionless variables
d2
in eqn [34], the dimensionless stress is sx ¼ sx
. Equation [35] can be rewritten to yield
c 2 d2 T 0
v2 sx v2 sx
2
A2 2 ¼ B2 expð gðt þ uxÞÞ [36]
vx vt
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
d εI0
where A ¼ and B ¼ :
c1 g d guðg εÞ
The initial conditions for eqn [36] are as follows:

sx ðx; 0Þ ¼ 0; sx ðx; NÞ ¼ 0 [37]
Now, applying the Fourier sine transform for eqn [36] with respect to t, by requiring that, for a physically meaningful system,
sx(x,t) and its first derivatives in t vanish as t approaches infinity. To obtain the analytical solution for eqn [37], Fourier sine and
Fourier cosine transformations are used. In this case, eqn [37] yields
rffiffiffiffi rffiffiffiffi
v2 2 2 2 2 expðguxÞ
Uðx; pÞ A psx ðx; 0Þ þ A p Uðx; pÞ ¼
2 2
B p [38]
vx2 p p g2 þ p2
where p is the Fourier sine variable and U(x,p) is the Fourier sine of sx(x,t) with respect to t, which is defined by
rffiffiffiffi Z N rffiffiffiffi Z N
2 2
Uðx; pÞ ¼ sx ðx; tÞsinðptÞdt, and the inverse Fourier sine of sx(x,t) is given by sx ðx; tÞ ¼ Uðx; pÞsinðptÞdp.
p 0 p 0
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To apply the Fourier sine transform with respect to t in eqn [38], one can use the following formulas (19):
2 rffiffiffiffi
v 2
Fs u x; t ; t; p ¼ p 2
Fs fuðx; tÞ; t; pg þ puðx; 0Þ:
vt 2 p
rffiffiffiffi [39]
2 p
Fs eat ; t; p ¼ ; ða > 0Þ:
p a2 þ p2
By applying the initial condition for eqn [38], one can obtain
rffiffiffiffi
v2 2 2 2 2 expðguxÞ
Uðx; pÞ þ A p Uðx; pÞ ¼ B p [40]
vx2 p g2 þ p2
Since the film surface is free to expand during the external heating process, the thermal stress at the surface is set to zero. The
relevant boundary conditions are
sx ð0; tÞ ¼ 0; sx ðN; tÞ ¼ 0 [41]
Now, applying the Fourier sine transform for eqn [40] with respect to x, by requiring that, for a physically meaningful system,
sx(x,t) and its first derivatives in x vanish as x approaches to infinity, as well as using the formulas (19)
2 rffiffiffiffi
v 2 2 v
Fc u x; t ; x; s ¼ s Fc fuðx; tÞ; x; sg uð0; tÞ:
vx2 p vx
2 rffiffiffiffi
v 2 2
Fs u x; t ; x; s ¼ s F s fuðx; tÞ; x; sg þ suð0; tÞ:
vx2 p
rffiffiffiffi [42]
ax 2 a
Fc e ; x; s ¼ ; ða > 0Þ:
p a2 þ s2
rffiffiffiffi
2 s
Fs eax ; x; s ¼ ; ða > 0Þ:
p a2 þ s2
The resulting equation is
rffiffiffiffi
2 2 1
sUð0; pÞ s2 Vðs; pÞ þ A2 p2 Vðs; pÞ ¼ B2 ps 2 [43]
p p ðg þ p2 Þðg2 u2 þ s2 Þ
where s is the Fourier sine variable and V(s,p) is the Fourier sine of U(x,p) with respect to x, which is defined by
2 2
Vðs; pÞ ¼ Uðx; pÞsinðsxÞdx, and the inverse Fourier sine of sx(x,t) is given by Uðx; pÞ ¼ Vðs; pÞsinðsxÞds.
p 0 rffiffiffiffi Z N p 0
2
Applying the boundary conditions by using the formula Uðx; pÞ ¼ sx ðx; tÞsinðptÞdt gives
p 0
Uð0; pÞ ¼ 0 [44]
So, eqn [43] reduces to
2 ps
Vðs; pÞ ¼ B2 2 [45]
p ðg þ p2 Þðs2 þ g2 u2 Þðs2 A2 p2 Þ
Applying the inverse Fourier sine transform for eqn [45] with respect to x, and using tables of Fourier sine transform 19), one can
obtain
rffiffiffiffi ZN
2
Uðx; pÞ ¼ Vðs; pÞsinðsxÞds
p
0
rffiffiffi ZN
2 B2 p 2 s
¼ sinðsxÞds
p ðg2 þ p2 Þ p ðs2 þ g2 u2 Þðs2 A2 p2 Þ
0
rffiffiffiffi ZN
2 B2 p 2 s s [46]
¼ sinðsxÞds
p ðg2 þ p2 Þðg2 u2 þ A2 p2 Þ p ðs2 A2 p2 Þ ðs2 þ g2 u2 Þ
0

2 B2 p s s
¼ F s ; s; x Fs ; s; x
p ðg2 þ p2 Þðg2 u2 þ A2 p2 Þ ðs2 A2 p2 Þ ðs2 þ g2 u2 Þ
rffiffiffiffi 2
2 B pðcosðApxÞ expð guxÞÞ
¼
p g2 u2
A2 ðp2 þ g2 Þ p2 þ 2
A
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Therefore,
rffiffiffiffi
2 B2 pðcosðApxÞ expðguxÞÞ
Uðx; pÞ ¼ [47]
p g2 u2
A2 ðp2 þ g2 Þ p2 þ 2
A
Applying the inverse Fourier sine transform for eqn [47] with respect to t, one can have
8
egt coshðgAxÞ e A t coshðguxÞ
gu
>
>
>
>
>
> ; t Ax
>
> gt
> gu
>
> gux
< e e
e A
t
B2 gu
sx ðx; tÞ ¼ 2 2 [48]
g ðu A Þ >
2
> e gAx sinh gt þ egux sinh t
>
> A
>
>
>
> ; t < Ax
>
>
>
: gux
gt gu
e e e A
t
Equation [48] gives the solution for the stress field in the film when subjected to an external heat pulse.
7.02.4 Micro/Nano Scale Transport Model in the Lattice Subsystem in Relation to the Boltzmann Equation
The Boltzmann transport equation can be used to formulate the energy transport in thin films. After considering the gray
body assumption of the substrate material, the Boltzmann equation reduces to the equation for the Phonon Radiative
Transfer in the film. Although the formulation of the governing equations is given in the previous study, some formulation
steps are included for the completeness of the analysis in the present study. The equation for radiative phonon transport in
a gray body can be written as (13)
Z1 !
1
Iu dm Iu
2
1 vIu vIu 1
þm ¼ [49]
v vt vx vsðu; TÞ
where, Iu ¼ Iu(x,m,u,t) and it is defined as
X
3
Iu ðx; m; u; tÞ ¼ vfu ðx; tÞZuDðuÞ [50]
p¼1
where v is the speed of the phonons, fu(x,t) is the density of the phonon ensemble in phase space at point x and time t, Z is the
Planck’s constant divided by 2p, u is the angular frequency of the phonons and ranges from 0 to uD, s is the phonon relaxation time
(which is temperature dependent), D(u) is the density of states, and p is the polarization index. There are three polarizations of the
phonons; two transverse (mutually orthogonal) and one longitudinal.
The heat flux in the medium in the x-direction is given as
XZ Z
uD
qx ðx; tÞ ¼ vx fu ðx; tÞZuDðuÞdudU

p
4p 0
XZ Z
1 uD
¼ 2p vmfu ðx; tÞZuDðuÞdudm [51]

p
1 0
Z1 ZuD
¼ 2p mIu ðx; m; u; tÞdudm
1 0
where vx ¼ vm (m ¼ cos q). In the following derivation, we will assume that the relaxation time is independent of the
phonon frequency u. Equation [49] by 2pm and integrating it with respect to m from 1 to 1 and with respect to u from 0 to
uD yields,
ZuD Z1 Z1 ZuD Z1
1
2p m Iu dm dmdu 2p mIu dmdu
ZuD Z1 ZuD Z1 2 [52]
2p v vIu 0 1 1 0 1
mIu dmdu þ 2p m2 dmdu ¼
v vt vx vsðTÞ
0 1 0 1
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The first term on the left-hand side of eqn [52] is simplified to

ZuD Z1
2p v 1 vqx ðx; tÞ
mIu dmdu ¼ [53]
v vt v vt
0 1
The last term on the right-hand side of eqn [53] may be simplified by using the definition of the heat flux as
ZuD Z1
2p mIu dmdu
0 1 qx ðx; tÞ
¼ [54]
vsðTÞ vsðTÞ
The first term on the right-hand side is identically zero because we are integrating it two times with respect to m. After the first
integration, the integrand contains only the first power of m and a second integration will make the expression 0.
ZuD Z1 Z1 !
1
2p m Iu dm dmdu
2
0 1 1
¼0 [55]
vsðTÞ
The second term on the left-hand side of eqn [52] may be simplified as follows:
ZuD Z1 X ZuD Z1
vIu vfu ðx; tÞ
2p m2 dmdu ¼ 2p m2 v ZuDðuÞdmdu [56]
vx p vx
0 1 0 1
If the ‘phonon gas’ is not very far from the equilibrium condition then we may write (12)
fu ðx; tÞzfuo ðTðx; tÞÞ [57]
where fuo ðTðx; tÞÞ is the equilibrium

density of phonon ensemble at a point x and time t corresponds to the temperature T(x,t) at that
point and time. For phonons, this is given by the Bose–Einstein distribution function. This allows the following approximations to
be made (13),
vfu ðx; tÞ vfuo ðTðx; tÞÞ vfuo ðTðx; tÞÞ dT
z ¼ [58]
vx vx vT dx
Substituting eqn [58] into eqn [52] yields
ZuD Z1 X ZuD Z1
vIu dfuo dT
2p m2 dmdu ¼ 2p m2 v ZuDðuÞdmdu
vx p dT dx
0 1 0 1
X ZuD Z1
1 dT dfuo
¼ 2p sm2 v2 ZuDðuÞdmdu
vs dx p dT
0 1 [59]
X ZuD Z1
1 dT dfuo
¼ 2p svx2 ZuDðuÞdmdu
vs dx p dT
0 1
1 dT
¼ k
vs dx
In the above expression, we used the result that the thermal conductivity k is defined as (13)
ZuD Z1
2p X df o
k¼ sv2 u ZuDðuÞdmdu
3 p dT
0 1
[60]
XZ Z
uD 1
df o
¼ 2p svx2 u ZuDðuÞdmdu
p dT
0 1
The last expression follows from the fact that the medium is isotropic, therefore, the average speed of the phonons in the three
coordinate direction is approximately the same, v2 ¼ vx2 þ vy2 þ vz2 z3vx2 . The rearrangements of the equations yields
vqx dT
s þ qx ¼ k [61]
vt dx
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The energy conservation relation is given as

vT
C þ V$q ¼ 0 [62]
vt
where C is the volumetric specific heat capacity and q is the heat flux vector. For one-dimensional heat transfer, the above relation
may be written as
vT vqx
C þ ¼0 [63]
vt vx
Differentiating eqn [61] with respect to x and assuming constant thermal conductivity k yields
v2 qx vqx d2 T vqx d2 T v2 qx
s þ ¼ k 2 0 ¼ k 2 s [64]
vxvt vx dx vx dx vxvt
Substituting eqn [64] into eqn [63] yields
vT d2 T v2 qx
C k 2 s ¼0 [65]
vt dx vxvt
Differentiating eqn [63] with respect to t and rearranging terms yields
v2 qx v2 T
¼ C 2 [66]
vtvx vt
Substituting eqn [66] into eqn [65] and rearranging terms finally yields the hyperbolic equation for micro-nano scale energy
transport in the lattice subsystem, i.e.,
v2 T vT d2 T
sC 2
þC ¼k 2 [67]
vt vt dx
Cv2 s
From the kinetic theory, it is known that k ¼ , which may be rearranged to yield
3
3k k
¼ Cs 0 ¼ Cs [68]
v2 vx2
Substituting the last expression in eqn [67] and simplifying yields

1 v2 T 1 vT d2 T
þ ¼ 2 [69]
vx2 vt 2 a vt dx
where a is the thermal diffusivity.

Consider the short-pulse heating situation where the volumetric source term is added to eqn [69] because of the absorption
of the pulse heating source. Since the pulse intensity varies with time, exponential function can be introduced to account for the
time decay of the pulse. Due to the general solution, let’s consider eqn [69] in which the volumetric source term is incorpo-
rated, i.e.,
v2 v v2
A Tðx; tÞ þ B Tðx; tÞ ¼ 2 Tðx; tÞ þ I0 dedx ebt [70]
vt 2 vt vx
I00 d
where I0 ¼ (I0 is the peak power intensity of the pulse, d is the absorption coefficient, and k is the thermal conductivity), b is the
k 0
rCp rCp
pulse parameter, A ¼ , r is the density, Cp is the specific heat, s is the relaxation time), and B ¼ are the coefficients.
ks k
The initial and boundary conditions appropriate to the pulse heating situation are given by
Tðx; 0Þ ¼ 0
vT [71]
ðx; 0Þ ¼ 0
vt
It should be noted that it is initially assumed that temperature is zero inside the substrate material and time derivative of
temperature is also zero, i.e.,
TðN; tÞ ¼ 0
vT [72]
ð0; tÞ ¼ 0
vx
Here, it is assumed that at a large depth below the surface the substrate material remains at the initial temperature. In addition,
no convection boundary is assumed at the surface during the short heating period. Applying the Fourier-Cos transform with respect
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to x, by requiring that, for a physically meaningful system, T(x,t) and its first derivatives in x vanish as x approaches infinity, as well as
using the formulas in the appendix, results in
v2 v 2 2 vU 2 I0 debt
A 2 Uðs; tÞ þ B Tðs; tÞ ¼ s Uðs; tÞ ð0; tÞ þ [73]
vt vt p vx p d2 þ s2
where s is the Fourier-Cos variable and U(s,t) is the Fourier-Cos of T(x,t) with respect to x, which is defined by
2 2
Uðs; tÞ ¼ Tðx; tÞcosðsxÞdx, and the inverse Fourier-Cos of U(s,t) is given by Tðx; tÞ ¼ Uðs; tÞcosðsxÞds:
p 0 p 0
By applying the boundary conditions for eqn [70], one can obtain
rffiffiffiffi
v2 v 2 I0 debt
A 2 Uðs; tÞ þ B Uðs; tÞ ¼ s2 Uðs; tÞ þ [74]
vt vt p d2 þ s2
Now, eqn [74] can be solved through applying the Laplace transform with respect to t,
rffiffiffiffi
vU 2 I0 d
Ap2 Uðs; pÞ þ BpUðs; pÞ A ðs; 0Þ Uðs; 0ÞðAp þ BÞ ¼ s2 Uðs; pÞ þ [75]
vt p d2 þ s2 ðp þ bÞ
where p is the Laplace variable and Uðs; pÞ is the Laplace of U(s,t) with respect to t.
rffiffiffiffi Z N
2
However, applying the initial conditions by using the formula Uðs; tÞ ¼ Tðx; tÞcosðsxÞdx gives
p 0
Uðs; 0Þ ¼ 0
vU [76]
ðs; 0Þ ¼ 0
vt
rffiffiffiffi
2 I0 d
Ap Uðs; pÞ þ BpUðs; pÞ ¼ s Uðs; pÞ þ
2 2 [77]
p d2 þ s2 ðp þ bÞ
Then, Uðs; pÞ can be given as

rffiffiffiffi
2 I0 d
Uðs; pÞ ¼ [78]
p d2 þ s2 ðp þ bÞðAp2 þ Bp þ s2 Þ
After Laplace inversion, as explained in the appendix, we have

0 1
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi!
B ebt e2A Bt t B2 4As2 C
rffiffiffiffi B cosh C
B 2A C
B C
2 I d
Uðs; tÞ ¼ 2 02 B p ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi !C [79]
p d þ s Ab Bb þ s B
2 2
2Ab B t B 4As C
C
B 2 2
@ þ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi e2A sinh
Bt
A
B 4As
2 2 2A
Then, the final solution is the inverse Fourier-Cos transform to U(s,t), i.e.,
rffiffiffiffi ZN
2
Tðx; tÞ ¼ Uðs; tÞcosðsxÞds [80]
p
0
There are two positive singularities for U(s,t), which are given as:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
B
sg1 ¼ Bb Ab2 and sg2 ¼ pffiffiffi:
2 A
Hence, the final solution can be given by the closed form
rffiffiffiffi Zsg1 Zsg2 ZN !
2
Tðx; tÞ ¼ Uðs; tÞcosðsxÞds þ Uðs; tÞcosðsxÞds þ Uðs; tÞcosðsxÞds [81]
p
0 sg1 sg2
where U(s,t) is given by eqn [79]. This integral can be numerically evaluated to obtain the value of T(x,t) at given (x,t). To do so, note
that although the range of integration is from 0 to infinity, U(s,t) generally decays with s, so one can ‘truncate’ the integral at a certain
finite (but large enough) value of s.
There are two positive singularities for U(s,t), so we rewrite the integral as a sum of three improper integrals then we numerically
evaluate them by using adaptive Gauss-Kronrod quadrature (20). This method is included in MATLAB, where the function
quadgk(fun,a,b,’RelTol’,1e-6,’AbsTol’,1e-6) attempts to approximate the integral of a scalar-valued function fun from a to b using
high-order global adaptive quadrature and take both relative error tolerance and absolute error tolerance as 106.
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7.02.5 Findings and Discussions
The findings of the electron kinetic theory and stress equations were presented earlier and follow the findings of the radiative
phonon transport equation under the appropriate subheading and in line with previous studies (17,21). In the solution of the
hyperbolic equation based on the kinetic theory approach, the surface heat source is considered. In addition, the free stress
condition is incorporated to account for the free expansion of the surface under the thermal load. The surface heat source assumes
the deposition of energy at the irradiated surface by the external source.
7.02.5.1 Micro/Nano Scale Energy Transport and Stress Fields after Incorporating the Electron Kinetic Theory Approach
The stress-free boundary condition represents the free expansions of the film at the surface. The discussions will be presented in line
with the previous study (17). Table 1 gives the parameters used in the simulations.
Figure 2 shows dimensionless lattice site temperature distribution inside the substrate material for different dimensionless heating
times. Lattice temperature increases along the x-axis due to energy gain from the excited electrons through the collision process. Since
electrons undergo several collisions with increasing distance, lattice site temperature accordingly increases along the x-axis. As the
heating period further increases, lattice site temperature increase becomes almost steady inside the substrate material. Temperature
gradient is high in the early heating period due to the high rate of energy gain of the lattice site from electrons through the collision
process in the early heating period. The temperature gradient gradually reduces along the x-axis as the heating time progresses.
Table 1 Properties used in the solution of temperature and stress fields
Property Numerical value
Cl 2.8 106 J m3 K1

Ce 2.1 104 J m3 K1
G 2.6 1016 W m3 K1
k 315 W m1 K1
d 109 m1
d 0.03 1013 s1
sp 0.024 1012 s
T0 300 K
q0 1
I0 1013 W m2
E 207 109 Pa
r 7930 kg m3
aTl 16 106 K1
n 0.3
Figure 2 Dimensionless lattice site temperature distribution inside the substrate material for different dimensionless heating periods. Reproduced
from Yilbas, B. S.; Al-Dweik, A. Y. Closed Form Solutions for Thermal Stress Field due to Non-Equilibrium Heating during Laser Short-Pulse Irradiation.
Phys. B Condens. Matter 2012, 407 (12), 2169–2175.
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Figure 3 Temporal variation of dimensionless stress at different dimensionless locations inside the substrate material for free stress at the surface.
Reproduced from Yilbas, B. S.; Al-Dweik, A. Y. Closed Form Solutions for Thermal Stress Field due to Non-Equilibrium Heating during Laser Short-Pulse
Irradiation. Phys. B Condens. Matter 2012, 407 (12), 2169–2175.
Figure 3 shows temporal variation of dimensionless thermal stress at different dimensionless locations inside the substrate
material. Temporal behavior of thermal stress is in the wave form and it propagates at a constant speed into the substrate material.
The maximum amplitude of the thermal stress slightly increases with progressing time, which is attributed to the temperature
gradient developed in the substrate material that modifies the stress field in the substrate material. The rise in the stress amplitude is
higher than its decay in the stress wave. This indicates that the stress wave gradually dies with progressing time while it propagates
into the substrate material. In addition, the thermal stress generated is compressive in the surface region, i.e., stress value is negative.
As the heating period progresses, it becomes tensile, i.e., stress value becomes positive. The compressive stress initiation at some
depth below the surface (x > 0) reveals that material undergoes contractions due to sudden thermal expansion of the surface. As the
heating period progresses, the temperature field inside the substrate increases resulting in thermal expansion of the substrate
material where it is initially compressed by the thermal expansion of the surface. Consequently, compressive stress is replaced with
tensile stress in the surface region with progressing time. The magnitude of compressive stress reduces with progressing time, which
is attributed to the high temperature gradient (dT/dx) developed in the solid bulk with progressing time.
Figure 4 shows dimensionless stress distribution inside the substrate material for different dimensionless heating periods.
Thermal stress is tensile in the surface region and it becomes compressive as the distance from the surface increases toward the solid
bulk. The tensile behavior of thermal stress is attributed to thermal expansion of the surface, since the stress-free boundary condition
is considered at the surface. As the heating progresses, the region of tensile stress extends further inside the substrate material. This is
because of the extension of the heated region inside the substrate material with progressing time. Therefore, the thermally expanded
region extends further inside the substrate material resulting in tensile stress in this region. The maximum magnitude of dimen-
sionless tensile stress is on the order of 30, which is about 20 MPa in a dimensional form. The maximum tensile stress is less than the
yielding limit of the substrate material and a crack does not form at the surface vicinity.
7.02.5.2 Temperature Field due to the Solution of Radiative Phonon Transport

The analysis presented below incorporates the volume heat source in line with the previous study (21). The heat pulse applied
externally forms the volumetric heat source inside the substrate material and exponentially decays with progressing time. The
physical properties used in the simulations are given in Table 2.
Figure 5 shows temporal variation of temperature for different depths below the surface for the heat pulse parameter,
ðb ¼ 0:05 1013 s1 Þ. The rate of temperature rise is high in the early heating period, which is more pronounced at the surface
(x ¼ 0 m). As time progresses, temperature rise becomes gradual. The rapid rise of temperature in the initial heating period is
associated with the internal energy gain of the substrate material due to the volumetric heat source. However, heat conduction
due to the wave motion accelerates the heat transfer from the surface region to the solid bulk. In addition, the heat pulse energy
decays with increasing time, which, in turn, results in less absorbed heat energy in the surface vicinity of the substrate material in
the late heating periods. Consequently, the energy transfer from the surface region through the wave nature of the heat
conduction and less absorbed energy within the surface vicinity lowers the rate of temperature rise in the surface region with
progressing time.
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Figure 4 Dimensionless stress distribution inside the substrate material for different dimensionless heating periods and for free stress at the
surface. Reproduced from Yilbas, B. S.; Al-Dweik, A. Y. Closed Form Solutions for Thermal Stress Field due to Non-Equilibrium Heating during Laser
Short-Pulse Irradiation. Phys. B Condens. Matter 2012, 407 (12), 2169–2175.
Table 2 Properties used in the simulations

1
2
a (m s ) b (s1) d (m1) I00 (W m2) A (s2 m2) B (s m2)
0.227 104 0.05 1013 & 0.15 1013 6.16 107 0.6 1020 2.1 1010 44052.86
800
Distance = 0 m Beta = 0.05E13 1/s

Distance = 16.2 nm
600 Distance = 32.3 nm
Temperature (K)
Distance = 78.7 nm
400
200
0
0.0E+00 3.0E-13 6.0E-13 9.0E-13 1.2E-12
Time (s)
Figure 5 Temporal variation of temperature at different depths below the surface. Reproduced from Yilbas, B. S.; Al-Dweik, A. Y.; Bin Mansour, S.
Analytical Solution of Hyperbolic Heat Conduction Equation in Relation to Laser Short-Pulse Heating. Phys. B 2011, 406 (8), 1550–1555.
Figure 6 shows temperature distribution inside the substrate material at different heating periods for the heat pulse parameter,
ðb ¼ 0:05 1013 s1 Þ. Temperature gradually decays in the surface region and it becomes sharp as the distance from the surface
increases toward the solid bulk. The gradual decay of the temperature in the surface region is attributed to the volumetric heat
source in the hyperbolic conduction equation. In this case, energy absorbed from the irradiated field increases the internal energy
gain of the substrate material in the surface region. As the distance from the surface increases beyond the absorption depth, energy
gain by the substrate material is governed by the wave form of the heat conduction, since absorbed energy from the irradiated
heat pulse energy almost diminishes at this depth. However, temperature decay becomes sharp at some depth below the surface as
the heating period progresses. This is attributed to less energy gain from the irradiated field with progressing time in the surface
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800
Time = 0.81 ps
Time = 0.40 ps
Beta = 0.05E13 1/s
600 Time = 0.27 ps
Temperature (K)
Time = 0.20 ps
400
200
0
0.0E+00 5.0E-09 1.0E-08 1.5E-08 2.0E-08 2.5E-08
Distance (m)
Figure 6 Temperature distribution inside the substrate material for different heating durations. Reproduced from Yilbas, B. S.; Al-Dweik, A. Y.;
Bin Mansour, S. Analytical Solution of Hyperbolic Heat Conduction Equation in Relation to Laser Short-Pulse Heating. Phys. B 2011, 406 (8),
1550–1555.
region. Consequently, energy transfer through conduction from the surface vicinity to the solid bulk increases with progressing
time. In addition, the rate of energy gain from the irradiated field is larger than the energy transfer through conduction from the
surface region to the solid bulk. This is more pronounced in the early heating period when the heat pulse intensity reaches its
peak; which in turn, results in increasing temperature difference between the surface region and the solid bulk. Since the heat
conduction is not only governed by the classical diffusion, the wave nature of the heat transfer, temperature decay becomes sharp
inside the substrate material during the long heating periods.
The conclusions derived from the present study are divided into two sections in line with the findings of the electron kinetic theory
approach and the equation for the radiative phonon transport. Therefore, the concluding remarks are presented into two
subheadings.
7.02.6.1 Electron Kinetic Theory Approach

Temperature rise in the early heating period is gradual. As the heating period progresses, temperature rapidly rises reaching its
maximum, which is more pronounced at the surface. The time occurrence of the peak temperature changes as the distance below the
surface increases. Temperature decay rate becomes small when the pulse intensity reduces 5% of its peak value. In this case, the
temporal gradient of temperature becomes small and the wave nature of the heating is replaced with the diffusion heating.
Temperature decay is sharp inside the substrate material during the heating cycle. This results in large temperature gradients and
stress fields below the surface. Temporal behavior of thermal stress reveals that the compressive stress waves are formed due to initial
contraction of the surface during the early heating period. The compression wave rapidly reaches its peak value and gradually decays
similar to the pulse intensity distribution. The generated stress wave propagates at a constant speed inside the substrate material. The
thermal expansion of the surface during the late heating period results in the tensile wave formation in the surface region. This
appears as a tensile tail in the compressive wave generated earlier. The magnitude of the tensile wave is significantly lower than that
of the compressive wave.
7.02.6.2 Radiative Phonon Transport

Temperature rapidly rises in the surface region, which is associated with the internal energy gain from the irradiated field in this
region. Temperature decay is gradual in the surface region and it sharply decays as the depth below the surface increases. Conse-
quently, temperature in the region below the absorption depth sharply reduces, since the internal energy gain of the substrate
material is due to the wave nature of the heat conduction only in this region. This is more pronounced at long heating periods.
Acknowledgments
The authors acknowledge the support of King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia, for this work.
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15. Yilbas, B. S. Improved Formulation of Electron Kinetic Theory Approach for Laser Short-pulse Heating. Int. J. Heat Mass Tran. 2006, 49 (13–14), 2227–2238.
16. Chen, G. Ballistic-Diffusive Heat-Conduction Equations. Phys. Rev. Lett. 2001, 86, 2297–2300.
17. Yilbas, B. S.; Al-Dweik, A. Y. Closed Form Solutions for Thermal Stress Field ue to Non-Equilibrium Heating during Laser Short-Pulse Irradiation. Phys. B Condens. Matter 2012,
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18. Kovalenko, A. Thermoelasticity (Basic Theory and Applications); Wolters-Noordhoff, Publishing: Groningen, The Netherlands, 1969.
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7.03 Thermal Stresses in Micro- and Nanostructures
BS Yilbas, King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
7.03.2 Analytical Treatment of Thermal Stresses at Micro/Nanosized Length Scales 22
7.03.2.1 Analysis of Temperature Field 22
7.03.2.2 Analysis of Stress Field 25
7.03.2.2.1 Stress-Free Boundary Condition 26
7.03.2.2.2 Stress Continuity Boundary Condition at the Surface 27
7.03.3 Analytical Approach Incorporating Elastoplastic Analysis 28
7.03.3.1 Analytical Formulation of Temperature Field due to High Intensity Laser Irradiation 28
7.03.3.2 Elastoplastic Stress Analysis due to High Power Laser Irradiation 29
7.03.4 Analytical Solution for Thermal Stress Incorporating Thermomechanical Coupling 32
7.03.5 Analysis of Plastic Wave Generation and Propagation due to High Intensity Pulse 35
7.03.5.1 Heating and Phase Change Analysis 35
7.03.5.2 Transiently Developing Vapor Jet 36
7.03.5.2.1 Continuity Equation 36
7.03.5.2.2 Radial Momentum 37
7.03.5.2.3 Axial Momentum 37
7.03.5.2.4 Energy Equation 37
7.03.5.2.5 Turbulence Kinetic Energy Equation, K 37
7.03.5.2.6 Rate of Dissipation Equation, ε 38
7.03.5.2.7 Species Transport Equation 38
7.03.5.2.8 Initial and Boundary Conditions 38
7.03.5.2.9 Numerical Solution 39
7.03.5.3 Elastoplastic Analysis 39
7.03.6 Findings and Discussion 40
7.03.6.1 Analytical Treatment of Thermal Stresses at Micro/Nanosized Length Scales 40
7.03.6.2 Temperature and Stress Fields due to High Intensity Laser Irradiation 41
7.03.6.3 Influence of Thermomechanical Coupling on Temperature and Stress Fields 42
7.03.6.4 Plastic Wave Generation and Its Propagation due to High Intensity Pulse Radiation 44
References 46
7.03.1 Introduction
Micro/nanostructures are widely used in the electronic and energy sectors because of the requirements of small devices in practical
applications. In addition, these structures find application in sensor technology and medicine. In order to generate or form such
structures, the challenges in manufacturing become unavoidable. One of the methods of developing micro/nanotextures is to use
high-energy beams through thermal processing. Although the process is rapid, high temperature gradients formed generate excessive
thermal stress levels during the process. Moreover, high-energy beams provide precision of operation, low cost, and local treatment.
These advantages make high-energy beams one of the possible processing techniques for micro/nanoscale manufacturing. Laser at
high power is one of the popular high-energy beam resources for manufacturing or texturizing the micro/nanoscale devices and
surfaces. The surface irradiation at short pulses with high energies causes generation of high heat fluxes in the irradiated region. Since
the process is rapid and involves high temperature, experimenting with the heating process requires expensive equipment and high
skill. On the other hand, laser heating analysis gives insight into the physical process that takes place during the laser heating pulse.
Depending upon the laser pulse intensity, the heating process can be classified as nonconduction limited or conduction limited
heating. In conduction limited heating, substrate material remains in the solid phase while phase change (melting and evaporation)
occurs in the nonconduction limited heating. As the substrate material is heated, its temperature rises to elevated temperatures,
which in turn results in thermal expansion of the substrate material. Consequently, depending on the thermal strain developed,
stress levels well in excess of elastic limit of the substrate material can be resulted. Moreover, since the process is transient, the stress
wave generated propagates into the substrate material. The thermal stress is, in general, generated in the solid substrate, since
substrate material in the liquid phase expands freely during the heating process. Consequently, regardless of the type of heating
process, thermal stress develops only in the solid phase of the substrate material. Since the analytical solution to the heating and
thermal stress problems provides useful information to reduce experimental time and cost, analytical investigation into the heating
problem is fruitful.

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22 Thermal Stresses in Micro- and Nanostructures
Considerable research studies were carried out to examine laser processing and thermal stress analysis (1–20). The main focus of
the previous studies is numerical modeling of thermal stresses during laser processing, which mainly deal with the uncoupled
thermal analysis. Although uncoupled analysis provides useful information on temperature and stress fields, it may not be very
appropriate for the time scale of irradiation less than the thermalization time of the substrate material. Therefore, care must be taken
when modeling the heating situation while incorporating the stress analysis. In addition, one of the methods forming the hard
surfaces at micro/nanosizes is rapid ablation of the surface by high-energy beams. In this case, the recoil pressure developed at the
interface of the ablated surface causes the generation of the plastic waves propagating into the substrate material. Since
the amplitude of the plastic wave is high, it creates metallurgical deformation in the vicinity of the ablated surface while modifying
the mechanical properties in this region. Therefore, the analysis of rapid vapor front generation and its propagation becomes
important for micro/nanoscale manufacturing using high-energy beams.
In this chapter, thermal analysis and stress fields generated during the laser irradiation of the surfaces are presented in relation to
the micro/nanoscale processing. The model studies associated with the various heating situations and the stress fields are presented
analytically and numerically. Although the analytical solutions to the heating and stress problems provide functional relations
between the response and the affecting parameters, solutions are limited with the certain assumptions and the boundary conditions.
On the other hand, numerical solution to the problem provides detailed insight into the physical process; it is costly and requires
excessive computation power to capture the physical insight. Since the analytical solution complements the numerical computation
of the problem, the analyses, including analytical and numerical approaches, are provided in this chapter. The plastic wave analysis
is also included to explore the microdefects in the micro/nanosizes formed during laser processing.
7.03.2 Analytical Treatment of Thermal Stresses at Micro/Nanosized Length Scales
When the size of the device becomes comparable to the characteristic length of the substrate material, such as the mean free path,
equilibrium processes are replaced with the nonequilibrium processes in the device. In addition, if the time of the process becomes
comparable to the thermalization time of the substrate material, the same effect takes place in the process. Consequently,
nonequilibrium transport in a thermal system needs to be incorporated into the analysis. Therefore, the governing equations
incorporated in the analytical approach need to be modified to include the nonequilibrium effects in line with previous studies
(21,22,29,31).
7.03.2.1 Analysis of Temperature Field

Laser short-pulse heating involved with time duration less than the thermalization time of the substrate material. In this case, the
Fourier heating law fails to predict correctly temperature rise in the substrate material. This is because of the assumption of infinite
heat wave speed and parabolic nature of the formulation of heating problem. Therefore, care must be taken to formulate the heating
problem at micro/nanolevels by incorporating nonequilibrium heat transport in the thermal system during the heating process. In
this section, mathematical formulation of the laser short-pulse heating of solid substrates is given, in line with previous studies
(21,22).
Consider the metallic substrates subjected to the laser irradiation pulse. Thermal separation of electron and lattice subsystems
modifies the energy equation to include thermal communication of the subsystems. Since the electrons undergo multiple collisions
with the lattice site, energy transport equation should be written in the integral form to allow the probability of the number of
collisions taking place in the irradiated region. The energy transfer in such a situation can be formulated as (23)
ZN Yð2s xÞ jx sj ZN Yð2s xÞ jx sj

DEtrans VfkB VfkB
¼ N sx 1 j exp T e ðs; tÞds Nsx 1 j exp Tl ðx; tÞds
AdxDt l2 2x l l2 2x l
N N
ZN Zs
I0 f Nsx jx sj
l2 Nsx þ Nxs l
N x
[1]
where

Qð2s xÞ
1j
Nsx x
¼ [2]
Nsx þ Nxs 2j
where f is the fraction of electron excess energy, which transfers to the lattice site during a single electron lattice site collision. The first
term on the left-hand side of eqn [1] is energy gain by the substrate material through the collisional process, the first and second
terms on the right-hand side represent electron and lattice energies, and the third term on the right-hand side is the energy gain of
the electrons due to the irradiated field.
The final temperature of the electrons in dx after the collisional process can be readily found from the conservation of energy, i.e.,
Total electron energy after collision ¼ Total electron energy in during dt Change of lattice site energy
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Thermal Stresses in Micro- and Nanostructures 23
Total electron energy after collision is

ZN Yð2s xÞ jx sj
VkB
N sx 1 j exp ðTe ðs; tÞ fTl ðx; tÞÞds [3]
l2 2x l
N
Total electron energy carried into dx during dt is

Qð2s xÞ
ZN Yð2s xÞ ZN 1 j Zs
VkB ð1 f Þ jx sj I0 ð1 f Þ 2x jx sj
N sx 1 j exp T e ðs; tÞds þ exp f 0 ðxÞdxds [4]
l2 2x l l2 2j l
N N x
Therefore, the conservation of energy yields

ZN Yð2s xÞ jx sj
VkB
N sx 1 j exp ðTe ðs; tÞ fTl ðx; tÞÞds
l2 2x l
N

Qð2s xÞ
ZN Yð2s xÞ jx sj ZN 1j Zs
VkB ð1 f Þ I0 ð1 f Þ 2x jx sj
¼ Nsx 1j exp Te ðs; tÞds þ exp f 0 ðxÞdxds
l2 2x l l2 2j l
N N x
[5]
Equations [1] and [5] can be rewritten after considering the electron distributions for the lattice element dxdx apart for electrons
passing an area A, i.e.,
ZN ZN Zjxj
DEtrans fk jx sj fk jx sj fk jx sj
¼ exp Te ðs; tÞds exp T l ðx; tÞds þ j exp Tl ðx; tÞds
AdxDt l3 l l3 l l3 l
N N 0
Zjxj ZN Zs
fk jx sj I0 f 1 jx sj
j 3 exp Te ðs; tÞds þ exp f 0 ðxÞdxds [6]
l l l2 ð2 jÞ l
0 N x
ZN Zs
I0 f j jx sj
exp f 0 ðxÞdxds
l2 ð2 jÞ l
N x
and
ZN Zjxj
k jx sj jk jx sj
2 exp l
ðTe ðs; tÞ fTl ðx; tÞÞds 2 exp
l
ðTe ðs; tÞ fTl ðx; tÞÞds
l l
N 0
ZN Zjxj ZN Zs
kð1 f Þ jx sj kð1 f Þ jx sj I0 ð1 f Þ jx sj
¼ exp T e ðs; tÞds exp T e ðs; tÞds þ exp f 0 ðxÞdxds
l2 l l2 l l2 ð2 jÞ l
N 0 N x
Zjxj Zs
I0 ð1 f Þ jx sj
exp f 0 ðxÞdxds [7]
l2 ð2 jÞ l
0 x
where k is the thermal conductivity, which makes use of the simple kinetic theory result for the electron thermal conductivity:
NVkB l
k¼ [8]
3
The energy content of the small lattice site element dx apart can be written as
DE ¼ AdxCl Tl ðx; tÞ [9]

DE DE
where Cl ¼ r Cp. The energy gain of the small lattice element during the small time interval dt is . The expansion of yields (23)
dt dt

DE v ðdtÞ v2
¼ Adx Cl ½Tl ðx; tÞ þ Cl ½T l ðx; tÞ þ . [10]
dt vt 2! vt 2
When the time increment approaches the thermal relaxation time (dt / ss), eqn [10] reduces to

ve DE v v
¼ xCl Tl ðx; tÞ þ ss ðTl ðx; tÞÞ [11]
vt dtAdx vt vt
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where e is the volumetric energy content of lattice site. The energy gain of the small lattice element through collisional energy
transport can also be written as

DE 1 DEtrans v DEtrans
¼ þ ss [12]
AdxDt Adx Dt vt Dt
Substituting eqn [6] into eqn [12] yields the change of lattice site energy, which is
0 1
B ZN ZN C
B fk jx sj fk jx sj C
B exp Te ðs; tÞds exp Tl ðx; tÞds C
B l3 l l3 l C
B N N C
B C
B C
B C
B Zjxj Zjxj C
B þ j exp ðx; ðs; C
B T l tÞds j exp T e tÞds C
B l 3 l l 3 l C
B 0 0 C
DE B C
¼B C
AdxDt B C
B ZN Z s C
B I f 1 jx sj C
B þ
0
exp f 0
ðxÞdxds C
B l2 ð2 jÞ C
B l C
B N x C
B C
B C
B ZN Z C
B s C
B I0 f j jx sj 0 C
B 2 ð2 jÞ exp f ðxÞdxds C
@ l l A
N x
0 1 [13]
B ZN ZN C
B exp T e ðs; tÞds exp Tl ðx; tÞds C
B l3 l l3 l C
B N N C
B C
B C
B C
B Zjxj Zjxj C
B þ j exp Tl ðx; tÞds j 3 exp Te ðs; tÞds C
B C
B l3 l l l C
vB B 0 0 C
C
þ ss B C
vt B C
B ZN Z s C
B I f 1 jx sj C
B þ
0
f 0 ðxÞdxds C
B 2 ð2 jÞ exp C
B l l C
B N x C
B C
B C
B ZN Z C
B s C
B I0 f j jx sj 0 C
B exp f ðxÞdxds C
@ l ð2 jÞ
2 l A
N x
Equations [7] and [13] are the energy transport equations of interest for the laser short-pulse heating process. However, for small
rise of electron temperature during the low intensity laser heating pulse prevents electron escape from the surface. Consequently, the
term j in eqns [7] and [13] becomes zero.
Equations [7] and [13] can be transformed into differential equations. The method of solution to be used in the following
analysis is the transformation of the simultaneous differential–integral eqns [7] and [13] using the Fourier integral transformation,
with respect to x (23). This is due to the fact that the resultant ordinary differential equations may then be handled much more
conveniently. After long algebra, the heat equation for the lattice site becomes (23)

v l2 v2 vT v2 T v v2 Tl v
1 þ ss 2
Cl l ¼ k 2l þ sp 2
þ I0 df expðdjxjÞ þ sp ½I0 df expðdjxjÞ [14]
vt f vx vt vx vt vx vt
Equation [16] is the hyperbolic form of energy equation and to obtain a closed form solution for eqn [14], the following steps
are introduced in line with the previous study (21).
Since the laser irradiated energy is absorbed in the surface vicinity, volumetric source consideration is necessary to resemble the
absorption process. The hyperbolic form of heat equation (eqn [14]) can be written as (23)
2
v l 2 v2 vTL v2 T L v v TL v

1 þ ss
C L
¼ k þ sp
k þ 1 þ sp
ðf dIðt Þexpðdjx jÞÞ [15]
vt f vx
2 vt vx
2 vt vx
2 vt
where ss is the electron–phonon characteristic time (ss ¼ CE/G), G is the electron–phonon coupling factor, l is the mean free path of
the electrons, f is the fraction of excess energy change, CL and CE are the lattice and electron heat capacities, respectively, k is the
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thermal conductivity, sp is the electron mean free time between electron–phonon coupling, IðtÞ ¼ I0 expðdtÞ where I0 is the laser
peak power intensity, expðdtÞ is the temporal distribution function of laser pulse, d is the absorption coefficient, x* is the lattice
depth, t* is the time variable, and TL and TE are the lattice site and electron temperatures, respectively. Introducing the following
equalities and dimensionless variables
fk CE
l2 ¼ ; ss ¼
G G
[16]
TE TL t
kd2 CE
qE ¼ ; qL ¼ ; x ¼ x
d; t ¼ ; a¼ ; ε¼
T0 T0 CE =G G CL
to eqn [15] yields finally
v 3 qL v2 qL v2 qL vqL
að1 þ mÞ 2
þ εa 2 2 b expðxÞexpðgtÞ ¼ 0 [17]
vx vt vx vt vt
where
sp G fI0 dðmg εÞ dCE
m¼ ; b¼ ; g¼ [18]
CL T0 G G
This model is the improved energy transport equation, including ballistic effects with volumetric source in dimensionless form.
Once the lattice site temperature is determined, the electron temperature can be found from (23)
vqL
¼ εðqE qL Þ [19]
vt
Therefore, the energy transport equations for lattice site and electrons are
v 3 qL v2 qL v2 qL vqL
að1 þ mÞ 2
þ εa 2 2 b expðxÞexpðgtÞ ¼ 0
vx vt vx vt vt
[20]
vqL
¼ εðqE qL Þ
vt
Now, assume a semi-infinite substrate material heated. The boundary conditions for the problem can be written as follows:
vqE vqE
ð0; tÞ ¼ 0; ðN; tÞ ¼ 0
vx vx [21]
qE ðx; NÞ ¼ q0 ; qL ðx; NÞ ¼ q0
Yilbas and Dweik (21) constructed the closed form solutions for temperature distribution with volumetric heat sources. The
solution of the boundary value problem can be given, when

ε ε
g>1 & g< or g < 1 & g > as follows:
1þm 1þm
ε
qL ðx; tÞ ¼ q0 þ H expð gðt þ uxÞÞ εH expðx gtÞ
ug
[22]
ðε gÞ
qE ðx; tÞ ¼ q0 þ H expð gðt þ uxÞÞ ðε gÞH expðx gtÞ
ug
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1g b
where u ¼ and H ¼ :
agðgð1 þ mÞ εÞ εðg2 þ gðaðm þ 1Þ 1Þ aεÞ
n ε o
It should be noted that the solution for qL(x,t) and qE(x,t) in eqn [22] is only valid for g > 1 & g < or
1þm
n ε o
g<1 & g> . In this case, ε is of order 102 for metals and g < 1 for the short-pulse heating situation.
1þm
7.03.2.2 Analysis of Stress Field

Thermal stress analysis can be performed for two situations, which are more probable to observe in the practical applications. The
first situation deals with the free surface expansion. In this case, the substrate surface is not constrained by the presence of the
second surface, which is intact with the heated surface. This situation is referred to as the free surface condition. In the second
situation, the heated surface is considered to be in mechanical contact with the semitransparent surface, such as coating or
overlaying. This arrangement results in constrained irradiated surface, which is called the stress continuity condition. In this case,
it is assumed that the stress formed due to thermal expansion at the irradiated surface continues at the interface of the contacting
other surface.
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The equation governing the momentum in a one-dimensional solid for a linear elastic case can be written as (24)
v2 sx
1 v2 sx
v 2 TL

2
2
2 ¼ c2
2 [23]
vx c1 vt vt
where c1 is the wave speed in the solid.
sffiffiffi
E 1þn
c1 ¼ and c2 ¼ raTL
r 1n
where n is Poisson’s ratio, r is the density of the solid, and aTL is the thermal expansion coefficient of the solid.
Our goal in this paper will be solving eqn [23] to find the exact solution for thermal stresses corresponding to the closed form
solutions for temperature distribution qL with volumetric heat sources. So by using the dimensionless variables in eqn [16], the
d2
dimensionless stress is sx ¼ sx
. Equation [23] can be rewritten after incorporation eqn [22], in which temperature is pre-
c2 d2 T0
sented. Therefore, eqn [23] becomes

v 2 sx 2
2 v sx 1
A ¼ B 2
expðgt guxÞ expðgt xÞ [24]
vx2 vt 2 gu
d pffiffiffiffiffiffiffiffiffiffi
where A ¼ and B ¼ εH:
c1 gd
The initial conditions for eqn [24] are as follows:
sx ðx; 0Þ ¼ 0; sx ðx; NÞ ¼ 0 [25]
Now, applying the Fourier sine transform for eqn [24] with respect to t, by requiring that, for a physically meaningful system,
sx(x,t) and its first derivatives in t vanish as t approaches; therefore, it results in
v2 2 2 2 B2 ðexpðguxÞ gu expðxÞÞ
Uðx; pÞ A ps x ðx; 0Þ þ A 2 2
p Uðx; pÞ ¼ p [26]
vx2 p p gu g 2 þ p2
where p is the Fourier sine variable and U(x,p) is the Fourier sine of sx(x,t) with respect to t, which is defined by
2 RN 2 RN
Uðx; pÞ ¼ s x ðx; tÞsinðptÞdt, and the inverse Fourier sine of sx(x,t) is given by sx ðx; tÞ ¼ Uðx; pÞsinðptÞdp:
p 0 p 0
By applying the initial conditions for eqn [26], one can get
rffiffiffiffi
v2 2 2 2 B2 ðexpðguxÞ gu expðxÞÞ
Uðx; pÞ þ A p Uðx; pÞ ¼ p [27]
vx2 p gu g2 þ p2
For boundary conditions, two cases are considered.
7.03.2.2.1 Stress-Free Boundary Condition

The thermal stress at the surface is set to zero. The relevant boundary conditions are
sx ð0; tÞ ¼ 0; sx ðN; tÞ ¼ 0 [28]
Now, applying the Fourier sine transform for eqn [27] with respect to x, by requiring that, for a physically meaningful system,
sx(x,t) and its first derivatives in x vanish as x / N results in
rffiffiffiffi
2 2B2 p s s
sUð0; pÞ s2 Vðs; pÞ þ A2 p2 Vðs; pÞ ¼ gu [29]
p pgu ðp2 þ g2 Þ s2 þ g2 u2 s2 þ 1
where s is the Fourier sine variable and V(s,p) is the Fourier sine of U(x,p) with respect to x, which is defined by
2 RN 2 RN
Vðs; pÞ ¼ Uðx; pÞsinðsxÞdx, and the inverse Fourier sine of sx(x,t) is given by Uðx; pÞ ¼ Vðs; pÞsinðsxÞds:
p 0 p 0
rffiffiffiffi
2 RN
p 0
Uð0; pÞ ¼ 0 [30]
So, eqn [15] will reduce to
2B2 p s s
Vðs; pÞ ¼ gu 2 [31]
pgu ðp þ g Þðs A p Þ s þ g u
2 2 2 2 2 2 2 2 s þ1
Applying the inverse Fourier sine transform for eqn [31] with respect to x yields
2 B2 pðcosðApxÞ expð guxÞÞ 2 2 pðcosðApxÞ expð xÞÞ
Uðx; pÞ ¼ 2 u2 B [32]
p gu 2 2 g p 1
A ðp þ g2 Þ p2 þ 2 A2 ðp2 þ g2 Þ p2 þ 2
A A
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Applying the inverse Fourier sine transform for eqn [32] with respect to t yields
8
>
> B2
>
> gt
gu t
gux gt
gu t
þ
>
> e coshðgAxÞ e A coshðguxÞ e e e A
>
> g3 uðu2 A2 Þ
>
>
>
> ; t Ax
>
>
>
>
>
> B2
> egt coshðgAxÞ þ eA t coshðxÞ þ ex egt eA t
1 1
>
< ð1 A2 g2 Þ
sx ðx; tÞ ¼ [33]
>
> B2 gu
>
> gAx
þ gux
gux gt
gu t
þ
>
> g3 uðu2 A2 Þ
e sinhðgtÞ e sinh t e e e A
>
> A
>
>
>
> ; t < Ax
>
>
>
>
> B2 1
>
> gAx
x
þ x gt
A1 t
>
: ð1 A2 g2 Þ
e sinhðgtÞ e sinh
A
t e e e
7.03.2.2.2 Stress Continuity Boundary Condition at the Surface

The thermal stress gradient at the surface is set to zero. The relevant boundary conditions are
vsx
ð0; tÞ ¼ 0; sx ðN; tÞ ¼ 0 [34]
vx
Now, applying the Fourier cosine transform for eqn [27] with respect to x, by requiring that, for a physically meaningful system,
sx(x,t) and its first derivatives in x vanish as x approaches N. This results in
rffiffiffiffi
2 v 2 p 1 1
Uð0; pÞ s2 Wðs; pÞ þ A2 p2 Wðs; pÞ ¼ B2 2 2 [35]
p vx p ðp þ g Þ s þ g u
2 2 2 2 s þ1
where s is Fourier cosine variable and W(s,p) is the Fourier cosine of U(x,p) with respect to x, which is defined by
2 RN 2 RN
Wðs; pÞ ¼ Uðx; pÞcosðsxÞdx, and the inverse Fourier cosine of sx(x,t) is given by Uðx; pÞ ¼ Wðs; pÞcosðsxÞds:
p 0 p 0
rffiffiffiffi
2 RN
p 0
v
Uð0; pÞ ¼ 0 [36]
vx

2 p 1 1
Wðs; pÞ ¼ B2 2 2 [37]
p ðp þ g Þðs A p Þ s þ g u
2 2 2 2 2 2 2 s þ1
Applying the inverse Fourier cosine transform for eqn [37] with respect to x gives
2 B2 ðA expð guxÞp þ gu sinðAxpÞÞ 2 B2 ðA expð xÞp þ sinðAxpÞÞ
Uðx; pÞ ¼ 3
2 2 þ [38]
p guA g u p A3 1
ðp2 þ g2 Þ p2 þ 2 ðp2 þ g2 Þ p2 þ 2
A A
Applying the inverse Fourier sine transform for eqn [38] with respect to t, one can have
8
>
> u
>
> B2
egt sinhðgAxÞ þ e A t sinhðguxÞ expð guxÞ egt e A t þ
gu gu
>
>
>
> g 3 uðu2 A2 Þ A
>
>
>
> ; t Ax
>
>
>
>
> B2 1 gt
>
> e sinhðgAxÞ eA t sinhðxÞ þ expð xÞ egt eA t
1 1
>
< ð1 A g Þ Ag
2 2
sx ðx; tÞ ¼ [39]
>
> B2 u gu
>
> egAx sinhðgtÞ þ egux sinh t exp gux egt e A t þ
gu
>
>
>
> g3 uðu2 A2 Þ A A
>
>
>
> ; t < Ax
>
>
>
> B2
>
> 1 gAx 1
sinhðgtÞ ex sinh t þ expð xÞ egt eA t
1
>
> e
: ð1 A g Þ Ag
2 2 A
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Equations [33] and [39] provide the closed form solutions for thermal stresses formed at micro/nanoscale depth inside the
substrate material subjected to laser short-pulse irradiation.
7.03.3 Analytical Approach Incorporating Elastoplastic Analysis
In laser heating applications at micro/nanoscales, the heat transfer results in excessive temperature gradients in the irradiated region.
This particularly occurs at high intensity radiations. In this case, the material behavior changes from elastic to plastic while causing
mechanical energy storage in the irradiated region. This alters the microstructure and hardness in the irradiated region. Therefore,
investigation into high intensity laser short-pulse heating and thermal stress analysis becomes essential. The analytical approach for
a high intensity exponential pulse heating situation is presented, and the resulting temperature field is incorporated into the
elastoplatic analysis in line with the previous study (25).
7.03.3.1 Analytical Formulation of Temperature Field due to High Intensity Laser Irradiation
The heat equation for a laser pulse decaying exponentially with time can be written as
v2 T I1 d bt dx 1 vT
þ e e ¼ [40]
vx2 k a vt
where I1 ¼ (1 rf)I0.
The substrate material is considered a semi-infinite body and heated by a laser beam on the surface. The convective
boundary condition is assumed to be on the substrate surface. In addition, the depth is considered to extend to infinity and
the temperature to go down to zero. Heating occurs in the surface region during the laser pulse. Therefore, the corresponding
boundary conditions are

vT h
At x ¼ 0 0 ¼ ðTð0; tÞ T0 Þ [41]
vx x¼0 k
and
At x ¼ N 0 TðN; tÞ ¼ 0 [42]
Initially, substrate material is assumed to be at uniform temperature. Therefore, the initial condition is
At t ¼ 0 0 Tðx; 0Þ ¼ 0 [43]
The Laplace transformation of eqn [40] with respect to t results in
v2 T I1 d edx 1
þ ¼ sTðx; sÞ Tðx; 0Þ [44]
vx2 k ðs þ bÞ a
Introducing the initial condition and rearranging the equation yields
v2 T I1 d edx
g2 T ¼ [45]
vx2 k ðs þ bÞ
where g2 ¼ s/a and s is the Laplace transform variable. Equation [45] has the solution
I1 dedx
Tðx; sÞ ¼ A1 egx þ A2 egx [46]
kðs þ bÞ d2 g 2
where A1 and A2 are constants. Introducing the boundary conditions will enable calculation of the constants A1 and A2, i.e., A1 ¼ 0,
and
I1 dðh þ dkÞ hT0

A2 ¼ þ [47]
kðs þ bÞ d2 g 2 ðh þ kgÞ sðh þ kgÞ
After substituting the values of A1 and A2 in eqn [46], it yields
I1 dðh þ dkÞegx hT0 egx I1 dedx

Tðx; sÞ ¼ 2 þ 2 [48]
kðs þ bÞ d g ðh þ kgÞ sðh þ kgÞ k d g 2 ðs þ bÞ
2
which gives the solution for the temperature distribution in the Laplace domain.
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The inverse Laplace transform of eqn [48] provides the temperature distribution within the substrate material in space (x) and
time (t). The mathematical arrangements of the Laplace inversion of eqn [48] are given in the previous study (26). Therefore, the
equation after the Laplace inversion is given as
8 9
>
> ð Þ x pffiffiffiffiffi ð Þ x pffiffiffiffiffi >
>
> e >
2 2
>
>
ad tdx
erfc pffiffiffiffiffi d at e ad tþdx
erfc pffiffiffiffiffi d at >
>
>
> 2 at 2 at >
>
>
> pffiffiffi pffiffiffi >
>
>
> h a p ffiffiffi h a p ffiffiffi >
>
>
> 2 b þ ad 2
þd a 2 b þ ad 2
þd a >
>
>
> >
>
>
>
k k >
>
>
> >
>
>
> >
>
>
> p ffiffiffiffiffiffiffiffiffiffiffi
ffi p ffiffiffiffiffiffiffiffiffiffiffi
ffi >
>
>
> x p ffiffiffiffi
ffi x p ffiffiffiffi
ffi >
>
>
> bt ðb=aÞxi erfc p ffiffiffiffi
ffi þ bt i bt ðb=aÞxi erfc p ffiffiffiffi
ffi bt i > >
I1 da ðh þ kdÞ
3=2 < e e e e =
2 at 2 at
Tðx; tÞ ¼ þ p ffiffiffi þ p ffiffiffi
k 2 >
> h a pffiffiffi h a pffiffiffi >
>
>
> 2 b þ ad2 bi 2 b þ ad2 þ bi >
> [49]
>
> k k >
>
>
> >
>
>
> >
>
>
> >
>
>
> >
>
>
> x h pffiffiffiffiffi >
>
>
> p ffiffiffi e hx=k e ðh 2
=k2
Þat erfc p ffiffiffiffi
ffi þ at dx ad2
bt >
>
>
> h a k ke e t e >
>
>
> þ
2 at
p ffiffiffi >
>
>
> >
>
>
> k h a2 h a2
a b þ ad ðh þ kdÞ
2
>
>
>
: þ b ad 2 >
;
k2 k2
h
x x h pffiffiffiffiffi
þ T0 erfc pffiffiffiffiffi ehx=k eðh =k Þat erfc pffiffiffiffiffi þ
2 2
at
2 at 2 at k
where erfc is the complementary error function. Equation [49] is the closed form solution for temperature distribution. The
temperature distribution can be expressed in a nondimensional form by introducing dimensionless quantities and substituting in
eqn [49]. The dimensionless quantities are
Tkd h
x
¼ xd : t
¼ ad2 t : T
¼ : h
¼ : b
¼ bt [50]
I1 dk
The dimensionless temperature distribution for a full pulse is then
8

pffiffiffiffi
3 9
> 2 x pffiffiffiffi x pffiffiffiffi x pffiffiffiffiffiffiffiffi
ffi >
>
> e x
et
erfc p ffiffiffiffi t
e x
et
erfc p ffiffiffiffi t
e b
e b
x
i erfc p ffiffiffiffi

t i >
>
>
> 6

b
7 >
>
>
> 2 t 2 t 2 t pffiffiffiffiffi
7 >
>
>
> 6

þ >
>
>
> 6 2ðb þ 1Þðh
þ 1Þ 2ðb þ 1Þðh
1Þ 2ðb
þ 1Þ h
b i 7 >
>
>6
> 7 >
>
>
> 6 7 >
>
>
> 6 7 >
>
>
> 6 p ffiffiffi
ffi 7 >
>
>
> 6 x
p ffiffiffiffiffiffiffiffi
ffi x
p ffiffiffiffi 7 >
>
> 6

7 >
2
b t e b x i erfc p ffiffiffiffi
eh x eðh Þ t erfc p ffiffiffiffi
t
>
> 4 e b t i h h x et eb t 5

>
>
>
> 2 t
2 t
e >
>
>
> þ p ffiffiffiffiffi þ >
>
>
< 2ðb
þ 1Þ h
þ b
i 2 ðh
Þ2 þ b
ðh
Þ2 1 ðb
þ 1Þðh
þ 1Þ >
=
T
ðx
; t
Þ ¼ ðh
þ 1Þ

>
> 2 pffiffiffiffi pffiffiffiffi pffiffiffiffi pffiffiffiffiffiffiffiffiffi 3>>
>
> x
et
erfc x x
et
erfc x g
e g
x
i erfc x >
>
>
> e p ffiffiffiffi t
e p ffiffiffiffi t
e p ffiffiffiffi g
t
i >
>
>
> 6 2 t
2 t
2 t
7 >
>
>
> 6 þ p ffiffiffiffiffi 7 >
>
>
> 6
2ðg þ 1Þðh þ 1Þ

2ðg þ 1Þðh 1Þ

2ðg þ 1Þðh g iÞ

7 >
>
>
> 6 7 >
>
>
> 6 7 >
>
> 6
> 7 >
>
>
> 6 7 >
>
>
> 6 pffiffiffiffi x
pffiffiffiffiffiffiffiffiffi x
p ffiffiffiffi 7 >
>
>
> 4 eg

t e g
x
i
erfc p ffiffiffiffi
t
i h
eh

x e ðh
2
Þ t erfc p ffiffiffiffi h
t

>

5 >
>
>
x et eg t >

>
>
> 2 t
pffiffiffiffiffi
2 t e >
>
>
: þ þ
þ 1Þðh
þ 1Þ >
;
2ðg
þ 1Þðh
þ g
iÞ
2
2 ðh Þ þ g ðh Þ 1

2 ðg
[51]
Equation [51] provides the closed form solution of temperature field for the exponentially decaying pulse, which can be
incorporated in the elastoplastic stress analysis.
7.03.3.2 Elastoplastic Stress Analysis due to High Power Laser Irradiation

Surface evaporation is resulted at high power intensities, and the vapor phase front departs from the surface with the velocity Ve and
the workpiece recesses towards the solid substrate with a velocity V because of the material removal from the surface during
evaporation. This situation allows one to write a momentum exchange across the vapor–solid interface. The heat equation involving
the vapor front generation can be written as
v2 T vT vT
k þ rCp V þ I0 1 rf expð btÞd expð dxÞ ¼ rCp [52]
vx2 vx vt
where Cp is the specific heat capacity, k is the thermal conductivity, V is the recession velocity, I0 is the laser peak intensity, rf is the
surface reflectivity, d is the absorption depth, and b is the pulse parameter defining the temporal variation of the pulse behavior.
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The solution of eqn [52] was obtained previously (25), and the resulting dimensionless surface temperature is (25)
2 vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
! 3
u
u ðV
Þ2
6t b e
b

t 2 2 v ! ffi3 3 7
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
6 u 7
6 4 u ðV
Þ2 7
6 4 4 t

55 7
6
erfc b t 7
6 b 4 7
6 7
6 7
6 7
6 7
6 7
6 ð2 V
ÞeðV
1Þt
ð2 V
Þ p ffiffiffiffi 7
6þ erfc t
7
6
2ðV 1Þ 7
6 2 7
6 7
6 7
6
7
1 6
b
1ÞV
ðV
Þ2
p ffiffiffiffi 7

T ð0; t Þ ¼
6 ðV V
7
ðV b 1Þ 6 7
t

e 4 erfc t
6 2b ðV
1Þ 2 7
6 7
6 7
6 7
6 0 1 7
6 7 [53]
6 7
6 B C 7
6 þB1 rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1 C b

t 7
6 @
6
2
Ae 7
7
ðV Þ
V
6 b þ 7
6 4 2 7
6 7
6 7
6 7
6 7
4 ðV
2Þ ðV
1Þt
V
5
þ e þ 1
2b
ðV
1Þ 2b
2

3
V
t

2
V t
6 erfc p ffiffiffiffi 1 þ ðV Þ t erfc pffiffiffiffi
7
6 2 t
2 t 7
arL 6 7
6 7
2k 6 7
4 2V
t
ðV
Þ2 þ ðV
Þ2 t
5
þ pffiffiffiffi e 4t 4
p
V
where T
ð0; t
Þ ¼ Tð0;tÞ
I and V ¼ :
1 ad
kd I0 ð1 rf Þ
The recession velocity (V) can be determined from the energy balance at the surface (27), which yields V ¼ , where Ts
rðCp Ts þ LÞ
is the surface temperature, which can be obtained from eqn [53], and rf is the surface reflectivity. The recoil pressure can be
calculated after considering the rate of momentum change across the receding surface (28). The rate of momentum, which occurs
across the receding surface, is (28)
Pr A ¼ rVVe [54]
where A is the area of irradiated surface, Pr is the recoil pressure, and Ve is the evaporating front velocity. Ve can be formulated from

kB Ts mL
Maxwell’s law for the velocity distribution of molecules (28), i.e., Ve ¼ e kB Ts , where m is the mass of an atom.
2pm
To solve for the stress distribution inside the substrate material, the equation governing the momentum in a one-dimensional
solid for linear elastic and plastic cases can be considered (24), i.e.,
v2 sx 1 v2 sx v2 T
2 2 ¼ c2 2 [55]
vx2 c1 vt vt
qffiffiffiffiffiffiffiffiffiffiffiffi
c1 is the wave speed in the solid, which is c1 ¼ rð1þhÞ
E .

0 0 for elastic case

Here h ¼ E [56]
E ðKÞ 1 0 for plastic case
p
It was shown that (29)

1 a K a1
¼ [57]
Ep ðKÞ E K0
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u
where K is the current yield stress, K0 is the yield stress, and a is a constant. Therefore, c1 becomes c1 ¼ u E a1 . For the perfectly
t k
ra
k0
rffiffiffiffiffi
E 1þy
plastic substrate material, K and K0 become identical. In this case c1 becomes c1 ¼ and the coefficient c2 is c2 ¼ raT ,
ra 1y
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where y is Poisson’s ratio, r is the density of the solid, and aT is the thermal expansion coefficient of the solid. The solution of the
stress equation for the stress boundary condition is (25)
8 9
>
> 2 0 pffiffiffiffiffi x 13 > >
>
> dx $erfc d at þ p ffiffiffiffiffi >
>
>
> 6 B
e
C 7 >
>
>
> 1 6 2 p ffiffiffi B 2 at C 7 >
>
> >
x 2 2
>
> 6 p ffiffiffiffiffi 4at þ d a d at
B C 7 >
>
> >
$e $e
>
> 2 ad þ b ad c1 =a
2 2 2 4 pt @ pffiffiffiffiffi x A 5 >
>
>
> e dx d at þ p ffiffiffiffi
ffi >
>
> >
$erfc
>
> 2 at >
>
>
> >
>
>
> >
>
>
> 2 3 >
>
>
> 0 r ffiffiffi 1 >
>
>
> >
>
>
> 6
c1 x t x 7 >
>
>
> 6 B e $erfc c1
a þ p ffiffiffiffiffi C7 >
>
>
> 6 B a 2 at C 7 >
>
>
> 2 6 2 B C 7 >
>
> >
2
a c 1 B C
c t
>
> 6 p ffiffiffiffiffi
x2
p
1
ffiffiffi 7 >
>
< þ 2 c2 þ ab c2 a2 d2 6 pt $e þ a$e B
4at a
B
C7
C =
sx ¼ C3 1 1 6 B r ffiffiffi A7 C 7
6 @ t x
>
> 4 c1 x
e a $erfc c1 þ pffiffiffiffiffi 5 >
>
>
> >
>
>
> a 2 at >
>
>
> >
>
>
> >
>
>
> >
>
>
> 2 3 >
>
>
> 0 pffib 1 >
>
>
> pffiffiffiffiffi >
>
>
> 6 xi x 7>>
>
> B e i bt þ p ffiffiffiffi
ffi C >
6 2 at C7 > 7
a $erfc
>
> 6 B >
>
>
> 6 2 p ffiffiffi B C >
>
>
>
1
6pffiffiffiffiffi$ex4at þ i b$ebt B
2
C77>>
> þ
> 2 b þ ad2 b þ c2 =a 6 pt B C 7 >
>
>
> 6 B pffib C7 >>
>
> 1
6 B p ffiffiffiffi
ffi C 7 >
>
>
> 4 @ xi x A 5 >
>
>
> e a $erfc i bt þ p ffiffiffiffiffi >
>
>
> 2 at >
>
: ;
8 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 9
>
> 1 pffiffiffiffiffiffiffiffi 2 >
>
>
> pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi þ ad e 2 ad ðtx=c Þ erf ad ðt x=c1 Þ
2 >
>
> >
1
>
> pðt x=c Þ >
>
>
> 1
2 >
>
>
> >
>
>
> ad c1 =a ad þ b
2 2
>
>
>
> >
> [58]
>
> >
>
>
> r ffiffiffiffi
ffi r ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1 >
>
>
> 0 >
>
>
> 1 c 2 c 2
c 2 >
>
>
< p ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi þ 1
e
1 ðtx=c 1 Þ erf 1
ðt x=c Þ C >
=
B pðt x=c Þ
a
1 x
þ C3 þ a2 B a a C
> B
1
2 C $1 t
> C> c1
>
>
>
@ c1 þ ab c21 a2 d2 A>>
>
>
>
> >
>
>
> >
>
>
> >
>
>
> >
>
>
> >
>
>
> p ffiffiffi p ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi >
>
>
> p ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1 þ i b e bðtx=c1 Þ erf i bðt x=c Þ >
>
>
> pðtx=c1 Þ
1 >
>
>
> þ >
>
>
: >
;
b þ c =a ad þ b
1
2 2
8 9
>
>
2
a2 d2 ead t c1 ec1 dt >
>
> 2 þ >
>
>
> þ bÞðc1 adÞ >
>
< ad þ b a d c1
2 2 2 2ðc 1 d =
þ C4 edx
>
> >
>
>
>
> c1 ec1 dt b2 ebt >
>
>
>þ
: þ ;
2ðc1 d bÞðc1 þ adÞ b ad b c1 d
2 2 2 2
2 3
a2 d2 ead ðtx=c1 Þ c1 ec1 dðtx=c1 Þ
2
6 2 þ 7
6 ad þ b a2 d2 c2 2ðc1 d þ bÞðc1 adÞ 7
6 1 7
þ C4 6 7$1 t x
6 7 c1
6 c1 ec1 dðtx=c1 Þ b2 ebðtx=c1 Þ 7
4þ þ 5
2ðc1 d bÞðc1 þ adÞ b ad b c1 d
2 2 2 2
x
b tc a tcx x
þ s0 e 1 e 1 $1 t
c1
pffiffiffi
I1 d2 c2 aac21 I1 c2 c21 da x
where C3 ¼ , C4 ¼ , and 1 t is a unit step function and erf(y) is the error function of the variable y,
k k c1
and C3 and C4 are the coefficients. To present the stress distribution in dimensionless form, the additional dimensionless quantities

c1 ksx
ks0
x
are defined, i.e., c
1 ¼ ; s
x ¼ ; s and U[1] is the unit step function, which is U½1 ¼ t .
ad I1 da2 c2 ðc
1 Þ2
0
I1 da2 c2 ðc
1 Þ2 c
1
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The dimensionless form of eqn [58] can be used to compute the stress distribution in the substrate material. In the case of
rffiffiffiffiffi
E
a plastic stress situation, c1 in eqn [58] is modified in accordance with c1 ¼ .
ra
7.03.4 Analytical Solution for Thermal Stress Incorporating Thermomechanical Coupling
Thermomechanical coupling incorporates the temperature field and stress fields under the thermal load. In some situations, it
becomes essential to incorporate in the governing heat equation describing the physical process. In this section, laser short-pulse
heating incorporating the thermocoupling effect is presented in line with the previous study (22). Since the heating duration is
short, nonequilibrium energy transport in the laser irradiated region is considered. In the nonequilibrium heating situation, thermal
separation takes place between the lattice site and the electrons giving rise to lattice and electron subsystems. The collisional process
between exited electrons and the lattice subsystem defines the energy transport in the irradiated material. Since the mechanical
response of the heated region is associated with the lattice subsystem, analytical solution of the energy equation coupled with the
momentum equation, through thermomechanical coupling, is considered in the lattice subsystem in line with the previous study
(23). Temperature equation in the lattice subsystem, which is similar to eqn [59], is
2
v l 2 v2 vTL v2 T L v v TL v
1 þ ss
C L ¼ k þ sp k þ 1 þ sp ðf dIðt
Þexpðdjx
jÞÞ [59]
vt f vx
2 vt
vx
2 vt
vx
2 vt
where ss is the electron–phonon characteristic time (ss ¼ CE/G), G is the electron–phonon coupling factor, l is the mean free path of
the electrons, f is the fraction of excess energy change, CL and CE are the lattice and electron heat capacities, respectively, k is the
thermal conductivity, sp is the electron mean free time between electron–phonon coupling, Iðt
Þ ¼ I0 expðdt
Þ; where I0
is the laser peak power intensity, expðdtÞ is the temporal distribution function of laser pulse, d is the absorption coefficient, x* is
the lattice depth, t* is the time variable, and TL is the lattice site temperature.
Equation [1] can be written in the absence of the volumetric source as
2 2 2
v v TL l v v vTL
V$q ¼ 1 þ sp
k
2 þ s s
CL
[60]
vt vx f vx
2 vt vt
vTL
where q is k .
vx
In order to account for the thermomechanical effect during the heating process, the energy transport equation (eqn [60]) should
be modified. For a deformable solid body, the specific enthalpy can be written as (30)
hhhðTL ; eÞ [61]
where e is the strain. The enthalpy can be written as

vh vh
rdh ¼ r dTL þ r de [62]
vTL e ve TL
It was shown that (30)

vh vCv
r y T0 [63]
ve TL vTL T0
where Cv is the lattice site volumetric specific heat and T0 is the reference temperature. However,
V$q ¼ rdh [64]
or

vTL ve
V$q ¼ CL
þ as T0 [65]
vt vt
where as is related to the coefficient of thermal expansion and it is

vCv
as h [66]
vTL
Rearrangement of eqn [65] yields

vTL as T0 ve=vt
V$q ¼ CL
1 þ [67]
vt CL vTL =vt
or

vTL h ve=vt
V$q ¼ CL
1þ a
[68]
vt ae vTL =vt

3GT0 2 as E
where ha ha ¼ ae ; ae ¼ ; and G ¼ is the thermomechanical coupling factor, which is shown to be small for
CL 3G 3ð1 2yÞ
most metals at room temperature (24).
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The strain can be written as

vU
e¼ [69]
vx
where U is the thermal displacement vector. Using eqns [68] and [69], it yields
vTL CL ha v
V$q ¼ CL þ ðV$UÞ [70]
vt
ae vt
or

vTL CL ha v2 U
CL ¼ V$qD [71]
vt
ae vt
vx
CL ha
Since ¼ as T0 , the equation describing the energy transport due to electron–phonon interactions (eqn [60]) can be written
ae
to include the thermomechanical coupling, i.e., combining eqns [60] and [71] yields
2
v l2 v2 vTL v2 TL v v TL v2 U
1 þ ss C L ¼ k þ sp k
2 as T0

[72]
vt
f vx
2 vt
vx
2 vt
vx vt vx
However, in the stress field, the equilibrium condition yields

vsx
v2 U

¼ r
2 [73]
vx vt
where r is the density and the stress sx
can be given as
vU
s x
¼ E Eae TL [74]
vx
where E is modulus of elasticity and ae is the coefficient of thermal expansion in strain.

Consider a semi-infinite substrate material heated with a time decaying source from the surface. Therefore, it becomes necessary
to solve the system of differential equations consisting of eqns [72]–[74] with the following boundary conditions:
vTL I0 vsx
ð0; t
Þ ¼ expðdt
Þ; TL ðN; t
Þ ¼ T0 ; ð0; t
Þ ¼ 0; sx
ðN; t
Þ ¼ Eae T0
vx
k vx
vTL
vsx

ðx ; NÞ ¼ 0; TL ðx
; NÞ ¼ T0 ; ðx ; NÞ ¼ 0; sx
ðx
; NÞ ¼ Eae T0 [75]
vt
vt
vU
ðx ; NÞ ¼ 0; Uðx; NÞ ¼ 0
vt
Introducing the equalities

fk CE
l2 ¼ ; ss ¼ [76]
G G
and dimensionless variables

1 dCE 2 Ud TL T0
sx ¼ ðsx
þ Eae T0 Þ; u ¼ ; qL ¼ ; x ¼ x
d
rae T0 G ae T0 T0
t
CE kd2 sp G dCE
t¼ ; ε¼ ; a¼ ; m¼ ; g¼ [77]
CE =G CL G CL G
2
as ae T0 r G
u¼ ; h¼
CL E dCE
to eqns [72]–[74] yields finally the dimensionless system
v 3 qL v2 qL v2 qL vqL v2 u
að1 þ mÞ 2
þ εa 2 2 u ¼0
vx vt vx vt vt vtvx
vsx v2 u [78]
2 ¼0
vx vt
vu
¼ qL ðx; tÞ þ hsx ðx; tÞ
vx
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with the dimensionless boundary conditions

vqL vsx
ð0; tÞ ¼ I0 expðgtÞ; qL ðN; tÞ ¼ 0; ð0; tÞ ¼ 0; sx ðN; tÞ ¼ 0
vx vx
vqL vsx
ðx; NÞ ¼ 0; qL ðx; NÞ ¼ 0; ðx; NÞ ¼ 0; sx ðx; NÞ ¼ 0 [79]
vt vt
vu
ðx; NÞ ¼ 0; uðx; NÞ ¼ 0
vt
where the dimensionless source amplitude I0 is related to the dimensional one I0 through the relation
I0
I0 ¼ [80]
kdT0
One can find that the improved model system (eqn [78]) admits the Lie point symmetry:
1v v v v
X¼ þ sx þ qL þu [81]
g vt vsx vqL vu
and the invariants of X are
x; egt qL ; egt sx ; egt u [82]
Then the corresponding invariant solution can be given as
qL ¼ wðxÞegt ; sx ¼ zðxÞegt ; u ¼ qðxÞegt [83]
This similarity solution reduces the boundary value problem to the second order system of ordinary differential equations
(ODEs):
d2 wðxÞ dqðxÞ
aðε g gmÞ þ gð1 gÞwðxÞ þ ug ¼0
dx2 dx
dzðxÞ
g2 qðxÞ ¼ 0 [84]
dx
dqðxÞ
hzðxÞ þ wðxÞ ¼ 0
dx
with the conditions
w0 ð0Þ ¼ I0 wðNÞ ¼ 0
[85]
zð0Þ ¼ 0 zðNÞ ¼ 0
Solving the second and third equation of the system in eqn [84] gives
1 dzðxÞ
qðxÞ ¼
g2 dx
[86]
1 d2 zðxÞ
wðxÞ ¼ hzðxÞ
g2 dx2
Substituting eqn [86] in the first equation of the system in eqn [84] gives
d4 zðxÞ d2 zðxÞ
A 4
B þ CzðxÞ ¼ 0 [87]
dx dx2
where A ¼ aðg þ gm εÞ; B ¼ gð1 g þ u þ hgaðg þ gm εÞÞ; and C ¼ hg3 ð1 gÞ.
One can see that A, B, and C are positive real numbers when ( mg þ g ε) > 0 and (1 g) > 0, i.e., when
n
ε
g<1 & g> as in which case ε is of order 102 for metals and g < 1.
1þm
The solution of eqn [87] can be given as
zðxÞ ¼ C1 expðl1 xÞ þ C2 expðl2 xÞ þ C3 expðl3 xÞ þ C4 expðl4 xÞ [88]
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
B B2 4AC B B2 4AC B þ B2 4AC B þ B2 4AC
where l1 ¼ ; l2 ¼ ; l3 ¼ ; and l4 ¼ .
2A 2A 2A 2A
For the case in which ( m g þ g ε) > 0 and (1 g) > 0, one can observe that l1, l2, l3, and l4 are real numbers.
Using the condition z(N) ¼ 0 gives C1 ¼ C3 ¼ 0. Then using the condition z(0) ¼ 0 gives C2 þ C4 ¼ 0. So eqn [88] can be
rewritten as
zðxÞ ¼ C2 expðl2 xÞ C2 expðl4 xÞ [89]
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Substituting eqn [89] in eqn [86] gives

1
qðxÞ ¼ ðC2 l2 expðl2 xÞ C2 l4 expðl4 xÞÞ
g2
2 2 [90]
l l
wðxÞ ¼ C2 22 h expðl2 xÞ C2 42 h expðl4 xÞ
g g
Using the condition w0 ð0Þ ¼ I0 gives
I 0 g2
C2 ¼ [91]
l32 l34 hg2 ðl2 l4 Þ
Then the final solution of the dimensionless system, eqn [77], can be given as
2 2
l l
qL ðx; tÞ ¼ C2 22 h el2 xgt C2 42 h el4 xgt
g g
sx ðx; tÞ ¼ C2 el2 xgt C2 el4 xgt [92]
1
uðx; tÞ ¼ C2 l2 el2 xgt C2 l4 el4 xgt
g2
Equation [92] gives the closed form solution for temperature, stress, and thermal displacement in the substrate material when
irradiated by the laser short-pulse.
7.03.5 Analysis of Plastic Wave Generation and Propagation due to High Intensity Pulse
The plastic deformation takes place at micro/nanolevel under the high pressure loading of the structures. One of the sources of
generating high pressures is ablation of the surface by laser short-pulse irradiation. In this case, rapid evaporation of the surface
results in a high rate of momentum exchange at the solid–vapor interface while generating recoil pressure at the interface. The high
pressure formation at the irradiated surface causes locally mechanical loading and plastic wave formation. The analysis related to
vapor front generation and the plastic deformation of the surface is given below in the light of the previous study (31).
7.03.5.1 Heating and Phase Change Analysis

Consider the surface which is irradiated by the high intensity laser beam. The axisymmetric heating model is appropriate to
resemble the situation. Since the process is involved with the phase changes, the presence of the mush zones in the irradiated region
becomes unavoidable. In order to capture the mush zone, where two phases mutually exist, in the model study, the energy method
is adopted. In the analysis, the laser output power intensity is considered Gaussian and its center is located at the center of the
coordinate system. The time exponentially varying laser pulse used in the simulations resembles the actual laser pulse. The heat
conduction equation for laser heating in solid phase due to a Gaussian intensity profile of laser output power can be written as

vT ks v vT v2 T
rs cps ¼ r þ ks 2 þ S0 [93]
vt r vr vr vz
where S0 is the volumetric source term, and it is in the form of

r2
S0 ¼ I0 ðtÞd 1 rf expðdzÞexp 2 [94]
a
I0(t), d, rf, and a are the laser peak power intensity, absorption coefficient, reflectivity, and Gaussian parameter, respectively.
The substrate material is initially assumed to be at a uniform temperature, T0, i.e.,
At time zero 0 t ¼ 0 : Tðr; z; 0Þ ¼ T0 ðwhich is specifiedÞ [95]
Laser heating is assumed to have no effect on the temperature rise at a depth of infinity below the surface; therefore, temperature
is assumed to be constant and equals to the initial temperature of the substrate material at this depth. The boundary conditions are
r at infinity 0 r ¼ N : TðN; z; tÞ ¼ T0 ðspecifiedÞ [96]
z at infinity 0 z ¼ N : TðN; z; tÞ ¼ T0 ðspecifiedÞ [97]

At the symmetry axis, temperature reaches maximum and the convection boundary condition is considered at the workpiece
surface, i.e.,
vTð0; z; tÞ
At symmetry axis 0 r ¼ 0 : ¼0 [98]
vr
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and
vTðr; 0; tÞ
At the surface 0 z¼0:k ¼ hðTðr; 0; tÞ T0 Þ [99]
vz
where h is taken as 10 W m2 K1 due to natural convection from the surface.
The evaporation temperature depends on the vapor pressure; however, pressure-dependent evaporation temperature is not
known in the open literature for steel vapor. Therefore, it is assumed that the substrate material has single melting and boiling
temperatures. A mushy zone (mutual existence of two phases) is developed across the interface of two phases, once the phase
change initiates. During the phase change process, enthalpy changes while temperature of the substrate material remains the same
in the mushy zone. Moreover, the nominal laser pulse length employed in the analysis is 24 ns; therefore, the flow in the vapor and
liquid layer during the heating process can be neglected. Consequently, during the short heating period, the fluid motion in the
liquid and vapor layers is assumed to have no effect on the heat transfer mechanism in these zones. Mass fraction of species content
in the mushy zone can be formulated via energy balance in the mushy zone. The energy equation for the differential element in the
mushy zone (31) is

vxm km v vT v2 T
rm Lm ¼ r þ km 2 þ S0 [100]
vt r vr vr vz
where xm is the mass fraction of liquid phase in the mushy zone, i.e.,
mm
xm ¼ [101]
mm þ ms
Equation [2] is valid in the mushy zone where 0 xm 1, i.e., temperature of the cells with 0 xm 1 is set to melting
temperature (T ¼ Tm). For the situation xm ¼ 1, liquid phase occurs and eqn [1] is used to determine the temperature rise in the
liquid heating using the liquid thermal properties in the equation. Moreover, the liquid heating continues until the boiling point is
reached in the substrate material; in which case, a new mushy zone is formed. In this case, eqn [2] is modified for a differential
element in the mushy zone subjected to evaporation (31), i.e.,

vx k v vT v2 T
rb Lb b ¼ b r þ kb 2 þ S0 [102]
vt r vr vr vz
where xb is the mass fraction of vapor phase in the mushy zone, i.e.,
mb
xb ¼ [103]
mm þ mb
Equation [102] is applicable for temperature T ¼ Tb and 0 xb 1 in the mushy zone (partially liquid partially vapor zone); in
which case, temperature of the cells with 0 xb 1 is set to the boiling temperature of the substrate material (T ¼ Tb). It should be
noted that xm is replaced with xb in eqn [102], which represents the fraction of vapor phase in the differential element. The
calculation of xb is the same as xm, provided that latent heat of fusion is replaced with latent heat of evaporation of the substrate
material in eqn [3] in the latter.
The boundary condition at the evaporating surface is introduced in relation to eqn [102]. In this case, the temperature along the
evaporated surface is kept at the boiling temperature of the substrate material, i.e., the cells in the evaporated region are kept at the
boiling temperature, i.e., in the mushy zone, at z ¼ zb 0Tðr; zb ; tÞ ¼ Tb , where zb represents the axial location at the evaporated
surface.
Equations [100] and [102] provide the relative position of solid–liquid and liquid–vapor interface in the substrate material.
Liquid–vapor interface determines the shape and size of the cavity generated during the evaporation process.
7.03.5.2 Transiently Developing Vapor Jet

The vapor front emerging from the laser-induced cavity is modeled numerically using a control volume approach. The laser
produced cavity shape and its temporal progression as predicted from the finite difference scheme are employed in the simulations.
In this case, the time-varying cavity shape, mass flux of the vapor, and the temperature distribution at the cavity surface are the
inputs for the simulations of the flow field due to vapor jet emanating from the cavity. In the flow analysis, the time averaged
conservation equations are accommodated for an unsteady, incompressible, axisymmetric turbulent flow situation resembling the
vapor jet expansion. The standard k-ε turbulence model is used to account for the turbulence. Moreover, the species transport model
is also used to account for the mass transfer of the vapor jet from the cavity into the stagnant water ambient. It should be noted that
all the unknown quantities are time-averaged since the Reynolds averaged Navier-Stokes equations are used.
7.03.5.2.1 Continuity Equation

The conservation of mass in the cylindrical coordinates for compressible transient flow situation can be written as
1 vðrrVr Þ vðrVz Þ vr
þ þ ¼0 [104]
r vr vr vt
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7.03.5.2.2 Radial Momentum

The vapor emanating from the cavity has radial momentum. Since the flow expansion takes place at high velocities, the flow field
becomes turbulent. This requires accommodation of the turbulence model. In this case, the k-ε turbulence model is used to account
for the turbulence. The momentum conservation in the radial direction for compressible transient turbulent flow situation can be
written as

vðrVr Þ 1 v rrVr2 vðrVr Vz Þ vp 2 v vVr v vVr v vVz Vr
þ þ ¼ þ meff r þ meff þ meff 2meff 2 [105]
vt r vr vz vr r vr vr vz vz vz vz r
7.03.5.2.3 Axial Momentum

The axial momentum of the vapor can be written after considering the compressible transient turbulent flow situation, i.e.,

vðrVz Þ 1 vðrrVr Vz Þ v rVz2 vp 1 v vVz v vVz 1v vVr
þ þ ¼ þ meff r þ2 meff þ meff r [106]
vt r vr vz vz r vr vr vz vz r vr vz
rCm K 2
where meff is the effective viscosity, which is meff ¼ m þ mt and mt ¼ :Cm ¼ 0.09, mt is the turbulence viscosity, m is the bulk
ε
viscosity of the vapor, and K is the turbulence kinetic energy generation.
7.03.5.2.4 Energy Equation

Since the flow due to the vapor expansion from the cavity is turbulence and the vapor front expands into the stagnant water, the
energy equation for the flow field should contain the species (vapor and water) transport of energy. In this case, the resulting energy
equation becomes

vðrEÞ 1 vðrVr rEÞ vðVz rEÞ 1 v vT v vT
þ þ ¼ rkeff þ keff
vt r vr vz r vr vr vz vz

1v m vYvapor v m vYvapor
þ rhvapor rD þ t þ hvapor rD þ t [107]
r vr Sct vr vz Sct vz

1v m vYwater v m vYwater
þ rhwater rD þ t þ hwater rD þ t
r vr Sct vr vz Sct vz
where E ¼ Ywaterhwater þ Yvaporhvapor, after neglecting the contribution of kinetic energy. Enthalpy of vapor and water is
ZT

hvapor ¼ Cpvapor dT ¼ Cpvapor T Tref [108]
Tref
ZT

hwater ¼ Cpwater dT ¼ Cpwater T Tref [109]
Tref
In eqns [107]–[109], the properties and parameters are
mt
keff ¼ k þ kt : kt ¼ Cp and D ¼ 2:88 105 m2 s1 : Sct ¼ 0:7 : Prt ¼ 0:85 : Tref ¼ 298:15 K [110]
Prt
7.03.5.2.5 Turbulence Kinetic Energy Equation, K

Since the flow is turbulence, turbulence kinetic energy generation can be modeled using the kinetic energy transport equation, which
yields

vðrKÞ 1 vðrrVr KÞ vðrVz KÞ 1 v meff vK v meff vK
þ þ ¼ r þ rε þ PK [111]
vt r vr vz r vr sK vr vz sK vz
where
2 2
vVz 2 vVr Vr vVz vVr 2
PK ¼ meff 2 þ þ þ þ [112]
vr vr r vr vz
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7.03.5.2.6 Rate of Dissipation Equation, ε

The turbulence kinetic energy dissipation is assumed to be of the same magnitude as the turbulence kinetic energy generation.
Therefore, transport equation for the turbulence dissipation can be written as

vðrεÞ 1 vðrrVr εÞ vðrVz εÞ 1 v meff vε v meff vε ε ε2
þ þ ¼ r þ C1 PK C2 r [113]
vt r vr vz r vr sε vr vz sε vz K K
where
2 2
vVz 2 vVr Vr vVz vVr 2
PK ¼ meff 2 þ þ þ þ [114]
vr vr r vr vz
and
sK ¼ 1; sε ¼ 1:3; C1 ¼ 1:44; C2 ¼ 1:92 [115]
7.03.5.2.7 Species Transport Equation

It is considered that the vapor front expands into the stagnant water resulting in the mixing of vapor and the water in the region
above the laser produced cavity surface. This requires the transport equation of vapor to be considered, i.e.,

v rYvapor 1 v rVr rYvapor v Vz rYvapor 1v m vYvapor v m vYvapor
þ þ ¼ r rD þ t þ rD þ t [116]
vt r vr vz r vr Sct vr vz Sct vz
provided that the species balance yields Ywater ¼ 1 Yvapor.
7.03.5.2.8 Initial and Boundary Conditions

The laser produced cavity recesses towards the solid material while the evaporated front expands into the stagnant water during the
heating period. This results in a temporarily extending cavity and the vapor front expanding from the cavity. In this case, the solution
domain evolves with time and the moving cavity surface should be accommodated at the interface of liquid and vapor phases
during the heating period.
Symmetry axis (at r ¼ 0): At the symmetry axis all the unknown quantities are considered to be maximum except the r-direction
velocity, which is zero, i.e., for all z values and r ¼ 0 (symmetry axis), the boundary conditions are

vVz vT vK
¼0 : Vr ðz; 0Þ ¼ 0 : ¼0 : ¼0 [117]
vr z ¼ z vr z ¼ z vr z ¼ z
r ¼0 r ¼0 r ¼0

vε vYvapor
¼0 : ¼0 [118]
vr z ¼ z vr z ¼ z
r ¼0 r ¼0
Far-field (outflow) (at z ¼ 0): At the outflow boundary perpendicular to the z-axis, the normal derivatives of all the unknown
quantities are considered to be zero except the r-direction velocity, whose value is zero as required from the continuity equation, i.e.,
for all r values and z ¼ 0 (at the free surface), the boundary conditions are

vVz vT vK
¼ 0 : V ð0; rÞ ¼ 0 : ¼ 0 : ¼0 [119]
vz z ¼ 0 vz z ¼ 0 vr z ¼ 0
r
r ¼r r ¼r r ¼r

vε vYvapor
¼0 : ¼0 [120]
vr z ¼ 0 vr z ¼ 0
r ¼r r ¼r
Far-field (outflow) (at r ¼ rmax): At the outflow boundary perpendicular to the r-axis, the normal derivatives of all the unknown
quantities are considered to be zero except the z-direction velocity, whose value is zero as required from the continuity equation, i.e.,
for all z values and r ¼ rmax (radial location far away from the symmetry axis), the boundary conditions are

vVr vK
Vz ðz; rmax Þ ¼ 0 : ¼0 : ¼0 [121]

vr z ¼ z vr z ¼ z
r ¼ rmax r ¼ rmax

vε
vYvapor
¼0 : ¼0 [122]
vr z ¼ z vr z ¼ 0
r ¼ rmax r ¼ rmax
Solid wall (at z ¼ f(r,t)): The surface of the substrate material including the cavity surface acts like a solid wall in the solution
domain and hence no-slip and no-temperature jump boundary conditions are considered. At the cavity surface, the vapor mass
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fraction is considered to be one, whereas the water mass fraction is considered to be zero. Once the cavity profile in axial and radial
directions is obtained from the numerical scheme for each time step, an algebraic equation is introduced, using the polynomial
fitting technique, to resemble the temporal behavior of the cavity shape through using the computed data available for time steps.
The vapor mass flow generated from the cavity surface recession during the heating period is considered the source of the mass of the
vapor jet emanating from the cavity surface. The details of the analysis are given in Ref. (31).
Initial condition (t ¼ 0): Initially the ambient water is assumed to be stagnant; therefore, the z- and r-direction velocity
components are zero. Initially, temperature is considered to be uniform and equal to 300 K in water ambient and the vapor mass
fraction is zero, whereas the water mass fraction is one throughout the domain.
7.03.5.2.9 Numerical Solution

The numerical solution has two parts. In the first part, the finite difference scheme used for the phase change process (eqns [93],
[100], and [102]) is introduced while in the second part numerical solution for the flow equations is presented.
7.03.5.2.9.1 Phase change process

Equation [93] is applicable to solid and liquid heating, eqn [100] is applicable to the mushy zone at the solid–liquid, and eqn [102]
is applicable to the mushy zone at the liquid–vapor interface. To discretize the governing equations, a finite difference scheme is
introduced. The details of the numerical scheme are given in Ref. (31). To compute the equations discretized for temperature field
and relative positions of solid–liquid and liquid–vapor interface, an implicit scheme is used, i.e., using the initial conditions, the
temperature in the whole domain is calculated for following time steps with the respective conditions.
The calculation domain is divided into grids. A grid independence test is performed for different grid size and orientation, and
the grid size resulting grid independent solution is used, which is 100 120 mesh points in the r- and z-axes. A computer program
based on implicit scheme is developed to compute the temperature field.
7.03.5.2.9.2 Transiently developing vapor jet (front)

A controlled volume approach is employed when discretizing the governing equations. A staggered grid arrangement is used in
which the velocities are stored at a location midway between the grid points, i.e., on the control volume faces. All other variables
including pressure are calculated at the grid points. This arrangement gives a convenient way of handling the pressure linkages
through the continuity equation and is known as the Semi-Implicit Method for Pressure-Linked Equations algorithm. The details of
this algorithm are given in Ref. (32).
The computer program used for the present simulation can handle a nonuniform grid spacing. Along the radial direction, a fine
uniform grid spacing is allocated at the inlet (in cavity symmetry axis region) while gradually increasing spacing is considered away
from the inlet (in the cavity edge region). Along the axial direction, again fine uniform grid spacing is used inside and near the cavity
while the grid spacing gradually increases away from the cavity. The number of grid points in the radial direction is 300, while 215 grid
points are used in the axial direction. Since the problem is involved with the moving boundary, the moving meshes are accom-
modated in the cavity to account for the cavity recession with time. It should be noted that the evolving of cavity due to recessing
towards the solid material during the heating period is accommodated through using the moving meshes in the solution domain. The
grid independence test is conducted, and grid size (215 300) resulting in grid-independent solution is used in the simulations.
Eight variables are computed at all grid points. These are the two velocity components, local pressure, two turbulence quantities,
temperature, and two mass fractions. The properties of substrate material used in the simulations are given in Table 1. The nominal
laser pulse length at full width at half maximum is 24 ns.
7.03.5.3 Elastoplastic Analysis

To investigate the effect of the elastic–plastic wave propagation on the deformation behavior and the distribution of stresses,
a commercial nonlinear explicit dynamic finite element (FE) code ANSYS LS-DYNA (33) is used. For modeling purposes, two-
dimensional axisymmetric FE analysis was found to be adequate. To incorporate the temporal variation in the recoil pressure
magnitude and its spatial distribution, the pressure predicted from the solution of momentum equation is used. The time
dependent pressure was applied on the top surface of the cavity. The cavity was meshed using the PLANE162 element. PLANE162 is
Table 1 Properties of water and vapor front used in the simulations
Water Vapor front
Density (kg m3) 998.2 50, 800

Viscosity (kg m1 s1) 0.001003 1.34 105
Mass diffusivity (m2 s1) 2.88 105
Specific heat capacity (J kg1 K1) 4182 2014
Thermal conductivity (W m1 K1) 0.6 0.0261
Molecular weight (g/mol) 18.0152 56
Reproduced from Yilbas, B. S.; Mansoor, S. B.; Arif, A. F. M. Laser Shock Processing: Modeling of Evaporation and
Pressure Field Developed in the Laser Produced Cavity. J. Adv. Manuf. Technol. 2009, 42 (3–4), 250–262.
www.iran-mavad.com
used for modeling 2D solid structures in ANSYS LS-DYNA (33). The element can be used either as a planer or as an axisymmetric
element. The element is defined by four nodes having six degrees of freedom at each node: translations, velocities, and accelerations
in the nodal x- and y-directions. The element is used in explicit dynamic analyses only.
Material behavior was idealized as strain rate–dependent isotropic plasticity. In this model, a load curve is used to describe the
initial yield strength, as a function of effective strain rate. The yield stress for this material model is defined as
sy ¼ s0 εt þ Ek εeff
p [123]
where s0 is the initial yield strength, ε is the effective strain rate,

t
εeff
p is the effective plastic strain, and Ek is given by
El Etan
Ek ¼ [124]
ðEl Etan Þ
where El is the modulus of elasticity and Etan is the tangent modulus for the material. The material properties used to model the
constitutive behavior of the steel are El ¼ 209 GPa, v ¼ 0.29, density ¼ 17 850 kg m3, and Etan ¼ 2.2 MPa.
7.03.6 Findings and Discussion
Thermal management at micro/nanolevels is important for manufacturing or processing of small devices. This is because of the
development of high temperature gradients in extremely small spaces in short time durations. Although the problem requires
general solution for various applications, some focused analysis is provided due to the space limitations in this chapter. The focused
analysis covers the laser short-pulse processing at micro/nanolevels and thermal stress formation in the irradiated region. The
findings of analytical solution to stress levels at micro/nanolevels are presented according to the subheadings below in line with the
previous studies (21,22,29,31).
7.03.6.1 Analytical Treatment of Thermal Stresses at Micro/Nanosized Length Scales

Since the energy transport takes place at micro/nanoscales, the nonequilibrium process dominates the heating and stress analysis. In
this case, the hyperbolic form of the heat equation is considered and temperature field in the irradiated region is formulated
accordingly. The resulting temperature field forms the bases for the development of the thermal stress field. The findings for the
temperature and stress fields are presented below in line with the previous study (21).
Figure 1 shows dimensionless lattice site temperature distribution along the substrate material for different heating periods.
Lattice site temperature increases with increasing depth below the surface, which is more pronounced with increasing heating
periods. This is associated with electron excess energy transfer to the lattice site through the collisional process with progressing
time. In this case, the number of electron lattice site collisions increases with progressing time, resulting in energy gain of the lattice
site. Since the electron excess energy transfer to lattice is considerably small during a single collision, successive collisions with
progressing time enhances lattice site temperature increase inside the substrate material. In addition, the number of collisions
increases with increasing depth, which in turn elevates lattice site temperature rise with increasing depth below the surface. Lattice
temperature increase is sharp in the surface region in the early heating period, and it becomes gradual as the depth below the surface
increases. This is associated with electron energy transfer through the collisional process, which increases with increasing depth
below the surface. As the heating period increases, lattice temperature along the depth below the surface becomes gradual.
1.000000
0.999999
t=10
L
0.999998 t=20
t=30
0.999997
0.999996
0 50 100 150 200 250 300
x
Figure 1 Dimensionless lattice temperature distribution for different heating durations. Reproduced from Yilbas, B. S.; Al-Dweik, A. Y. Exact
Solution for Temperature Field due to Non-Equilibrium Heating of Solid Substrate. Phys. B: Condens. Matter 2011, 406 (23), 4523–4528.
www.iran-mavad.com
Figure 2 shows dimensionless thermal stress developed inside the substrate material for different heating periods for stress-free
surface boundary condition. Thermal stress is tensile in the surface region for all heating periods, and it becomes compressive at
same depth below the surface. The tensile stress behavior is attributed to the free expansion of the surface during the heating period.
However, thermal expansion replaces thermal contraction at same depth below the surface; in this case, material in this region is not
free to expand, and free expansion of the surface results in contraction in this region. However, as the heating period progresses, the
temperature gradient in the surface region reduces, causing less thermally induced strain in the surface region. This lowers the
maximum tensile stress magnitude in the surface region. The wave nature of heating results in wave nature of thermal stress fields in
the irradiated region. As the thermal stress reduces at the surface region, compressive stress magnitude increases below the surface.
Moreover, the depth of the tensile stress region increases below the surface as the heating period progresses. In the case of stress
continuity at the surface, stress wave is modified in the surface region such that peak stress reduces with progressing time. Moreover,
the stress field inside the substrate material becomes compressive for all heating periods, which is because of the constraint
introduced at the surface. The peak stress moves further into the substrate material with progressing time.
7.03.6.2 Temperature and Stress Fields due to High Intensity Laser Irradiation
The high intensity laser pulses result in the surface evaporation and recoil pressure generation at the solid–vapor interface. This
causes plastic wave formation in the substrate material while modifying the metallurgical properties in the irradiated region. The
findings related to the recoil pressure and the behavior of the plastic wave are presented below in the light of the previous study (29).
Figure 3 shows dimensionless stress with time at different locations inside the substrate material for elastic and plastic wave
cases. It should be noted that the stress wave for the elastic case propagates faster than that corresponding to plastic case, since the
4.0E-03
t=10
2.0E-03 t=20
t=30
0.0E+00
σ
–2.0E-03
–4.0E-03
–6.0E-03
0 50 100 150 200 250 300
x
Figure 2 Dimensionless stress distribution inside the workpiece for stress-free boundary condition at the surface. Reproduced from Yilbas, B. S.; Al-
Dweik, A. Y. Exact Solution for Temperature Field due to Non-Equilibrium Heating of Solid Substrate. Phys. B: Condens. Matter 2011, 406 (23), 4523–4528.
Figure 3 Dimensionless stress distribution with dimensionless time at various depths below the surface. Reproduced from Yilbas, B. S.; Mansoor,
S. B.; Arif, A. F. M. Laser Shock Processing: Modeling of Evaporation and Pressure Field Developed in the Laser Produced Cavity. J. Adv. Manuf.
Technol. 2009, 42 (3–4), 250–262.
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Figure 4 Time–distance history of stress distribution for elastic and plastic cases. Reproduced from Yilbas, B. S.; Mansoor, S. B.; Arif, A. F. M. Laser
Shock Processing: Modeling of Evaporation and Pressure Field Developed in the Laser Produced Cavity. J. Adv. Manuf. Technol. 2009, 42 (3–4), 250–262.
wave speed in elastic case is c1 ¼ OE/r, while in the plastic case c1 ¼ OE/(ra). Moreover, stress wave developed in the elastic case is
due to the temperature gradient inside substrate material, and its amplitude is less than the yield stress of the substrate material. It
can be observed that the time corresponding to initiation of both waves is shifted as the time progresses. This is because of the stress
wave speeds, which are different for elastic and plastic cases.
Figure 4 shows the time–distance history of elastic and plastic wave propagation in the substrate material. The amplitude of the
stress at the surface, which is set as boundary condition, reduces with time, i.e., it becomes less than the yield strength of the
substrate material at t* ¼ 0.32. Therefore, beyond this time, elastic wave propagation inside the substrate material is considered and
Figure 4 is plotted accordingly. Since the stress wave for the elastic condition propagates faster than that corresponding to the plastic
case, the stress waves meet at a depth of x* ¼ 9.2 (1.49 mm) below the surface. The depth from free surface to the point where two
waves meet undergoes a plastic deformation, since the plastic wave propagates up to the point when the waves meet.
7.03.6.3 Influence of Thermomechanical Coupling on Temperature and Stress Fields

Thermomechanical coupling between temperature and stress fields modifies the heat equation considered for nonequilibrium
energy transport. In this case, energy absorbed by the irradiated material is partially dissipated through heat transfer and partially
used for thermal expansion of the substrate material. Therefore, the findings for temperature and stress fields differ from those
corresponding to the uncoupled analysis. The findings from the coupled analysis are presented below in line with the previous
findings (22).
Figure 5 shows dimensionless lattice site temperature distribution along the dimensionless depth inside the substrate material
for different dimensionless heating periods. Temperature decays sharply in the surface region, which is more pronounced in the
early heating period. This is attributed to the laser pulse intensity distribution, which decays exponentially with time. Therefore,
high power intensity results in rapid rise of temperature at the surface and sharp decay of temperature in the surface region of the
Figure 5 Dimensionless temperature distribution along the dimensionless depth inside the substrate material for different dimensionless time.
Reproduced from Yilbas, B. S.; Al-Dweik, A. Y. Non-Equilibrium Heating of a Solid Surface by a Short-Pulse Laser: A Closed Form Solution Including
Thermomechanical Coupling. J. Therm. Stresses, in press.
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substrate material. Since the diffusional energy transport is considerably small during a short heating period, a high temperature
gradient does not result in a high rate of heat diffusion in the surface region. This suppresses temperature rise below the surface
while contributing to the sharp decay of temperature in the surface region. Lattice site temperature depends on the energy transport
from the electron subsystem to the lattice subsystem through electron–phonon collisions. In this case, reducing power intensity
lowers the electron energy gain from the irradiated field. Consequently, lattice site temperature reduces sharply inside the substrate
material with progressing time. In addition, collisional energy transport from the electron subsystem to the lattice subsystem is not
high during the short heating period due to few collisions taking place between electrons and lattice site. Therefore, lattice site
temperature decays sharply along the depth because of less energy transfer from the electron subsystem to the lattice subsystem.
Figure 6 shows dimensionless thermal stress distribution along the dimensionless depth inside the substrate material for
different dimensionless heating periods. Since the stress-free boundary condition is set at the surface, thermal stress remains zero at
the surface due to surface free expansion. Thermal stress is compressive, and it increases in the surface vicinity, reaching its
maximum at some depth below the surface. The location of the maximum stress remains almost the same for different heating
periods. As the depth below the surface increases, thermal stress reduces sharply first and the decay becomes gradual as the depth
increases further towards the solid bulk. Since the stress field is formed in the lattice subsystem, temperature distribution in the
lattice subsystem defines the behavior of thermal stress inside the substrate material. The compressive nature of the thermal stress is
associated with the sharp decay of temperature in the surface region. Since the decay of temperature changes along the depth, stress
distribution changes along the depth accordingly.
Figure 7 shows temporal variation of thermal displacement at different locations along the dimensionless depth inside the
substrate material. The magnitude of displacement is negative at the surface because of the excessive thermal loading in the early
Figure 6 Dimensionless stress distribution along the dimensionless depth inside the substrate material. Reproduced from Yilbas, B. S.; Al-Dweik, A. Y.
Non-Equilibrium Heating of a Solid Surface by a Short-Pulse Laser: A Closed Form Solution Including Thermomechanical Coupling. J. Therm. Stresses, in
press.
Figure 7 Temporal variation of dimensionless displacement at different locations along the dimensionless depth inside the substrate material.
Reproduced from Yilbas, B. S.; Al-Dweik, A. Y. Non-Equilibrium Heating of a Solid Surface by a Short-Pulse Laser: A Closed Form Solution Including
Thermomechanical Coupling. J. Therm. Stresses, in press.
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heating period. In this case, thermomechanical coupling suppresses the rise of thermal expansion at the surface in the early heating
period. As the heating period progresses, this behavior gradually disappears and the displacement approaches zero as the time
progresses further. This behavior changes at some depth below the surface. Displacement becomes positive, indicating the thermal
expansion in this region. This is attributed to the high rate of contraction in the surface region, which causes thermal expansion in
the region next to the surface vicinity. Displacement approaches zero as the depth below the surface increases towards the solid bulk.
7.03.6.4 Plastic Wave Generation and Its Propagation due to High Intensity Pulse Radiation
In order to generate the plastic wave, the formation of recoil pressure at the solid–vapor interface is essential. In this case, surface
evaporation and melting during the heating pulse need to be formulated. The recoil pressure is obtained from the momentum
exchange at the interface of the irradiated surface and the plastic wave propagation is predicted using the ANSYS code (33). The
findings are discussed below in the light of the previous study (31).
Figure 8 shows cavity shape at t ¼ 19.7 ns of the heating pulse. The presence of a mushy zone particularly at the vapor–liquid
interface is evident; however, the size of the mushy zone at solid–vapor interface is considerably small. This is due to the latent heat
of evaporation, which is significantly larger than the latent heat of melting, i.e., energy stored in the vapor–liquid mushy zone at
evaporation temperature is larger than that at melting temperature.
This rise of the pressure in the cavity can be observed from Figure 9. The pressure levels in the order of 25 GPa are generated in the
cavity. The occurrence of maximum pressure close to the cavity edge is also observed from Figure 9, in which pressure variation along the
axial distance at symmetry axis is shown. Increasing heating duration lowers the recoil pressure in the cavity. This may occur because of
one or all of the followings: (1) vapor jet penetration into the stagnant water ambient lowers the axial as well as radial momentum of the
jet as the time progresses, and (2) the cavity size increases, because of the evaporation of the cavity wall due to absorption of the laser
beam, and expansion of the jet in the radial as well as axial directions enhances in the cavity, lowering the recoil pressure.
Figure 10 shows von Mises plastic strain along the radial direction within the vicinity of the surface for the three heating periods.
Plastic strain increases significantly at the edge of the cavity. This increase is almost twice the value at the central region of the cavity.
It should be noted that radial location r ¼ 0 corresponds to the symmetry axis. Moreover, increasing heating period enhances von
Mises plastic strain. This is because of the pressure variation with time, i.e., increasing evaporation rate with time increases the
pressure rise in the cavity, particularly in the region of the cavity edge. However, increase in von Mises plastic strain between 6 ns and
8 ns is much higher than between 8 ns and 10 ns. This is again due to temporal variation of evaporation and pressure buildup in the
cavity, which rises at a fast rate in the early heating period.
Figure 11 shows temporal variation of depth of maximum plastic strain. The depth of plastic strain corresponds to the depth of
plastically deformed zone. The depth of plastic deformation increases gradually up to 3 ns, and this increase becomes rapid until
7 ns and it becomes gradual after 8 ns of heating duration. This is mainly because of the temporal variation of evaporation rate and
pressure developed in the cavity, which vary significantly with progressing time. The maximum depth of plastic region reaches
20 mm below the surface after 10 ns of the heating period. However, this occurs in the region close to the irradiated spot edge. It
should be noted that vapor expansion in the radial direction after 8 ns of heating period results in gradual rise of pressure in the edge
of the cavity. This in turn lowers the magnitude of mechanical pressure load and suppresses the rapid enhancement of depth of
plastic deformation.
Figure 8 Cavity shape and phases around the cavity for 19.7 ns of heating duration. Reproduced from Yilbas, B. S.; Mansoor, S. B.; Arif, A. F. M. Laser
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Figure 9 Pressure distribution along the symmetry axis at different heating durations. Reproduced from Yilbas, B. S.; Mansoor, S. B.; Arif, A. F. M. Laser
Figure 10 von Mises plastic strain in the radial direction at different heating periods. Reproduced from Yilbas, B. S.; Mansoor, S. B.; Arif, A. F. M. Laser
Since the analysis related to thermal stress field at micro/nanolevels is involved in a wide spectrum of applications, due to the space
limitations in this chapter, the focused study on thermal stress is provided in detail. Therefore, thermal stress analysis at micro/
nanolevels includes the laser processing of devices under the short-pulse irradiation. Because of the short heating duration and small
device size, nonequilibrium energy transport takes place in the irradiated substrate material. In addition, irradiated energy is
absorbed in the surface skin of the substrate material, and volumetric heat source resembling the absorption process is incorporated
in the analysis. Thermomechanical coupling and plastic wave propagation at micro/nanolevels are included in formulating the
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Figure 11 Temporal variation of location of maximum von Mises plastic strain in the substrate. Reproduced from Yilbas, B. S.; Mansoor, S. B.;
Arif, A. F. M. Laser Shock Processing: Modeling of Evaporation and Pressure Field Developed in the Laser Produced Cavity. J. Adv. Manuf. Technol.
2009, 42 (3–4), 250–262.
thermal response of the irradiated material. The conclusions derived from the thermal stress analysis are presented below in line
with the previous studies.
In the case of laser short-pulse heating the surfaces, a closed form solution for thermal stress is obtained using the Lie symmetries
technique. Two boundary conditions for thermal stress were introduced, namely stress-free surface and stress continuity at the
surface. The stress-free condition corresponds to the free expansion of the surface during the heating period, while stress continuity
resembles the presence of transparent solid film at the surface. The findings revealed that lattice site temperature rise is sharp in the
early heating period, and it becomes gradual as the heating period progresses. This is attributed to the collisional energy transfer
from electrons to lattice site during the heating period. Thermal stress developed in the surface region is tensile while it becomes
compressive at the same depth below the surface for the stress-free boundary condition. This is attributed to free expansion of the
surface. The thermal stress wave propagates into the substrate material at a constant speed and thermal stress behavior in the surface
region is modified due to stress continuity condition at the surface; in which case, the peak stress reduces with progressing time. In
the case of stress continuity at the surface, thermal stress becomes compressive inside the substrate material for all heating periods.
In order to observe the coupled field problem associated with temperature and stress fields at micro/nanolevels, the thermo-
mechanical coupling between the thermal and stress fields is incorporated in the analysis. It is found that lattice temperature decay is sharp
in the surface region of the substrate material, which is particularly true in the early heating period. This is associated with deposition of the
high intensity irradiation at the workpiece surface in the early heating period. As the distance increases from the free surface towards the
solid bulk as well as the heating time progresses further, lattice temperature decay becomes gradual because of electron excess energy loss
during the collisional process. Lattice temperature follows almost temporal variation of laser intensity distribution at the surface. Thermal
stress developed in the surface region is compressive, and the location of the maximum stress in the substrate material remains almost the
same for different heating periods. Thermal stress increases to attain its maximum at some depth below the surface and it decays gradually
with increasing depth towards the solid bulk. Thermal loading in the lattice subsystem results in negative displacement in the surface
region, which is associated with the thermomechanical coupling between the temperature and stress fields. As the depth below the surface
increases, displacement becomes positive, and it decays gradually with increasing depth below the surface.
The findings due to high intensity irradiation at the surface reveals that the temperature gradient in the surface region is lower
than that corresponding to the region next to the surface vicinity. Because of the recoil pressure, stress levels well in excess of the
elastic limit of the substrate material take place, which in turn results in the propagation of plastic stress wave into the substrate
material. Once the magnitude of recoil pressure reduces considerably, an elastic wave is generated. Since the elastic stress wave
travels faster than its counterpart corresponding to the plastic wave, both waves meet at some depth below the surface. The depth
where the two waves meet defines the depth of the plastic deformation below the irradiated surface. In the present case, the recoil
pressure becomes negligibly small after t* ¼ 0.032 and the depth where two waves interact is about x* ¼ 9.2 (1.49 mm).
The plastic wave propagation because of the recoil pressure formation at the vapor–solid interface is predicted numerically. The
findings revealed that the complex flow structure takes place within the cavity formed during the evaporation process. The radial
expansion of the vapor front enhances the pressure increase in the region of cavity edges. Since the rate of evaporation varies with
time, pressure buildup in cavity edges also varies with time. The impact loading of the surface due to high recoil pressure results in
a high level of von Mises stress. The rate of plastic deformation is high during the heating period of 3–8 ns. The depth of a plastically
deformed region on the order of 20 mm below the surface occurs after a 10 ns heating period.
References
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2. Ramos, J. A. Closed-Form Analytical Solution to the Temperature Distribution inside a Finite Thickness Body Interacting with a Moving Gaussian Laser Beam. Lasers Eng. 1999,
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3. Simon, G.; Grotzke, U.; Kross, J. Analysis of Heat Conduction in Deep Penetration Welding with a Time-Modulated Laser Beam. J. Phys. D: Appl. Phys. 1993, 26, 862–869.
4. Al-Adawi, M. K.; Abel-Naby, M. A.; Shalaby, S. Laser Heating of a Two Layer System with Constant Surface Absorption: An Exact Solution. Int. J. Heat Mass Transfer 1995,
38 (5), 947–952.
5. Yilbas, B. S. Analytical Solution for Time Unsteady Laser Pulse Heating of Semi-Infinite Solid. Int. J. Mech. Sci. 1997, 39 (6), 671–682.
6. Yilbas, B. S.; Shuja, S. Z. Heat Transfer Analysis of Laser Heated Surfaces-Conduction Limited Case. Appl. Surf. Sci. 1997, 108, 167–175.
7. Yilbas, B. S.; Kalyon, M. Laser Repetitive Pulse Heating with Convective Boundary Condition at the Surface. J. Phys. D: Appl. Phys. 2001, 34, 222–231.
8. Yilbas, B. S. A Closed Form Solution for Temperature Rise inside Solid Substrate due to Time Exponentially Varying Pulse. Int. J. Heat Mass Transfer 2002, 45, 1993–2000.
9. Li, K.; Sheng, P. Plane Stress Model for Fracture of Ceramics during Laser Cutting. Int. J. Mach. Tools Manuf. 1995, 35, 1493–1506.
10. Wang, H. G.; Guan, Y. H.; Chen, T. L.; Zhang, J. T. A Study of Thermal Stresses during Laser Quenching. J. Mater. Process. Technol. 1997, 63, 550–553.
11. Peyre, P.; Fabbro, R. Laser Shock Processing: A Review of the Physics and Applications. Opt. Quantum Electron. 1995, 27, 1213–1229.
12. Chu, J. P.; Rigsbee, J. M.; Banas, G.; Elsayed-Ali, H. E. Laser-Shock Processing Effects on Surface Microstructure and Mechanical Properties of Low Carbon Steel. Mater. Sci.
Eng. 1999, 260A, 260–268.
13. Yilbas, B. S.; Sami, M.; Shuja, S. Z. Laser-Induced Thermal Stresses on Steel Surface. Opt. Laser Eng. 1998, 30, 25–37.
14. Yilbas, B. S.; Naqavi, I. Laser Heating and Thermal Stresses Time Exponentially Heating Pulse Case. Trans. Can. Soc. Mech. Eng. 2006, 30, 113–142.
15. Kalyon, M.; Yilbas, B. S. Analytical Solution for Laser Evaporative Heating Process: Time Exponentially Decaying Pulse Case. J. Phys. Part D: Appl. Phys. 2001, 34, 3303–3311.
16. Yilbas, B. S.; Sami, M.; Al-Ferayedhi, A. Closed Form and Numerical Solutions to the Laser Heating Process. Proc. Inst. Mech. Eng., Part C 1998, 212, 141–151.
17. Yilbas, B. S.; Yilbas, Z. Some Aspects of Laser-Metal Vapour Interaction. Pramana J. Phys. 1988, 31 (5), 365–381.
18. Yilbas, B. S.; Ageeli, N. Thermal Stress Development due to Laser Step Input Pulse Intensity Heating. J. Therm. Stresses 2006, 29 (8), 721–751.
19. Yilbas, B. S.; Ageeli, N. Thermal Stresses due to Exponentially Decaying Laser Pulse and a Convection Boundary at the Surface. Lasers Eng. 2006, 16, 235–265.
20. Yilbas, B. S.; Shuja, S. Z.; Arif, A. F. M. Elastic Displacement of the Surface due to a Laser Heating Pulse. Proc. Inst. Mech. Eng., Part C 2001, 215, 1271–1282.
21. Yilbas, B. S.; Al-Dweik, A. Y. Exact Solution for Temperature Field due to Non-Equilibrium Heating of Solid Substrate. Phys. B: Condens. Matter 2011, 406 (23), 4523–4528.
22. Yilbas, B. S.; Al-Dweik, A. Y. Non-Equilibrium Heating of a Solid Surface by a Short-Pulse Laser: A Closed Form Solution Including Thermomechanical Coupling. J. Therm.
Stresses 2013, 36, 1308–1321.
23. Yilbas, B. S. Improved Formulation of Electron Kinetic Theory Approach for Laser Short-Pulse Heating. Int. J. Heat Mass Transfer 2006, 49, 2227–2238.
24. Kovalenko, A. D. Thermoelasticity, Basic Theory and Applications. Academy of Sciences of The Ukranian USSR, Institute of Mechanics, Translated by Macvean, D. B.; Alblas, J.
B.; Wolters-Noordhoff Publishing: Groningen, The Netherlands, 1969.
25. Yilbas, B. S.; Al-Ageeli, N. Thermal Stresses due to Time Exponentially Decaying Laser Pulse: Elasto Plastic Wave Propagation. Int. J. Mech. Sci. 2004, 46, 57–80.
26. Kalyon, M.; Yilbas, B. S. Analytical Solution for Thermal Stresses during the Laser Pulse Heating Process. Proc. Inst. Mech. Eng., Part C 2001, 215, 1429–1445.
27. Yilbas, B. S.; Sahin, A.; Davies, R. Laser Heating Mechanism Including Evaporation Process Initiating the Laser Drilling. Int. J. Mach. Tools Manuf. 1995, 35 (7), 1047–1062.
28. Yilbas, B. S.; Shuja, S. Z.; Arif, A. F. M.; Gondal, E. Laser Shock Processing of Steel. J. Mater. Process. Technol. 2003, 135, 6–17.
29. Lin, X. Numerical Computation of Stress Waves in Solids; Akademie Verlag: Berlin, 1996.
30. Tzou, D. Y. Macro-to-Microscale Heat Transfer; Taylor and Francis: Washington, DC, 1997.
31. Yilbas, B. S.; Mansoor, S. B.; Arif, A. F. M. Laser Shock Processing: Modeling of Evaporation and Pressure Field Developed in the Laser Produced Cavity. J. Adv. Manuf.
Technol. 2009, 42 (3–4), 250–262.
32. Patankar, S. V. Numerical Heat Transfer; McGraw-Hill: New York, 1980.
33. http://www.ansys.com, ANSYS Inc., Canonsburg, PA 15317, USA.
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7.04 PVD Technology in Fabrication of Micro- and Nanostructured Coatings
M Aliofkhazraei, Tarbiat Modares University, Tehran, Iran
N Ali, Nanosmat Ltd., Manchester, United Kingdom
7.04.2 Surface Preparation 52
7.04.3 Vacuum Evaporation 52
7.04.4 Evaporation Sources 52
7.04.4.1 Materials and Applications 53
7.04.5 Gas Sputtering Coating 53
7.04.6 Ion Plating 53
7.04.6.1 General Principles 53
7.04.6.2 Materials and Applications 53
7.04.7 Active Reaction Evaporation 53
7.04.7.1 Reactive Ion Plating 53
7.04.7.2 Arc Evaporation Ion Plating 54
7.04.7.3 Sputter Ion Plating 54
7.04.7.3.1 Materials and Applications 54
7.04.7.4 Sputtering Plating 55
7.04.7.4.1 Principles 55
7.04.7.5 Ion Implantation 56
7.04.7.5.1 Principles 56
7.04.8 Application of PVD Technology for Fabrication of Micro- and Nanocoatings 56
7.04.8.1 Fabrication of Coatings 56
7.04.8.2 Characterization of Coatings 71
7.04.8.3 Properties of PVD-Coated Samples 74
7.04.8.3.1 Electrochemical Behavior 75
7.04.8.3.2 Tribological Behavior 78
References 81
7.04.1 Introduction
This chapter involves all techniques applied for synthesis of inorganic coats through condensation or vapor phase reaction on the
surface of a substrate. This does not comprise thermal or thermochemical diffusion operation, but it includes ion implantation,
although it is essentially a coating process. The common limitations of almost all physical vapor deposition (PVD) techniques are in
the creation of rather thin (107–104 m) layers, while chemical vapor deposition (CVD) is applied for both thin layers and those
thicker than 1 mm. Owing to their abrasion resistance and corrosion resistance benefits to engineering pieces, such coats are very
important in engineering applications. In addition, they have a wide market in electronic and optic devices, decorations, and
architecture. For these reasons, various advances have been made in all aspects, and since each application has its own requirements,
different techniques are combined to produce new ones. Indeed, this large overlap between PVD and CVD techniques implies that
their complete segregation and distinction are difficult. The commercial success of many species of these two processes is considered
shaky ground, since their characteristics have not been fully recognized and they have not been able to find their way to the market.
Table 1 briefly introduces their processes and characteristics (1–42).
All vapor processes involve operations in the container. Whether in vacuum or in a container resistant to high temperature and
corrosive gases (such as those used in CVD), the sample has to be resistant. This fact causes a limitation in piece size. Since the substrate
can be skillfully applied against coating supplies, again the particles’ shape and size are limited only by investment costs in the workshop.
Tiny particles – like those used in coating – are kept in large quantities in the basket and in plated barrels. Large pieces such as plane
landing parts are coated with Al in containers that are 2–3 m in diameter, while the glass sheets of the windows with dimensions of
6 m 8 m are coated in a workshop with a length of 60 m in open space. The majority of these processes are performed in batch form.
However, vacuum evaporation on paper or plastic sheets might be accompanied by air that is blown or through a supply pump.
The PVD process includes processes that indicate the main controlling factors of PVD and have wide applications. The nature of
a created coat also corresponds with PVD processes. PVD coats are produced either from evaporation from a melting source or by

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50 PVD Technology in Fabrication of Micro- and Nanostructured Coatings
Table 1 A comparison between characteristics of the process
Coat applications and its

specific properties Coating materials Throwing power Process temperature ( C) Method
Electronics, optic, and decorations. Mainly the metals, especially Al Direct orientation Ambient temperature up to Evaporation
Coating operation is easy (a few numbers of the alloys 600 C, typically below in vacuum
and simple compounds) 200 C
Abrasion resistance for tools, molds, etc. Typically nitrogen Direct orientation 200–400 C Ion implantation
Its effect is deeper than the depth of (boron and carbon) The best one for nitrogen is
the primary implantation. Exact local below 200 C
operation; excellent process control
Electronics, optics, and decorations; Ion coat: aluminum and other Average to good
Ambient temperature to 0.7 Ion coat
resistance to corrosion and abrasion, metals (some alloys) of the coat’s melting Active reaction
dry lubrication, and thicker Tin and other compoundsb temperature; the optimum evaporation (ARE)a
engineering coats condition is high
temperatures
Electronics, optics, and decorations; Metals, alloys, glasses, oxides, Direct orientation Ambient temperature to 0.7 Sputtering
commonly thin coats; excellent tin, and other compoundsb of the melting temperature
process control of the metallic coats; the
optimum state is at the
temperature of 200 C for
nonmetals
Thin abrasion-resistant layers on Metals (especially refractory Very good 300–2000 C Chemical vapor
metallic and carbide molds, tools, metals), tin, other compounds, Typically 600–1200 C deposition (CVD)
etc.; delicate structures of the pyrolyzed carbon, and
refractory metals and carbon or pyrolyzed boron nitride
pyrolyzed boron nitride
a
Active evaporation (including sputtering and arc evaporation).
b
Compounds: oxides, nitrides, carbides, silicides, and borides of Al, B, CR, Hf, Mo, Nb, Ni, Re, Si, To, Ti, V, W, and Zr.
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La2Zr2O7/YSZ Deposited by Electron Beam-physical Vapor Deposition. J. Alloys Compd. 2009, 473, 509–515; Sáfrán, G.; Reinhard, C.; Ehiasarian, A. P.; Barna, P. B.; Szekely,
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Deposition on the Thermal Cycle Life of Thermal Barrier Coatings Fabricated by Electron Beam Physical Vapor Deposition. Surf. Coat. Technol. 2008, 202, 3507–3512; Ma, W.;
Gong, S.; Li, H.; Xu, H. Novel Thermal Barrier Coatings Based on La2Ce2O7/8YSZ Double-ceramic-layer Systems Deposited by Electron Beam Physical Vapor Deposition. Surf.
Coat. Technol. 2008, 202, 2704–2708; Lamborn, D. R.; Wilke, R. H. T.; Li, Q.; Xi, A.; Snyder, D. W.; Redwing, J. M. Growth of Thick MgB2 Films by Impinging-jet Hybrid
Physical-chemical Vapor Deposition. Adv. Mater. 2008, 20, 319–323; Kelly, M.; Singh, J.; Todd, J.; Copley, S.; Wolfe, D. Quantitative Microstructural Analysis of Thermal Barrier
Coatings Produced by Electron Beam Physical Vapor Deposition. Ceram. Eng. Sci. Proc. 2008, 28, 71–80; Kelly, M.; Singh, J.; Todd, J.; Copley, S.; Wolfe, D. Metallographic
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S.; Woo, S. K.; Jung, Y. G.; Paik, U.; Lee, K. S. Influence of Subsurface Layer on the Indentation Damage Behavior of YSZ Thermal Barrier Coating Layers Deposited by Electron
Beam Physical Vapor Deposition. J. Korean Ceram. Soc. 2008, 45, 549–555; He, X.; Meng, B.; Sun, Y.; Liu, B.; Li, M. Electron Beam Physical Vapor Deposition of YSZ Electrolyte
Coatings for SOFCs. Appl. Surf. Sci. 2008, 254, 7159–7164; Hagarova, M.; Stepanek, I. Properties of Thin Coating Deposited on Tool Steel after Different Technological
Conditions of Physical Vapour Deposition Process. Kovove Materialy 2008, 46, 165–172.
injection of atoms from a solid source bombarded with ionized gases (sputtering). The vapor might be released as a flow of neutral
atoms in vacuum (evaporation in vacuum) or be partially ionized. A share of ionized current (e.g., 0.1%) is generally mixed with
ionized gas and deposited on earthed or biased substrate (sputtering and ion plating). But a strongly ionized current that develops
plasma is absorbed with a substrate with bias, which is called as plasma arc evaporation. Besides, an ionized ray may get 100%
concentrated and accelerated up to very high energy levels for penetration in the substrate (ion implantation). This chapter discusses
only the processes with commercial application. The second part discusses CVD approaches based on categorized chemical reac-
tions (43–66). Among the technique applied for PVD coatings in cutting tools, one can name reactive magnetron sputtering.
Alumina growth in Ar–O2 gas mixtures induces some problems due to the presence of insulating layers on targets, and hysteresis
impacts with respect to oxygen gas flow. Selinder et al. explain a technology for deposition of crystalline alumina (i.e., reactive high-
power impulse magnetron sputtering) (28). Here, pure Al was utilized as the target material, and the cemented carbide (WC–Co)
substrates were kept at 500–650 C. With respect to oxygen gas flow, hysteresis effects were mitigated. This, in turn, enabled stable
growth at a high deposition rate. The high-power impulses contributed to obtaining a crystalline oxide coating. Based on X-ray
diffraction (XRD) and cross-section transmission electron microscopy (TEM) that were carried out, it was verified that a-alumina
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PVD Technology in Fabrication of Micro- and Nanostructured Coatings 51
Figure 1 Scanning electron micrographs of the surfaces of the alumina coatings (left), and cross-sectional fracture surfaces (right). Deposition
temperatures from top to bottom: 650, 575, and 500 C. Reproduced from Selinder, T. I.; Coronel, E.; Wallin, E.; Helmersson, U. a-Alumina Coatings on
WC/Co Substrates by Physical Vapor Deposition. Int. J. Refract. Met. Hard Mater. 2009, 27, 507–512.
films were formed. Technological testing of these PVD alumina coatings, with modern Al–titanium nitride (TiN) as the standard,
showed considerably improved crater wear resistance in steel turning. Figure 1 shows scanning electron micrography (SEM) of the
surfaces of the alumina coatings.
Wang et al. successfully deposited thick silicon carbide films on stationary graphite substrates at a deposition rate of 125 nm s1
(67). To do so, they applied the thermal plasma PVD technique and used ultrafine SiC powder that fed into a hybrid plasma jet and
completely evaporated. Then, the relationship between the processing parameters and the morphology, deposition rate, compo-
sition, and crystal structure was examined. Here, the typical conditions of substrate, including the temperature of 1400–1700 C and
chamber pressure of 250 Torr, were applied, and the findings were compared with the results of rotating substrate deposition at the
substrate temperature of 750 C. The findings revealed that for rotating substrate deposition and stationary substrate deposition, the
deposition rate and composition involve different processing parameter dependences. Moreover, based on the applied deposition
conditions, the films demonstrated dense cross-sections or cauliflower-like structures. Like any other transition metal carbides,
titanium carbide involves excellent wear-resistant properties in machining of stainless and high-speed tool steels. Wolfe et al.
successfully deposited TiC on 304 stainless steel using reactive ion beam-assisted (RIBA) electron beam-PVD (EB-PVD) (68).
Depending on the processing parameters, the hardness values were determined as varying from 1100 to 3500 VHN0.050. Here,
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surface morphology and texturing degree well corresponded with the processing conditions. In addition, ion bombardment led to
a strong surface and growth texture in primarily the (111) orientation. Moreover, a shift from the (111) orientation to (200) was
observed at high substrate temperatures.
Schulz et al. reported that application of the scratch test indicates that the electron irradiation of the specimen for obtaining
a higher substrate temperature before deposition of TiN by reactive sputtering allows one to obtain a considerable improvement of
the coating adhesion (69). This can be mainly because of the reduction of contaminants adsorbed at the highly active sample surface
after the sputter cleaning. Another explanation for this phenomenon might be the electron beam, which facilitates the chemical
transition of the iron oxides on the sample surface into cubic FeO. Here, preheating to a high sample temperature and maintaining
this temperature during the deposition by an electron beam involve various advantages. This is due to the fact that after surface
sputtering of the substrates, any readsorption of gases on the surface will be reduced. In addition, the higher coating adhesion and
higher temperature during deposition result in modified coating properties. A smaller deposition rate and smaller nitrogen content
were found in comparison to other coatings deposited under the same conditions but with lower temperatures. This presumably
shows that the combination of a high surface temperature and the processes (especially induced by the electron beam) reduces the
incorporation of nitrogen into the TiN layer.
7.04.2 Surface Preparation
None of the vapor deposition approaches offers acceptable adhesion for engineering purposes unless the substrate is completely
clean. The required cleaning standard is very different from the one required for surface welding operations or sputtering operations.
Here, cleaning involves the removal of surface layers of pollution that are the thickness of several molecules. This preparation
process cannot be performed in the air. The best bombardment technique is the ionic technique, assuming that many PVD processes
have experienced such an operation. Cleaning through ion bombardment is performed by low-pressure gas discharge. The
workpiece is attached to the ground with a voltage of 2–5 kV. The produced positive argon ions by electrical discharge are accel-
erated toward the workpiece at high energy levels, and the surface atoms are sputtered due to the impact. Hence, the layer is cleaned
through creation of an erosion process that scatters the pollution and substrate layer into the container. In CVD processes, the only
requirement is to adequately degrease the substrate and clean it from its surface oxide layers. Typically, the only thing required
before the coating process is a cleaning cycle, including reduction of gas at high temperature (34).
7.04.3 Vacuum Evaporation
Vacuum evaporation, which might have the widest range of application in PVD techniques, is the simplest and oldest of them,
although it involves some limitations. Some of these limitations can be decreased through applying coat materials with ionized
output, but some of them are very complicated and cannot yet be considered important industrial processes. Vacuum evaporation is
typically performed at a complete vacuum (0.1–1.0 MPa) in which the mean free path of the gas atom (i.e., the average path traveled
by the atom before it hits other atoms) is 1–100 m. Since this distance is much longer in container dimensions, the atom evaporated
from the evaporation source travels in a direct path, and coating is not possible around the corners without physical movement of
the substrate around the corners or further coating in some spots. Vaporizing of coating materials is performed through thermal
evaporation. The vapor contains a large amount of single or clustered atoms, although in some processes partial vapor ionization is
possible. Except in the case of ionization presence, the particle energy is very low and is not large enough required for evaporation
(about 0.1–1 eV).
The coated substrate usually has a ground contact, lacks any potential difference, and can be both heated and cooled. Among the
PVD processes, the rate of vacuum evaporation process is the highest and can even reach up to 75 mm min1; however, its effective
level is up to 2 mm min1. To keep the final polishing of the lower surface, it is possible to perform a deposition process; however,
adhesion of the thermal evaporation coats completely depends on the cleanness of the substrate immediately after the deposition
process. In many unconventional industrial applications, the cleaning cycle is removed through ion bombardment, and then
adhesion deteriorates (5,26,31,51,70–74).
7.04.4 Evaporation Sources
Vacuum evaporation at perceptible temperatures implies that the substance vapor pressure is 1 Pa. This requires that the temper-
ature be higher than melting temperature for many materials. Hence, it is required to use a crucible that is able to contain the melt
without reacting with it. Source heating is performed through direct electrical heating (e.g., using W of Mo crucibles, or heating an
electronic ray of the material in a water-circulating copper crucible). Here, an exception is Al, which is vaporized in a refractory
electrically conductive container made of boron nitride–titanium dioxide, where the melted metal does not react with W.
Considering various vapor pressures of the alloy components, alloy deposition is possible despite the limitations. Although
sometimes it is possible to avoid this by putting the fine powder of the alloy in a superheated container, where the powder will experience
its sudden and overall evaporation, the reaction between the powder and container imposes some limitations. Electron ray heating is
a particular melting, known as skull melting, where only the source (but not the crucible) is heated, and thus the problems induced by the
reaction between melt source and crucible are avoided. By ray vacillation between crucibles containing each of the constituents and,
subsequently, ray power regulation for appropriate vapor generation for each of them, it is possible to obtain an alloy coat structure.
However, this system is very complicated, and the ray produced has to be protected from metal vapor (62,75–79).
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7.04.4.1 Materials and Applications

The main application of vacuum evaporation is limited to coatings of single metals such as Al (which by itself comprises 90% of the
evaporated materials), Cr, Ag, and so on. Here, a tiny number of components can be evaporated without composition change. Engi-
neering application of the vacuum coats involves some limitations, since in the general aerospace applications, Al and Ni–Cr (for
corrosion protection) and Al and Ag are used as solid lubricants. The hard Cr or Al2O3 coats are deposited on steel tools or WC, but now
sputtering coats have replaced this. The most important application field of this coat is for decoration purposes. For instance, Cr is utilized
for car decorations, Al is used for packing and forged ornaments, and fluorides are used for rainbow effects. Evaporation coats for
electronic applications are Al and Ta on the plastic film of capacitors; Al–Si and Ni–Cr via sudden evaporation for capacitors with a thin
layer; and Si, GaAs, and CdS for semiconductors and cellular phones. The optic coats also include Al and Ag for mirrors and reflectors, and
as coats on large windows, and the recognized evaporation coat of MgF2 as an antireflective coat on lenses.
7.04.5 Gas Sputtering Coating
Typically, throwing power is negligible during the vacuum evaporation process since it is affected by the path and direction. However, the
presence of gas molecules in the coating chamber reduces the mean free path of the vapor atoms and - in cases with high enough number
of hits - the coating atoms will not hit to the surface of substrate in direct path. At the pressure of 1 Pa, the mean free path is 5 mm. Thus, in
a system with an ordinary source in distance of 200 mm from the substrate, vapor atoms experience above 50 impacts in each path and
collide with substrate in almost all directions and paths. Now, the collision and entering path of the atoms is relatively controlled by a gas
diffusion process. Here, the pressure range is 0.1–5 Pa where the throwing power is reinforced without any noticeable decrease in
evaporation rate. Gas injection to the coat chamber introduces new parameters that lead to coat quality improvement and expansion of
the range of materials applied as the coat in deposition. The main parameters in this process are the electrical state (neutral or ionized)
and chemical state of the gas (neutral or active) (17,31,72,75).
7.04.6 Ion Plating

7.04.6.1 General Principles
Ion plating comprises evaporation in an electrically inert form for industrial applications through an ionized gas as a sputtering envi-
ronment. Through constant gas injection and controlled pumping, dynamic pressure is maintained as 1 Pa, for instance for Ar. The
dynamic pressure preference is due to the fact that it prevents gas impurities in the container. The evaporation source is connected to the
ground, while substrate gets a negative charge at 1–2 kV. The evaporated atoms gain energy from colliding with ionized argon. In contrary
to the origin of the term ‘ion plating’ the ionization level of vapor flow does not exceed 0.1%. Thereby, the term ‘ion plating’ is completely
irrelevant but still completely accepted. The combination of the high energy (z10 eV) of the evaporated atoms with the constant
bombardment of substrate with gas ions leads to the excellent adhesion of the thin layer. This condition in a dense coat is feasible through
proper selection of the deposition parameters. The presence of the gas also guarantees adequate throwing power. Here, like the vacuum
vapor technique, the evaporative materials are melted and gas ionization is enhanced using a hot electron-emitting filament. In this
regard, various techniques have been introduced that all claim high density and adhesion of the thin layer; but in all these techniques, the
substrate has to be kept at high direct current (DC) potential or is attached to a radiofrequency (RF) generator.
7.04.6.2 Materials and Applications

The deposition rate of this technique is less than that of vacuum evaporation since some plating materials are sputtered from the
substrate. Nevertheless, it equals the highest rates in PVD techniques. Through deposition at 0.7 of melting temperature, it is
possible to obtain dense deposits. Grain size distribution of the deposit (columnar, co-axis, etc.) is controlled through appropriate
selection of deposition rate, gas pressure, potential waste of the substrate, and substrate temperature. Over the past two decades,
ionic plating has been an interest for many researchers, but now its important industrial applications have been practically
developed. Similar to vacuum evaporation, the main limitation of this technique is application of evaporable metals, along with
some limitations related to the crucible. In addition, since the substrate holder (which is required for parts vacillation and rotation)
is placed at high potential, equipment complication is more than that of simple vacuum evaporation. Electrodeposition of Al for its
corrosion protection is not a practical issue. Also, thermal spray of Al is not appropriate for some pieces, but the thin layers of Al in
coatings are very common for complicated plane parts.
Here, a competing or even alternative ion plate is electrodeposition. For some cases, such as Cd or where the risk of hydrogen-
induced brittleness for high-strength steel substrates exists, and also because of the toxic nature of the solution, some countries
banned using them. For these reasons, Cr is increasingly deposited on plastics for car ornaments. The thin solid lubricant layers such
as Ag are applied in aerospace applications on the bearing. Also, it is used in the case of severe heat, irradiation, and vacuum. In
general, every material that can be subjected to the vacuum evaporation process can yield ionic plating with higher and more
favorable adhesion and density.
7.04.7 Active Reaction Evaporation

7.04.7.1 Reactive Ion Plating
Both vacuum evaporation and ion-plating techniques need coating materials that can be evaporated without any change in
their composition. However, there is a growing high demand for abrasion-resistant oxide coats, nitrides, carbides, and so on,
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which is due to the fact that discharge irradiation (ARE) – which is recognized as an active ion coat – has made various
advances. Here, the main principles are similar to the function of ion plating, except for with electrical discharge, an active gas
is utilized instead of the inert gas. The metallic part of the compound is embedded in an active vapor gas. Gas activity is
enhanced by radiation discharge, and the reaction occurs in the gas phase or in a more common way on the substrate surface.
Therefore, for instance, a thin, hard, scratch-resistant TiN can be produced by titanium evaporation in a low-pressure radiation
discharge mix of Ar and N.
7.04.7.2 Arc Evaporation Ion Plating
An indirect heating process is applied through the active approaches discussed here for plating materials evaporated in radiation
discharge with low ionization. Besides, through arc evaporation, a solid metallic target is utilized. This target, which is installed as
local and temporary between the sources (cathode) or the container (expanded anode), collides with a local anode; however, unlike
the created arcs in the environment, there are no illuminant electrical discharge paths. The high density in the arc root (above
109 W m2) results in intense evaporation of the metal vapor that – unlike ion plating and other forms of ARE – is strongly ionized
and adsorbed as negatively charged.
The substrate is subjected to severe bombardments by metallic ions that result in a clean and heated surface without any change
in the properties of the coating material. By gas injection, the parameters for creation of ion coat conditions are regulated.
Application of the arc for evaporation of a solid target eliminates many limitations of the completely melted sources. Therefore, the
active metals with high melting temperature can be melted without any crucible-associated problems. Source plurality can be
organized by vertical, horizontal, downward, or any other dip angle for rate and uniformity improvement. The combination of high
substrate temperature and high energy ions leads to creation of coats with excellent adhesion and density; however, drops thrown
from the target can lead to high roughness of the coat surface compared to the other active methods.
7.04.7.3 Sputter Ion Plating
Another important commercial approach to deal with limitations of evaporation synthesis – which does not involve coat
supply melt – is ion bombardment sputtering. Sputtering does not require plating supply to be melted; thus, the range of
applicable materials in this technique is wider. The sputter ion plating (SIP) process can be conducted using both inert and
active gases, although its rate is much slower than that of evaporation approaches. The SIP technique involves a high purity
level as well as control of the components and pieces in the system. Furthermore, it is suitable for operations both in large
containers and in packages with various sizes. This set of factors gives specific commercial advantage to this technique over
other similar ones.
7.04.7.3.1 Materials and Applications

For SIP and various ARE techniques, the mainly used compounds are oxides, carbides, and nitrides that are applied through
adjusting and synchronizing the synthesis rate of the metallic compound with partial pressure of oxygen, ethane, or nitrogen.
Although the thin molybdenum disulfide layers are synthesized and the other components such as borides and silicides are utilized
as the coat, there are no wide industrial applications for them yet. In this regard, TiN is a very commonly utilized component. Now,
the thin TiN layers with thickness of 5 mm are applied in bearings and a wide range of applications such as simple drills, complex
gearboxes, rods, wiredraws, hones, cutting tools in the mills, and shaping tools. By plating these tools, it is possible to enhance their
life up to 3 times. In addition, cutting speed and quality of the piecework can be enhanced in this way. The thin abrasion-resistant
layers are golden and are utilized to provide scratch resistance in ornamental tools such as stainless steel or a golden watch frame.
Typically, substrate temperature is kept above 400 C in tribological applications, but the thin layers for ornamental purposes can be
deposited at much lower temperatures (17,31,70,72,75).
Although TiN has the widest range of applications in composition of thin abrasion-resistant layers, it is utilized on a limited scale
compared to other materials such as titanium carbide, titanium carbonitride, titanium–aluminum nitride, and hafnium, chromium, or
zirconium carbide or nitride. For the specific applications, for instance once the temperature above 500 C is not suitable, they can be
used. Research about thin coats with suitable surface conditions is still in progress, and, beyond any doubt, they will incorporate with
multilayer coating systems in the future. In the optic-electronic field, ARE and its fabrication techniques allow fabrication of scratch-
resistant and flameproof coat for evaporable components. Also, there is a suitable market for thin (<0.1 mm), transparent, conductive
In–Sn layers that are deposited as deicing layers in cases such as deposition on plane windows.
Today, there is an emphasis on thin layers with suitable tribological surfaces; however, also the metallic and, rarely, alloy coats
can be fabricated through ionization-assisted approaches. Sputtering ion coats produce dense, adhesive, and pure coats of
refractory metals. Also, Al and Cd coats have been reported for corrosion protection. Another application of ion plating is for the
edges of Al and Cu conductors in some electronic devices. However, the main operation and application field of these techniques
is in deposition of thin coats of material, including metals, alloys, and components where deposition is not possible through
electrodeposition. Now, several gas-applying active techniques are competing, and there is considerable overlap between them in
some cases such as TiN coats synthesis, but there is still a long way to go before claiming which of them will succeed in this area.
In the past, the different characteristics of these techniques resulted in different coat properties despite applying the same
precursor, but it seems that these differences have been reduced due to better control and familiarity with the processes. So, it can
be claimed that the final dominance and superiority of a technique are largely controlled by its commercial aspects rather than
technical properties.
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7.04.7.4 Sputtering Plating

7.04.7.4.1 Principles
Sputtering plating is performed in a cleaning cycle through ion bombardment before evaporation coating. Through Ar ion
bombardment, the material is sputtered from the negative pole of the substrate. The sputtered materials are in the form of high-
energy atoms concentrated in the surrounding surfaces. This high energy content of ion bombardment is enough to cope with
any bond energy under the substrate. The source, which is called the ‘target’ also performs the evaporation process by ion
bombardment rather than by heating. For these reasons, the sputtering coating process can be applied to deposit a wide range of
coating materials. Such an advantage makes sputtering coating the easiest and best coating technique and introduces it as a process
with the widest range of applications in the synthesis of engineering optic and electronic thin layers. In this approach, the target is
a solid and can be an alloy, compound, or plastic alloy containing several powders at which ionized gas potential is applied in DC
or RF form. The applied gas can be in inert or active form. Also, the substrate can be earthed or biased. The layer temperature in this
technique is affected by various factors, but it is typically below 200 C, unless high temperatures are needed.
Here is also a set of problems. The required gas pressure (z0.5 Pa) reduces the mean free path up to 30 mm. Therefore, once it
does not tend to lose high energy of the coat, with its various advantages, the substrate has to be placed almost at this distance. This
does not mean that balance-throwing power has occurred, and the target also has to be similar to the substrate in terms of the shape
and size. Although there are also other obstacles, the most dramatic one is the low deposition rate. In the best state, the simple diode
system cannot have a coating rate above 0.1 mm min1. In more complicated systems equipped with ancillary ionization sources,
the deposition rate can reach up to 0.4 mm min1. This low deposition rate not only is troublesome but also leads to the generation
of a high amount of gas in the deposit. The deposition rate of the layer (0.1 mm min1) almost equals three single layers in each
second, which equals values reported for the oxygen entering rate in partial pressure of 1 MPa. So, this vacuum is suitable to retain
thin oxygen-free layers. It is also possible that warm deposition be required after thermal treating for adsorption of the discharged
gas in the closed environment. A magnetron source is considered a breakthrough that is able to provide high deposition rates. This
will be explained in this chapter. Despite the problems of the sputtering technique, this method can be applied in cases where the
other deposition techniques cannot work appropriately, and it produces excellent, although thin, coats.
7.04.7.4.1.1 Substrate polarization

In ordinary sputtering operations, ionization potential is applied only in the target while the substrate is connected to the ground;
but via a different technique, called bias sputtering, the substrate also is polarized at the potential below the target ionization
potential. The polarization effect of the substrate is a deviation of a share of ionic bombardment in the substrate, and then obtains
some benefits through ion plating. This different approach can be considered a type of ion coating through which sputtering is
applied instead of evaporation for vapor generation from the coat. Based on the applied ionized gas and combination of the thin
coat layer, the substrate pole can be positive or negative.
7.04.7.4.1.2 Gas ionization

Sputtering coats began to be applied in 1920. Two main disadvantages of this technique are the necessity to limit their operation to
electrically conductive targets (since the insolents are charged during the bombardment and reject gas ions) and the low coating rate
induced by the rather inefficient ionization rate of the Ar. Using an RF generator, the problems and complications associated with
insolent targets charged with DC bombardment have been solved. If an insolent or nonconductive target is coupled with an RF
generator, the created spatial charge is effectively removed and the surface gets a negative charge. Typically, the applied frequencies
are above 10 MHz, and the RF poles are typically 5.2 kV in peak-to-peak form. Hence, the target can be an insolent or oxide material
directly sputtered on the substrate, although the oxide erosion rate is typically 10% of that of similar metals. A valuable feature of RF
sputtering is direct coat synthesis from nonmetallic targets.
The primary efforts made for increase of ionization output of the simple DC diode system were successful and promoted
sputtering rates up to 3 times higher. But magnetron sputtering enhanced deposition rates up to a level comparable to that of
vacuum evaporation. Undoubtedly, the general acceptance of sputtering coats in current technology is because of magnetron
sputtering. The magnetics beyond the target are arrayed in a manner so that a magnetic flue line is parallel to the target along the
piece length and also located in right angles of the electrical field. The entrapped electrons in this blocked and intersected zone are in
spiral form and are compressed parallel to the target. Hence, once the length of the electron motion pass increases, it is very likely
that the collision numbers between ionized gases and the gas atoms enhance. Therefore, in the upper part of the target surface,
which is bombarded and created a strong flow of coated atoms, an ionization zone is developed. This technique is applied for
synthesis of magnetic coats only when the target temperature is kept higher than Curie temperature, unless the ferromagnetic targets
will lead to magnetic field limitation and limitation of the electrically discharged electrons effect. Here, there are various parameters
that vary based on polarization, target type, and magnetization. The magnetron sources coupled with various polarized RF
generators have significantly developed a sputter-plating perspective that is now applied in a wide range.

7.04.7.4.2.1 Materials
As with ion plating and ARE, and also in sputter plating, element sources in inert gas plasma are used for component deposition.
Supplies that themselves are chemical compounds are also utilized, but there is always a small change in the coat. There are various
effective factors in the selection of active sputter plating from a metallic or composite target, but both of these techniques are widely
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applied. This is mainly owing to the wide range of available materials applied as the target in the sputtering process. The fabrication
of polytetrafluoroethylene (PTFE) coats and some polymers is possible now, where the target has various sizes and shapes varying
from metallic plates with a length of several meters to simple or formed disks, rings, nodes, cylinders, buttons, and so on. Here, the
limitations are usually financial rather than technical.
7.04.7.4.2.2 Applications
In this section, a list of numerous applications of sputter-plating techniques is introduced. Note that some of these layers are only
50 Å in thickness.
Engineering
B Resistance to corrosion and oxidization, like Ni–Cr, M–Cr–Al–Y, and polymers; and
B Resistance to abrasion, such as TiN, other nitrides, W, Mo, carbides, borides, and carbon.
Diamonds
B Lubricants such as Ag, In, MoS2, PTFE, selenites, silicides, and tellurides.
Electronics
B Penetration layers such as Si(ON), silicides, and TiN; and
B Semiconductors such as GaAs, GaP, InAs, and InP.
Electro-optic
B Lens covers such as MgO and MgF2;
B Thin transparent conductive layers such as In–Sn–Ox;
B Blur-proof coats such as TiO2–Ag, Cd–Sn–Ox, Cr(N), and SnO2;
B Interference filters such as Ge, metallic oxides, fluorides, and ZnSe–S;
B Luminescents and light-emitting diodes (LEDs) such as MoO3 and ZnSe; and
B Optical conductors such as selenites, sulfides, and tellurides.
7.04.7.5 Ion Implantation

7.04.7.5.1 Principles
Ion implantation does not create a coating; rather, it produces a strong ray with very high-energy ions (which are extremely higher
than those produced in ARE or sputtering) that diffuse to the substrate and change it instead of the coat. The process is rather similar
to carbon plating. In this regard, Deamaley et al. have performed various tasks in Harwell and focused on ionized nitrogen ions. It is
worth mentioning that boron and carbon rays have been previously studied. Nitrogen ion rays with energy of 80–150 KeV are
directly guided toward a workpiece surface and penetrate a depth of 0.1 mm. The process is performed in the vacuum and then is
considered a direction-dependent approach. The cross-section of the ray is square and expands at 20 , which covers
a 150 mm 150 mm workpiece in a fixed or rotating state. Based on the coat target, operation time is 1–10 h, and temperature
increase does not exceed several centigrade. Hence, the thermally operated and polished pieces can be ion implanted without any
distortion risk. Here, the only noticeable change is the slight surface polish (80).
Once the implanted ions are scattered in the substrate, some dislocations and other defects are entrapped and then interlock the
other defects. The remaining ions compose semistable nitrides in some alloys that are decomposed to create Martensitic hardening.
Here, the exception is gas nitrification of the stainless steel in which the stable nitrides are formed. The result of these processes is
hardness and abrasion resistance, friction coefficient reduction, and tendency toward scaling, and the generation of compressive
surface stresses that improve fatigue and wear strength. The key and very effective characteristic of this process is keeping surface
properties after abrasion up to a depth that might be a 100 times deeper than the initial implantation depth. It is believed that
a share of implanted nitrogen ions penetrates to the front part of the abraded surface and keeps the initial properties.

In commercial aspects, ion implantation is applied for various steels; WC and WCo materials; alloys of titanium, nickel, cobalt,
aluminum, and copper; as well as chromium and even diamond plating. The extrusion pieces and mold are specifically used for
plastic industry applications such as rubber-, paper-, and fabric-cutting blades. There are various limitations for steel and carbide
application at temperatures below 250 and 450 C, respectively. Nevertheless, there are various activity grounds for metals shaping
and general engineering where a 10 times and 3–4 times improvement of lifetime has been reported for carbides and noniron
alloys, respectively. An exception for this last case is titanium, which has increased life improvement factors for dentistry devices of
up to 700 times. Here, operation costs have been estimated as 10–30% of the initial part.
7.04.8 Application of PVD Technology for Fabrication of Micro- and Nanocoatings

7.04.8.1 Fabrication of Coatings
Cho et al. modeled film growth by PVD on rotating substrates using a kinetic Monte Carlo algorithm on a two-dimensional
hexagonal lattice (81). The main objective of this work was to elucidate the evolution of porosity during the deposition of thermal
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barrier coatings (TBCs). The model was applied on an atomic scale that incorporates the impact of surface diffusion and the
interplay between surface topography and the varying vapor incidence angle. Substrate rotation creates voids with a periodicity that
relies upon the amount of material deposited per revolution. Initiation of pore generation and morphology of the pores are strongly
controlled by the presence of shadowing features on the surface, in the form of either stochastic or crystallographic peaks and
valleys. These features evolve during columnar growth or preexisting roughness, which is typical of polycrystalline oxide substrates.
Furthermore, different forms of anisotropy are formed in the microstructure because of the ‘sunrise–sunset’ pattern of vapor
incidence that is characteristic of TBC deposition on, for instance, turbine airfoils. Once comparing these data with the observations
on actual TBCs, it was found that the simulations, despite their simplicity, have various key microstructural features characteristic of
these complex films. Tremendously high temperatures and harsh atmospheric conditions in the hot section of aircraft engines
during operation lead to degradation and structural failures of turbine components. Replacing these components is a very costly
process. Using the TBC composed of ZrO2–8 wt.% Y2O3 (8YSZ) applied through EB-PVD to turbine components offers unique
properties of thermal protection and resistance against oxidation-induced erosion and corrosion. Nevertheless, the life of turbine
components is still limited because of the premature failure of the TBC. It is assumed that the life of the coated components can be
increased by reducing the thermal conductivity of the TBC. To do so, it is required to create multiple nondistinct or distinct interfaces
and alloy additions such as Nb-oxide. This leads to reduction of the thermal conductivity and oxygen transport through the coating.
Singh et al. introduce the microstructural results of standard 8YSZ, layered 8YSZ, Nb-oxide alloyed 8YSZ, as well as functionally
graded 8YSZ with Nb-oxide deposited by EB-PVD (82). The initial results strongly imply that multiple interfaced TBC involves
higher oxidation-resistant properties in comparison to the standard and alloyed TBC.
Knotek et al. developed cathodes for reactive and nonreactive DC-arc PVD through applying sintering and high-pressure hot
isostatic pressing (HIP) techniques and using commercial TiB2 powders (83). In this regard, high-purity basic materials were doped
with traces of different additives to enhance HIP processing behavior that, in turn, results in pycnometric density as well as thermal
and electrical conductivity beneficial to arc evaporation. Factors including thermal and electrical properties, density, and homoge-
neity were examined on cathode materials. It must be noted that these materials were previously tested in arc evaporation equipment
with respect to different parameters, such as particle emission, thermal and electrical behavior, spot movement characteristics, bias
current, and behavior under reactive as well as nonreactive gas atmospheres of various pressures. The tests performed indicated that
the physical properties of cathode material are strongly controlled by behavior during evaporation testing. In addition, appropriate
results were revealed for thermally and electrically conductive materials of high density. Moreover, deposition of the coatings (reactive
Ti–B–N as well as nonreactive Ti–B) on several substrates with cathodes indicated good results in previous evaluation tests. The
developed coatings were analyzed through measuring the deposition rate, microhardness, critical scratch load, and structural
parameters. The dominant coating properties include high hardness and low droplet yield at favorable deposition characteristics.
The deposition of ceramic thermal barrier coatings for high-temperature applications involves many attractions for many
researchers. Particularly, in the case of thermal stresses superimposed by mechanical stresses, the metallic base material expands
much more than the ceramic top layer. Hence, the coating cannot withstand the interfacial stresses and will spall off. Thus, such
ceramic coatings should have a particular type of microstructure to guarantee that the complete system would satisfy the desired
properties such as thermal shock resistance. Through the PVD techniques, it is possible to adopt the microstructure of coatings with
respect to the several applications. The EB-PVD technique is particularly appropriate for deposition of TBCs since it involves
a relatively high deposition rate and can possibly influence the microstructure of the coating. Based on the temperature of the
substrate, the energy of the condensing film changes. It is clear that the mobility of the adatom enhances with increasing temperature,
as long as there is no adatom reflection at a too-hot surface. Lugscheider et al. examined the relationship between the heating method
of the substrates during deposition and the resulting microstructure of the coatings (84). The main objective of their work was to
achieve coatings of a columnar microstructure with a thickness of about 200 mm through the EB-PVD technique to deposit partially
stabilized zirconia. Here, two different types of heat source were investigated: an indirect one using a resistance heater and a direct
one using an electron beam (see Figure 2). The other deposition parameters such as apparatus geometric, deposition rate, substrate
temperature, gas pressure, and so on remained constant. The temperature was measured by thermocouples for both substrate heating
techniques. It seems that the type of heating source plays a key role owing to the different coating microstructures. As a result, various
surface temperatures are obtained while measuring the same temperature at the back of the specimens.
Ensinger et al. coated the inner walls of aluminum and steel tubes using thin amorphous carbon films by rare gas ion beam
sputtering at temperatures below 200 C (85). Based on adhesion measurements with the pin-pull test, it was found that the films
had adequate adhesion. Besides, corrosion tests in aqueous media revealed that the films may be appropriate for corrosion
protection. However, for homogeneous coatings, the ion beam and tube axis have to be well aligned. The problem with homo-
geneity can be dealt with in cases where the tubes are rotated. For long tubes, beam-guiding elements around the tube would
possibly improve the situation. As the main advantage of this technique, it can be mentioned that the technique offers good
adhering and dense homogeneous films at low sample temperatures. Nevertheless, the situation becomes tough in the case where
the tubes have a small diameter and/or when they are long. The technique does not work in tubes with a small diameter and, in
general, a large aspect ratio length and/or diameter. Another limitation of this approach is that the process time for large tubes is
long, particularly for coating materials with low sputtering coefficients. Movchan et al. synthesized gradient TBCs along with the
bond coat through one and the same technological cycle by EB-PVD of a MCrAlY ingot (86). Then, they applied the same process for
an Al–Al2O3–ZrO2(Y2O3) tablet (a pressed multicomponent powder mixture) and finally for a ZrO2–7 wt.% Y2O3 ceramic ingot.
At the applied evaporation temperature, vapor pressure of the tablet components reduces as Al / Al2O3 / ZrO2(Y2O3).
In addition, the evaporation of these components continues in the same order. Consequently, a transition zone (with composition
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Figure 2 EB-PVD plant with (a) a radiation heating system; and (b) an electron beam heating system. Reproduced from Lugscheider, E.; Barimani, C.;
Döpper, G. Ceramic Thermal Barrier Coatings Deposited with the Electron Beam-physical Vapour Deposition Technique. Surf. Coat. Technol. 1998,
98, 1221–1227.
and structure gradients – the transition gradient zone (TGZ)) is developed between the bond coat and outer ZrO2–7 wt.% Y2O3
ceramic layer during the deposition process. Aluminum, Al2O3, and ZrO2 contents of the tablet are the main controllers
of TGZ constitution and structure. As a result, a thin layer of b-phase (NiAl) smoothly transitions to an Al2O3 layer and then to
ZrO2–7 wt.% Y2O3 because of liquid aluminum participation in the coating deposition process.
Fuke et al. presented a generic computational model based on the cosine law of evaporation for predicting coating thickness on
complex workpieces (87). Here, the surface of the workpiece is indicated as a mesh of finite elements. Then, a ray-tracing algorithm
was employed to calculate the accumulated coating thickness on each element considering its location in the vapor plume. Coating
thicknesses estimated by the computational model were consistent with those predicted by analytical models and experimental
results. In addition, an approach was also introduced to characterize and predict the efficiency of the process and the time needed to
achieve the minimum coating thickness. A computational model was applied to simulate a turbine blade coating procedure. There
is some potential future research that can be relevant to current and future manufacturing applications. The static model proposed
in the research could be extended further to incorporate vapor plume dynamics via real-time images of the melt pool and a model of
the melt pool. Moreover, the computational geometry algorithms applied should be extended to comprise shadowing influences,
which can be important in complex shapes. The simulation capability of the model might be applied to optimize the motion of the
workpiece in the vapor plume for improvement of coating uniformity. Another potential future work is to expand this model to
comprise multiple vapor plumes, which are commonly addressed in alloy coatings, and to define a range of operating conditions for
specific microstructures. Figures 3 and 4 show schematic and real EB-PVD coating chambers.
Harry et al. investigated cracking of coatings deposited on steel substrates (88). The coatings on substrate systems were composed
of pure tungsten films and films of solid solutions of carbon in tungsten. These films were deposited through direct current reactive
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Figure 3 Schematic of an EB-PVD coating chamber. Reproduced from Fuke, I.; Prabhu, V.; Baek, S. Computational Model for Predicting Coating
Thickness in Electron Beam Physical Vapor Deposition. J. Manuf. Process. 2005, 7, 140–152. Source: Penn State Applied Research Lab.
Figure 4 Photo of an EB-PVD coating chamber. Reproduced from Fuke, I.; Prabhu, V.; Baek, S. Computational Model for Predicting Coating Thickness
in Electron Beam Physical Vapor Deposition. J. Manuf. Process. 2005, 7, 140–152. Source: Penn State Applied Research Lab.
magnetron sputtering on stainless-steel substrates. The systems were strained in a uniaxial way with a microtensile device installed on
an SEM device. Based on analysis of the mechanical response from the experimental data, it was found that the straining of the samples
indicates an evolution of the density of cracks in the coating. This can be described using an empirical equation based on the Weibull
distribution function. It was found that there is a negative correlation between the density of cracks, which corresponds to the crack
saturation of the coating, and the coating thickness. Also, the critical parameters associated with their mechanical stability were
determined using the experimental results. These parameters are the strain energy release rate for crack extension through the film
(Gfc) and the fracture toughness (KfIc) of the coatings. These values are in the range of 0.2–14 J m2 and 0.1–2.5 MPa m1/2,
respectively. Wada et al. studied texture evolution in ZrO2–4 mol.% Y2O3 thermal barrier coating layers deposited through the
EB-PVD process based on morphological and crystallographic observation (89). Here, the preheating temperature and the deposition
time strongly affect the structures and orientations of the columnar grains grown in the coating layer. In a sample deposited at 1211 K,
only {1 0 0} planes ((1 0 0) and (2 0 0)) are observed after 120 s. Nevertheless, it must be noted that {1 1 1} planes were observed at
925 K from 12 to 300 s. They discussed the kinetics of crystal selection and the obtained orientations of the coating layer on the basis of
the ‘competitive crystal growth model.’ This model predicts a linear correlation trend between the lifetime of a crystal and the
reciprocal of the sine of the angle between the fastest growth orientation and the crystal orientation. A comparison between the
experimental examinations of the lifetimes of oriented crystals and the estimates based on this model indicated a good agreement.
EB-PVD–zirconia coatings are widely applied as thermal barrier coating materials for gas turbine applications. Using these
materials enables the gas turbine to function at higher temperatures, which in turn results in increased turbine efficiency. Estimation
of the lifetime of thermal barrier coatings by evaluation via simulation and modeling is a very important task. This might be because
not only the turbine efficiency but also its reliability are very important issues. To develop a model of an anisotropic EB-PVD
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Figure 5 The EB-PVD deposition process. Reproduced from Bouzakis, K. D.; Lontos, A.; Michailidis, N.; Knotek, O.; Lugscheider, E.; Bobzin, K.;
Etzkorn, A. Determination of Mechanical Properties of Electron Beam-Physical Vapor Deposition-thermal Barrier Coatings (EB-PVD-TBCs) by Means of
Nanoindentation and Impact Testing. Surf. Coat. Technol. 2003, 163–164, 75–80.
coating, one must have knowledge about the mechanical behavior of the coating material. Bouzakis et al. examined the mechanical
properties of the coatings through advanced experimental analytical procedures (see Figure 5) (90). Here, stress–strain curves for
the studied coatings were determined using a continuous, finite element method (FEM)-supported simulation of indenter pene-
tration into the coating surface. In addition, to define its time-dependent plasticity (apparent creep) under dynamic load, the
superficial EB-PVD ZrO2 coating was investigated using an impact tester. Besides, FEM-supported algorithm presented in Ref. (90)
was employed to determine the critical stresses for apparent creep of the coating.
Over the last two decades, the focus of the investigations on high-temperature, oxidation-resistant coating systems for refractory
metals has been on a variety of silicides (e.g., Mo and Ta silicides). This is mainly owing to their superior resistance to oxidation.
However, commercialization attempts have been mainly failed due to the diffusion of silicon from the coating to the substrate. This,
in turn, results in not only the depletion of silicon from the coating but also the creation of less oxidation-resistant subsilicides. As
a consequence, the formation of a high-temperature diffusion barrier layer for silicon is assumed to be considerably important. Also,
the addition of carbon to the system (e.g., during the synthesis of MoSi2–SiC composite thin films on molybdenum substrates)
leads to the diffusion of both silicon and carbon into the substrate – which necessitates the development of a barrier layer for both
elements. Govindarajan et al. studied the possibility of using a novel approach (i.e., reactive RF sputtering) for synthesis of
a diffusion barrier (based on the Mo–Si–C–N quaternary system) for both silicon and carbon (91). The findings of this work
indicated that reactive RF magnetron sputtering of a composite target in an argon–nitrogen atmosphere leads to development of an
amorphous layer, of an as-yet-undetermined stoichiometry – which thwarts diffusion of both silicon and carbon into the
molybdenum substrate. It must be noted that this layer is thermally and chemically stable up to at least 1260 C.
TBCs made using EB-PVD demonstrate a thermal conductivity that is significantly influenced by using a hierarchy of pores
generated during the deposition process. These pores are present in the form of narrow gaps, aligned spheroids, and random spheres
at particular spots within the coatings. Lu et al. studied models about the effects on thermal conductivity of pores with these forms
and spatial arrangements taken from the literature, and then combined them with new results (92). Then, they provided an
explanation for the overall relationships between the relative density and pore morphology of a coating and its thermal conduc-
tivity. In addition, the correlations between conductivity and elastic modulus were explored to determine the viability of modulus
measurements as a user-friendly conductivity probe. It seems that there is a tight correlation at typical porosity levels for the pore
types commonly found in EB-PVD TBCs. Xu et al. applied EB-PVD to deposit double-ceramic-layer (DCL) TBCs of
La2(Z0.7Ce0.3)2O7 (LZ7C3) and La2Ce2O7 (LC) (25). Then, the composition, interdiffusion, surface and cross-sectional morphol-
ogies, and cyclic oxidation behavior of DCL coating were examined. It was found that both LZ7C3 and LC coatings are effectively
synthesized using a single LZ7C3 ingot through the proper control of the deposition energy. The findings of this work indicated that
the chemical compatibility of the LC coating and thermally grown oxide (TGO) layer is unstable. Moreover, LaAlO3 is formed
because of the chemical reaction between LC and Al2O3, which is the main composition of the TGO layer. Furthermore, the
interdiffusion of Zr and Ce between LZ7C3 and LC coatings considerably affected the thermal cycling behavior of DCL coating.
Failure of DCL coating is induced by sintering of the LZ7C3 coating surface, the chemical incompatibility of LC coating, and the TGO
layer, as well as abnormal oxidation of the bond coat. So far, no studied single material meets all of the requirements for high-
temperature applications, so DCL coating is a breakthrough in development trends of TBCs.
Using diamond-coated tools, it is possible to largely enhance the productivity of machining highly abrasive materials such as high
silicon–aluminum alloys (e.g., the ones used in the automotive industry). Cemented-carbide diamond-coated tool inserts are still
significantly interesting products in relation to this, because of various problems including inadequate adhesion of diamond to the
substrate and uncertain reproducibility of their machining performance in manufacturing. To deal with these difficulties, it is required
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to have a better understanding of the influence of CVD conditions such as methane concentration, reactor pressure, and substrate
temperature. Taher et al. coated cemented tungsten carbide tool inserts with 6 wt.% Co (WC–Co) using diamond films deposited at
five different methane concentrations (1–9 vol.%) (93). In addition, the initial results of the influence of methane concentration
variation were discussed regarding the physical characteristics of the diamond coating (i.e., the surface morphology, crystal structure,
chemical quality, surface roughness, and residual stress). Optimum physical properties of diamond-coated tool inserts using hot-
filament CVD are obtained in the case of using diamond coatings deposited at methane concentrations of 1–3%. Schafer studied
the potential changes in cutting efficiency of nickel–titanium K-files previously subjected to the PVD coating (94). Here, TiN coatings
were deposited by various process parameters. A total of 84 nickel–titanium K-files (size 35) were randomly divided into 7 groups
with 12 instruments in each one. Through the groups A to F, which served as experimental groups, the instruments were coated using
TiN by applying different process parameters, with a key emphasis on substrate temperature, applied voltage, coating thickness, and
ion bombardment. In group K, which applied as control, the samples were not coated by TiN. The cutting efficiency of all instruments
was determined by using a computer-driven testing device in a rotary working motion. In addition, the special plastic samples with
a cylindrical canal were applied. It must be noted that the maximum penetration depth of the instruments into the lumen was
considered the criterion for cutting efficiency. The results indicated that the instruments of groups A, F, and C achieved noticeably
higher penetration depths compared to the uncoated instruments of the control group (p < .05). Furthermore, the cutting efficiency of
PVD-coated nickel–titanium files was increased by up to 26.2% in comparison with uncoated instruments.
Matsumoto et al. studied the microstructure, elastic modulus, and thermal cycle life (as a function of the substrate rotation speed
during deposition) for ZrO2–4 mol.% Y2O3 coatings synthesized through EB-PVD (35). The findings of this work indicate that when
applying stationary deposition, the obtained coatings have a dense structure with a relative density of around 95%. In comparison,
a columnar structure with intercolumnar gaps was observed in coatings deposited on rotating substrates. The columnar grains
present a ‘C’-shaped structure, which straightens and becomes more uniform by increasing the rotating speed (see Figure 6). This, in
turn, prolongs the thermal cycle life of the coatings. Higher substrate rotation speeds result in the creation of elongated vertical gaps
that decrease the elastic modulus and shrink the defect size of the coatings. Moreover, compared to stationary-deposited and
plasma-sprayed coatings, the coatings grown on rotating substrates presented a slower increase in modulus at high temperatures.
Here, the main reasons for longer thermal cycle life can be attributed to the low elastic modulus, high resistance to sintering, and
smaller defect size of coatings deposited at high rotation speeds.
Over the last three decades, there has been a growing shift of interest from the strip-coating business in fully continuous or
semicontinuous PVD-based coating processes. In this regard, magnetron sputtering is considered the predominant technology for
deposition of thin coatings (w<100 nm) on polymer webs and thin metal foils. However, since the deposition rate obtained with
magnetron sputtering is too low, there is no economic justification for its application in the metal sheet and strip businesses. Thus,
the high-rate EB-PVD seems to be a suitable modern technology (probably together with jet vapor deposition (JVD)) for high-vapor-
pressure or low-boiling-point metals such as zinc and magnesium. A new PVD process, developed by Baptiste et al. at Corus, may
alleviate some of drawbacks and should combine the advantages of both EB-PVD and JVD (52). The technique is based on the fully
studied technology of levitation of conductive materials in high-frequency electromagnetic fields. Through the appropriate
induction coil design, it is possible to achieve high-power-density metals with low vapor pressures like aluminum, nickel, and
copper. Besides, the process enables easy evaporation of the alloys. Using a properly designed vapor distribution system, it is
possible to direct the produced vapor to the substrate. This achieves excellent coating uniformity as well as very high vapor utili-
zation. Efficiency of the proposed technique is discussed. Besides, extra advantages of this technology (i.e., the creation of plasma
Figure 6 Microstructure of EB-PVD YSZ coatings deposited at different rotational speeds. The observation was performed in the plane perpendicular to
the axis of rotation during deposition. Reproduced from Matsumoto, M.; Wada, K.; Yamaguchi, N.; Kato, T.; Matsubara, H. Effects of Substrate Rotation
Speed during Deposition on the Thermal Cycle Life of Thermal Barrier Coatings Fabricated by Electron Beam Physical Vapor Deposition. Surf. Coat.
Technol. 2008, 202, 3507–3512.
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Figure 7 SEM images of uncoated and coated holes with tilting angles of 0–56 . Reproduced from He, X.; Meng, B.; Sun, Y.; Liu, B.; Li, M. Electron
Beam Physical Vapor Deposition of YSZ Electrolyte Coatings for SOFCs. Appl. Surf. Sci. 2008, 254, 7159–7164.
during evaporation) are elaborated. Further upgrade of this technology, together with POSCO in Korea, should demonstrate its
technical and economic feasibility for application in the metal strip-coating business. In addition, it is assumed that there are
various other valuable applications for this technology in other fields of PVD coating (e.g., in coating of nonflat surfaces).
He et al. prepared yttria-stabilized zirconia (ZrO2–Y2O3, or YSZ) electrolyte coatings through EB-PVD at a deposition rate as high
as up to 1 mm min1 (41). Here, YSZ coating was made of a single cubic phase, and no phase transformation took place after
annealing treatment at 1000 C. Using the SEM device, a typical columnar structure and feather-like characteristics were observed in
every columnar grain. Besides, there were various micron-sized gaps and pores in columnar grain boundaries (see Figure 7). Using
TEM imaging, many white lines were found. It seems that the lines originate from the alignment of nanopores existing within
feather-like columnar grains. The element distribution was homogeneous along the cross-section of the coating, except for Zr with
a slight gradient. A characteristic anisotropic behavior in electrical conductivity was observed in the coating. In the direction
perpendicular to the coating surface, the electrical conductivity was significantly higher than that in the direction parallel to the
coating surface. An explanation for this phenomenon might be the typical columnar structure for EB-PVD coating and the existence
of many grain boundaries along the parallel direction.
Lugscheider et al. reported the deposition behavior of zirconia on laser-drilled surfaces (95). Here, specimens were synthesized
using the laser-drilled holes with a diameter of 200 mm and tilting angles of 08, 158, 308, 458, and 568. VPS-MCrAlY-coated nickel-
based superalloy was used as substrate material. In addition, EB-PVD was applied to deposit the zirconia thermal barrier coatings. In
the next step, the extent by which the tilted holes were closed by the deposition process was investigated. By increasing the tilting
angle, the holes were closed during the deposition of the thermal barrier coating followed by reduction of coating thickness. As
additional tests, a gas (argon) flowed through the holes during the deposition process. Because of the lower ambient temperature to
the holes caused by the cold gas stream, the holes were closed faster by the ceramic vapor in comparison to the deposition without gas
flow. Another influence of the gas flow was the creation of nonstoichiometric zirconia near the holes, indicated by the darker color.
Li et al. conducted the reactive sputtering of aluminum oxide in a planar magnetron system using a mixture of O2 and Ar reacting
with and bombarding an aluminum target (96). The aluminum target was powered by a pulsed DC bias. This current serves as a tool
to discharge the gathered ions on the insulating AlOx film surface during the positive duty cycle and suppresses arc formation. Here,
a seven-turn helical antenna is placed below the magnetron-sputtering system in the vacuum system and delivers RF power to create
secondary plasma in the chamber. This plasma can effectively ionize the sputtered flux, which, in turn, results in achieving ionized
PVD (IPVD). In this system, a gridded energy analyzer (GEA) and a quartz crystal microbalance (QCM) are installed in the substrate
plane. They facilitated determination of the ion and neutral deposition rates. An RF-compensated Langmuir probe was applied to
measure electron temperature and electron density. RF power of 500 W can noticeably rise the deposition rate of AlOx up to half of
the Al deposition rate in metallic mode at the total pressure of 1.33 Pa (10 mTorr). At 3.33 Pa (25 mTorr), the ionization fraction of
Al atoms reaches 90%. Moreover, the RF power extends the range of O2 partial pressure in which the sputtering takes place in the
metallic state. The secondary RF plasma makes the films smoother and denser because of a moderate state of ion bombardment.
Moreover, deposition rates and ionization fractions vary as a function of O2 partial pressure. These variations can be verified using
the combined variation of sputtering at the target, electron temperature, and electron density.
Since the TBCs are potential candidates to improve the performance of jet engines, they have been applied in combustors for
over 15 years. However, it is only in the last few years that they have been actively employed in the harsh turbine environment of
nozzle guide vane platforms. The direction of recent studies is to apply TBCs on turbine vane airfoils and rotating blades, where the
maximum efficiency can be realized. Toward this goal, a large number of works have been conducted in the last 6 years. Toriz et al.
review one such Rolls-Royce program (as a flight service evaluation of TBCs) (97). This work indicates that TBC systems can survive
in the turbine environment for over 16 000 h; however, particulate erosion might be a problem. The study also reviews the service
condition of vanes with TBCs applied by PVD and presents some advantages of this technique over plasma-sprayed coatings (e.g.,
longer thermal cycle lives, smoother surface finishes, better surface finish retention, and superior erosion resistance).
Aubert et al. synthesized coatings of pure chromium and carbon- or nitrogen-doped chromium using cathodic magnetron
sputtering (98). Here, the doping elements were presented either by the gas phase by reactive sputtering or through the direct
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sputtering of composite targets of chromium and chromium carbide and of chromium and chromium nitride. Cr–C and Cr–N
coatings indicated hardness of up to 3500 HV 50 gf and exhibited fretting wear, fatigue, and corrosion properties that are favored to
those of electrolytic hard chrome. XRD indicated the presence of supersaturated solid solutions of carbon and nitrogen in chromium
for concentrations of carbon and nitrogen up to several wt.% with no evident nitride and carbide development, as would be
estimated through the binary Cr–C and Cr–N phase diagrams. Hard nitrides of group IVb metals are capable of displaying not only
gold-yellow but also other fashionable colors such as bronze, brown, violet, dark blue, and almost black by slightly adjusting their
stoichiometrical composition. Recently, an ever-increasing interest in this type of coating has been reported for millinery goods such
as watch cases, bracelets, lighters, jewels, and so on. Because of the extreme sensitivity of the human eye toward small color
differences, the exact reproduction of tints is still delicate. This fact restricts the number of available deposition techniques for
decorative purposes in comparison to those in which it is possible to precisely control the deposition parameters. Zega discussed the
optical characteristics and other quality requirements of these coatings as well as the factors affecting color and various possibilities
of the process through its monitoring in reactive plasma-assisted physical deposition methods (99).
Hayden et al. attached a helicon antenna (placed remotely outside of the vacuum system) to a magnetron-sputtering system
(100). This enhances electron temperature, which, in turn, rises the ionization of the sputter flux for achieving IPVD. Unlike other
IPVD devices with immersed coils, no shadowing and contamination problems were found in this system. This is mainly due to the
fact that the helicon antenna is placed outside of the vacuum system. Moreover, the target-to-substrate distance can be kept low. In
this project, a quartz crystal oscillator (QCO) and a multigrid filter were applied at 2 kW magnetron power, 4 kW helicon power,
45 mTorr argon gas, and, with a copper target, ionization fractions to the substrate of 51 10% and a deposition rate of
847 42 A min1. Without using an antenna, the ionization fraction to the QCO and the deposition rate are 30 6% and
815 41 A min1, respectively. Various remote sources are imagined to be positioned radially around a sputtering chamber,
controlling uniformity while further increasing the ionization. Because it obtains 21% additional ionization when using only one
source, without any contamination risk inside the vacuum chamber, the helicon source indicates good premises for a secondary
plasma source in IPVD applications.
Quinto et al. measured the microhardness of hard coatings of TiN and HfN prepared through CVD and of TiN, HfN, ZrN, and
TiAlN prepared through PVD at ambient temperature and 1000 C (101). The results indicated that the microhardness of the PVD
coatings was considerably higher than that of the CVD counterparts at room temperature. However, all microhardness values were
inclined to converge at 1000 C. PVD coatings contained high residual compressive growth stresses associated with lattice distortion
and very fine grain size. Low residual stresses in high-temperature CVD coatings are induced by the thermal expansion mismatch
between coating and substrate. One explanation for the differences in grain morphology and crystal texture is varying conditions of
energetic bombardment and deposition temperature in the several employed PVD methods. Furthermore, the faster decrease in
microhardness with temperature in PVD coatings is induced by the high residual energy and finer grain size.
Jeong et al. evaluated the hydroxyapatite (HA) coating on the Ti–35Nb–xZr alloy by applying EB-PVD (12). In this regard, the
Ti–35Nb–xZr ternary alloys containing Zr content ranging from 3 to 10 wt.% were synthesized using an arc melting furnace. HA
coatings were prepared through the EB-PVD, and then crystallization treatment was carried out in Ar atmosphere at 300 and 500 C
for 1 h. The Ti–35Nb–xZr alloys indicated an equiaxed structure with the b phase, where the b phase peak increased with Zr
contents. Moreover, the hardness and elastic modulus of Ti–35Nb–xZr alloys decreased by the rise of Zr content. The thickness of
the HA-coated layer and Ca–P ratio of the HA-coated surface after heat treatment at 500 C was approximately 150 nm and 1.67,
respectively. The synthesized HA thin film consisted of small droplets with spherical shape by crystallization. Through the anodic
polarization curves, HA-coated and heat-treated Ti–35Nb–10Zr alloys demonstrated higher corrosion potential than other samples.
Via its crystallization, HA coated film on the Ti–35Nb–10Zr alloy shows high polarization resistance.
To improve the surface hardness of steel, it is possible to plasma nitride the substrate before deposition of a TiN layer. The success
of this combined treatment is strongly controlled by the intermediate thermal modification performed between plasma nitriding
and TiN deposition. D’Haen et al. took some additional steps after plasma nitriding and before TiN deposition, and they inves-
tigated the effect of the obtained interface on the adhesion of the coating (102). These combined treatments are performed on
austenitic stainless-steel AISI 304 as well as on cold work tool steel 1.2379. In the case of coating the plasma-nitrided steel surface
with only a thin Ti intermediate layer prior to deposition of the TiN layer 1.5 mm thick, flaking of the TiN coating is seen with AISI
304, even when no external load is applied. For the cold work tool steel, the TiN coating flakes when a very low external load is
inserted in a scratch adhesion test. Nevertheless, no flaking was observed for both steel types in the case in which the nitrided sample
is first cooled down, and the plasma is subsequently heated and then sputter etched before the deposition of the Ti–TiN layer.
Bi et al. applied EB-PVD to synthesize two-layer-structure TBCs NiCoCrAlY ([bond coat] þ [6–8 wt.%] Y2O3-stabilized ZrO2 [YSZ
top coat]) on a Ni-base superalloy (103). To promote the oxidation resistance of the bond coat, pretreatments were performed in
a vacuum. Then, the thermal cyclic life of the TBC system was assessed by applying thermal cyclic tests. The findings of this work
indicated that the pretreatments in the vacuum at 1273 K enhanced the thermal cyclic life of the TBCs by making an improvement in
the oxidation resistance of the bond coat. Based on results of thermal cyclic tests, it was noticed that the TBCs produced by EB-PVD
were degraded mainly at the interface between the bond coat and ceramic coat, because of spallation of the YSZ top coat from the
bond coat. In addition, based on the results of microstructure observation and composition analysis, the failure mechanism was
proposed as follows: First, microcracks are initiated in the YSZ top coat along columnar boundaries, and then propagate through the
whole top coat. The cracks developed at the TGO layer, because of the microcracks growing, are considered to lead to abnormal
thermally grown oxides of the bond coat under the cracks. This, in turn, results in stress accumulation because of the volume
increase, which is a significant factor in weakening the interface combination of the top coat and bond coat. During the following
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Figure 8 Cross-sectional SEM morphologies and element distributions for the bond coat after the thermal cyclic tests: (a) as deposited; (b) pretreated
for 2 h; and (c) pretreated for 24 h. Reproduced from Bi, X.; Xu, H.; Gong, S. Investigation of the Failure Mechanism of Thermal Barrier Coatings
Prepared by Electron Beam Physical Vapor Deposition. Surf. Coat. Technol. 2000, 130, 122–127.
cooling process, compressive stresses are introduced. These stresses have a tendency to separate the YSZ top coat from the bond coat
and finally result in failure of the TBC system. Figure 8 shows cross-sectional SEM morphologies and element distributions for the
bond coat after the thermal cyclic tests.
Kelly et al. developed the proposed metallographic technique and evaluation method to evaluate the microstructure of porous
translucent ceramic coatings synthesized through the PVD technique (39). The findings of this work indicated that the technique
offers remarkable advantages over the traditional evaluation techniques typically applied for thermal barrier coatings. Also, the
surfaces created by these techniques were quantitatively examined for descriptive parameters, including grain size and inter-
columnar porosity. This evaluation offers new quantitative information on microstructure through the thickness of the coating.
Moreover, it was revealed that there are quantitative differences between the coatings produced by varying deposition parameters.
Similar to the standard quantitative metallographic evaluation, the precision of this method is limited by the quality of metallo-
graphic preparation, operator error with image analysis, position determination, and resolution of the imaging device. All in all, this
technique provides a required tool in the larger effort to define the structure of TBCs (produced by EB-PVD) for completing the link
between system processing, material structure, and coating performance. This approach is found to have the ability to observe and
measure micron-scale and larger structural features quantitatively. Besides, the additional crystallographic and submicron features
have a key role in material performance, and will require additional techniques not yet investigated. For an accurate description of
the complex structure of PVD films, it is required to apply a combination of techniques. This will permit one to better understand
the relations between processing parameters, structure, and performance.
Thermal conductivity is considered among most important properties in the design of TBCs for high-temperature gas turbine
blades. An et al. examined thermal conductivities of several TBCs (104). Then, the EB-PVD was applied to deposit single-layer and
multilayer coatings on nickel-base superalloy substrates. Here, the coatings consisted of Al2O3 and ZrO2 partially stabilized with
8 wt.% Y2O3 (i.e., 8YSZ). Upon observation of the single-layer 8YSZ coating, a columnar microstructure with (200) texture and
[200] direction oriented almost perpendicularly to the plane of the coating was noted. The tendency to form a columnar structure
and the intensity of (200) texture in multilayer coatings with alternating layers of Al2O3 and 8YSZ were reduced by increasing the
number of layers (see Figure 9). In both the single-layer and multilayer coatings, the 8YSZ layer was composed almost entirely of
a tetragonal (t) phase with an insignificant amount of monoclinic (m) phase. This was in contrast to the microstructure of bulk 8YSZ
(a source material used for deposition), which contained a considerable share of m phase plus t phase. Whereas bulk Al2O3
consisted of a-phase, there is only g-phase in the Al2O3 layers of coatings. The laser flash method was applied to measure the thermal
conductivities of the coatings. The thermal conductivity data of the single-layer 8YSZ coating were in good agreement with the data
on bulk ZrO2 stabilized by 5.3 wt.% Y2O3 reported in the literature. This can be attributed to the microstructural similarity between
these two. The thermal conductivity data of multilayer coatings were fully justified using a set of heat-transfer model computations
within the limits of experimental errors involved in the measurements (Figure 10).
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Figure 9 Microstructures of EB-PVD coatings: (a) one layer of 8YSZ coating, (b) two layers of Al2O3 and 8YSZ, (c) eight layers of Al2O3 and 8YSZ, (d)
260 layers of Al2O3 and 8YSZ, (e) the layer structure of the 260-layer coating, (f) 810 layers of Al2O3 and 8YSZ, and (g) the layer structure of the
810-layer coating. Reproduced from An, K.; Ravichandran, K. S.; Dutton, R. E.; Semiatin, S. L. Microstructure, Texture, and Thermal Conductivity
of Single-layer and Multilayer Thermal Barrier Coatings of Y2O3-stabilized ZrO2 and Al2O3 Made by Physical Vapor Deposition. J. Am. Ceram. Soc. 1999,
82, 399–406.
Figure 10 OP three-dimensional wear scars of (a) uncoated and (b) TiN-coated specimens. (c) Representative line profiles taken along the white lines
in (a) and (b). The curvature of the Al-cylinder is also given in (c) for comparison (OP). Reproduced from Björk, T.; Berger, M.; Westergard, R.; Hogmark,
S.; Bergström, J. New Physical Vapour Deposition Coatings Applied to Extrusion Dies. Surf. Coat. Technol. 2001, 146–147, 33–41.
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George et al. applied the PVD process to deposit single-crystalline zinc oxide (ZnO) on Au-coated Si (1 0 0) substrates in an inert
gas atmosphere (10). To do so, they used a mixture of ZnO and graphite powder as precursor for the production of nanoneedles. The
ZnO nanoneedles that were synthesized had an approximate tip diameter of 30 nm and an average length of w5 mm. The XRD
patterns and high-resolution TEM (HRTEM) measurements indicated the mainly crystalline phase of wurtzite single-crystalline
structure, with a preferred (0001) growth direction. Furthermore, field emission from these nanoneedles was examined, where a low
turn on voltage of 5.07 V mm1 at a current density of 10 mA cm2 was recorded.
Hâkansson et al. investigated TiN coatings deposited on steel substrates via five commercially available PVD techniques (i.e.,
low-voltage electron beam evaporation, triode high-voltage electron beam evaporation, random-arc evaporation, steered-arc
evaporation, and magnetron sputtering) (105). It was revealed that all of the films were in a mode of compressive stress with
interplanar distances 1.7% higher than reference bulk values. The number density and average sizes of droplets and craters were
lower in the steered-arc sample compared to those of the random-arc specimen. Cross-sectional TEM (XTEM) analyses revealed that
all of the films had columnar structures with clearly defined substrate–film interfacial layers. The films appeared dense except for the
magnetron-sputtered sample, which demonstrated intercolumnar porosity. Scanning TEM (STEM) energy-dispersive X-ray (EDX)
analyses indicated noticeable variations in the microchemistry of the substrate–film interfacial zones that consisted, depending on
the sample, of renucleated near-surface substrate grains, intentionally (or, in at least one case, unintentionally) introduced foreign
material, gas bubble-like inclusions, and so on. However, in most cases, the microchemistry of these interfacial zones was
understandable based on the substrate pretreatment and/or choice of film growth parameters.
The bearing surface of dies for extrusion of aluminum experiences very harsh wear conditions. To diminish wear and thus obtain
a longer service life, these dies are commonly made of hot work tool steel and surface treated by nitriding. Bjork et al. studied both
commercial and experimental PVD coatings using a device simulating the bearing wear in an extrusion die (106). The tested surfaces
through the hot work tool steel were coated with TiN, CrN, (Ti,Al)N, and TiB2, respectively. Cross-sections of intermetallic Al–Fe
layers were on uncoated steel. To simulate the extruded material, an aluminum cylinder heated up to 550 C was used as a counter
body in a block-on-ring configuration. As comparison, the tool steel was also tested in uncoated conditions. Before performing the
wear testing, the test surfaces were subjected to a series of investigations to characterize their roughness, hardness, thickness, and
intrinsic stress. The results indicated that the coatings of CrN, and especially (Ti,Al)N and TiB2, are the potential candidates for
effective reduction of the wear in extrusion dies. SEM cross-sections of intermetallic Al–Fe layers on uncoated steel can be seen in
Figure 11. Compared to the uncoated steel, these coatings are mechanically, thermally, and chemically stable when sliding against
hot aluminum. The findings of this work also demonstrated that the mechanical strength of the TiN coating gradually degenerated
during this test, which might be attributed to poor chemical inertness when exposed to hot aluminum. Figure 12 shows the typical
appearance of the wear scar of the TiN-coated specimen.
Figure 11 Cross-sections of intermetallic Al–Fe layers on uncoated steel (SEM). (a) A thick layer of adhered Al with an intermetallic compound layer.
(b) Cracking of the intermetallic layer. Reproduced from Björk, T.; Berger, M.; Westergard, R.; Hogmark, S.; Bergström, J. New Physical Vapour
Deposition Coatings Applied to Extrusion Dies. Surf. Coat. Technol. 2001, 146–147, 33–41.
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Figure 12 Typical appearance of the wear scar of the TiN-coated specimen (SEM). (a) Overview of an area displaying a transition from unworn coating
(at A) to gradually thinned coating (at B) to complete coating removal and substrate exposure (at C). (b) Close-up of D in (a) revealing an unworn
area (at A) and gradually worn coating (at B). Reproduced from Björk, T.; Berger, M.; Westergard, R.; Hogmark, S.; Bergström, J. New Physical
Vapour Deposition Coatings Applied to Extrusion Dies. Surf. Coat. Technol. 2001, 146–147, 33–41.
Xu et al. applied EB-PVD to deposit DCL TBCs of La2(Zr0.7Ce0.3)2O7 and YSZ (21). Based on a thermal cycling test at 1373 K in
an air furnace, it was found that the DCL coating has a much longer lifetime compared to the single-layer LZ7C3 coating. It must be
noted that this lifetime is even longer than that of the single-layer YSZ coating. Prolongation of the thermal cycling life of DCL
coating significantly relies on the superior sintering resistance of LZ7C3 coating, the similar thermal expansion behaviors of the YSZ
interlayer with LZ7C3 coating and the TGO layer, and the unique growth modes of columns within DCL coating. Furthermore, the
failure of DCL coating mainly results from the reduction–oxidation of cerium oxide; the crack initiation, propagation, and
extension; the unusual oxidation of the bondcoat; the degradation of the t0 -phase in YSZ coating; and the outward diffusion of Cr
alloying element into LZ7C3 coating (see Figures 13–15).
Laxman et al. investigated factors such as phase constituents, morphology, and microstructure of TGO for a series of TBCs (107).
These factors are regarded as a function of EP-PVD time, (Ni,Pt)Al bondcoat surface treatment, and subsequent oxidation in air. To
characterize the TBCs, photostimulated luminescence spectroscopy (PSLS) and focused ion beam (FIB) in situ lift-out (INLO)
specimen preparation for scanning TEM were applied. Here, photostimulated luminescence was observed only from a-Al2O3 on
grit-blasted bondcoat for all YSZ deposition times. On the other hand, from metastable Al2O3 phases, including a-Al2O3, it was
observed for the TGO on as-coated (i.e., not grit-blasted) bondcoat. Regarding the luminescence intensity of the a-Al2O3, the
luminescence intensity from the metastable Al2O3 phases decreased with an increase in deposition time and corresponding
thickness of YSZ. The luminescence intensity from the metastable Al2O3 phases decreased on subsequent oxidation in air at 1000,
1050, and 1100 C for 0.5, 10, and 50 h, respectively; while that of a-Al2O3 increased. The preliminary formation of the TGO during
EB-PVD deposition consisted of a mixed-oxide zone. Besides, the relative thickness of the mixed-oxide zone for TGO grown on the
as-coated bondcoat surface was higher than that of TGO grown on the grit-blasted bondcoat surface. The observations of this work
indicated that the variation in the presence of metastable Al2O3 in the TGO for as-processed TBCs affects the overall growth of TGO
during short-term isothermal oxidation, specifically by temperature drop.
Molybdenum disilicide is considered one of the most important intermetallics at high-temperature applications. Govindarajan
et al. synthesized functionally graded materials (FGMs) of molybdenum disilicide composites (108). The main objective of this
study was to develop an oxidation-resistant coating system for high-temperature applications (up to 1600 C). In this regard, the
concepts of FGMs and combustion synthesis were employed. The main focus is on the preliminary research performed on char-
acterizing the structure–property-processing relationships during the sputter deposition of thin films of molybdenum and silicon.
Here, the thin films were deposited on glass and stainless-steel substrates using DC magnetron sputtering and RF magnetron
sputtering for molybdenum and silicon, respectively. The investigated processing variables are the cathode power, substrate bias,
and chamber pressure. Based on the determined sputtering rates for both molybdenum and silicon, it can be stated that these rates
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Figure 13 Morphology of DCL coating after 2007 cycles: (a) a surface photograph, (b) the surface at 300 magnification, (c) along the central cross-
section, and (d) the cross-section along a spalled area. Reproduced from Xu, Z.; He, S.; He, L.; Mu, R.; Huang, G.; Cao, X. Novel Thermal Barrier Coatings
Based on La2(Zr0.7Ce0.3)2O7/8YSZ Double-ceramic-layer Systems Deposited by Electron Beam Physical Vapor Deposition. J. Alloys Compd., 509, 4273–4283.
Figure 14 Photograph of an LC coating (a) and its cross-section (b) after 300 cycles. Reproduced from Xu, Z.; He, S.; He, L.; Mu, R.; Huang, G.; Cao,
X. Novel Thermal Barrier Coatings Based on La2(Zr0.7Ce0.3)2O7/8YSZ Double-ceramic-layer Systems Deposited by Electron Beam Physical Vapor
Deposition. J. Alloys Compd., 509, 4273–4283.
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Figure 15 Photograph of an 8YSZ coating (a) and its cross-section (b) after 1556 cycles. Reproduced from Xu, Z.; He, S.; He, L.; Mu, R.; Huang, G.;
Cao, X. Novel Thermal Barrier Coatings Based on La2(Zr0.7Ce0.3)2O7/8YSZ Double-ceramic-layer Systems Deposited by Electron Beam Physical
Vapor Deposition. J. Alloys Compd., 509, 4273–4283.
vary linearly with the cathode power. Low-pressure PVD processes such as thermal evaporation and the many variants of sputtering
are known to employ almost collisionless vapor transport to a substrate. This, in turn, leads to the development of line-of-sight
deposition. Therefore, the deposition of uniform coatings on complex shapes using these approaches needs substrate rotation or
a multiple evaporation source approach. Typically, the line-of-sight requirement prevents application of these processes entirely.
However, the recently developed rarefied-gas jet-based deposition processes have been found to operate at much higher pressures
where a considerable amount of gas phase collisions occur. Using the vapor scattering from a laminar flow that propagates around
a nonplanar substrate, it is possible to apply non-line-of-sight deposition. Experiments performed by Hass et al. revealed that the
coating thickness around the circumference of a stationary, nonrotated fiber placed perpendicular to the axis of a gas jet containing
aluminum atoms is strongly controlled by the jet’s Mach number and the chamber pressure near the substrate (109). Highly
uniform coatings of aluminum on cylindrical fibers were achieved without fiber rotation through employing gas jets with low Mach
numbers (<0.1). Here, direct-simulation Monte Carlo (DSMC) simulations were applied to understand the involved fundamental
phenomena and to examine the role of the process conditions on the coating’s uniformity.
Since the beginning of the 1980s, PVD of hard coatings such as titanium nitride has been realized in industrial sectors (110). Two
PVD processes, low-voltage electron beam and cathode arc deposition, were responsible for the initial commercial success of hard
coatings on high-speed steel tooling. Since that time, two other PVD processes have been broadly developed in the industrial world:
high-voltage triode electron beam and unbalanced magnetron sputtering. There are various similarities and differences between these
four PVD hard-coating processes. However, it is not possible for all of the commonly applied PVD hard coatings to be appropriately
deposited in the four systems. Titanium nitride and titanium carbonitride are two commonly applied PVD tool coatings, and they can
be grown in all four PVD systems. It is possible to easily deposit titanium aluminum nitride using the unbalanced magnetron process
and cathodic arc process as long as targets are used. Considering the different vapor pressures of titanium and aluminum, uniform
composition cannot be maintained with the electron beam processes. Recently, new PVD hard coatings have been developed and
applied. Diamond-like carbon tested for some nonferrous cutting applications and metal–carbon films have yielded promising
results. Because of their very high hardness (up to 5200 HV), polycrystalline nitride superlattice coatings made of thin alternating
layers of two hard coatings such as titanium nitride and niobium nitride can be considered potential alternatives for abrasive cutting
situations. Work is being undertaken for potentially even better tool coatings. A comprehensive project is underway to produce the
superhard crystalline carbon nitride, which is expected to be as hard as or even harder than diamond. In a similar way, cubic boron
nitride (CBN) coatings are still very much in their initial development stage. Thin CBN coatings can now be deposited up to about
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2000 Å in thickness; however, the stress in the films prevents producing thicker films. Now, it is possible to synthesize aluminum
oxide in the DC magnetron mode when pulsed power is used. It must be noticed that this previously has been a very difficult task to
perform by PVD approaches, except in the very slow RF sputtering mode, but it can now be deposited.
There is only a limited amount of information about hard coatings obtained by PVD on ceramic substrates. PVD coating
on ceramic substrates is conducted for further improvement of the material properties (e.g., wear resistance). Knotek et al.
deposited coatings using reactive magnetron sputtering on Si3N4, Al2O3, and Al2O3 þ TiC ceramic (111). As a reference,
coated high-speed steel and cemented-carbide substrates were applied here. Coating systems consisted of the complex hard
materials of the Cr–Al–C–N and Ti–V–C–N systems. Through the RF bias, it was able to deposit these coatings on electrically
insulating substrates. Model wear tests yielded information on the wear resistance of the coated ceramics. Furthermore,
thermal stability of the coatings was verified through the annealing tests.
Meng et al. applied the EB-PVD technique to synthesize YSZ electrolyte coatings for planar solid oxide fuel cells on porous
NiO–YSZ substrates using a deposition rate as high as 1 m min1 (34). Here, a sol infiltration treatment was carried out to improve
the gas tightness of EB-PVD coating by infiltrating the coating specimen in a zirconium and yttrium sol bath, followed by a heat
treatment. Followed by infiltration treatment, the sol had penetrated into the coating and the impregnation depth reached up
to 3 mm. Simultaneously, the intergranular pores and gaps of as-deposited coating had been filled using the decomposed
products of the sol. After performing the infiltration treatment 8 times, the gas permeability coefficient dropped from
6.78 105 cm4 N1 s1 for as-deposited coating to 6.54 106 cm4 N1 s1 for the coating. Next, unit cells were assembled, and
the open circuit voltage increased from 0.820 V for unit cells with as-deposited electrolyte coating to 1.036 V for cells with electrolyte
coating after eight infiltration treatments. After eight treatments of sol infiltration, the maximum output powder density of
150 mW cm2 was obtained at 800 C for unit cells with electrolyte coating.
Eguchi et al. presented a design of an ultrahigh vacuum magnetron-sputtering apparatus through equipment for in situ auger
electron spectroscopy (AES) measurements and plasma diagnostics (70). The apparatus consists of three chambers. Under ultrahigh
vacuum conditions, the sample can be easily moved from the sputtering chamber through a transfer chamber to the AES analysis
chamber. Then, these three chambers are separately pumped. Besides, the samples can be charged and discharged through a lock
chamber without vacuum interruption. The sputtering unit is equipped with a quadrupole mass spectrometer and an optical
multichannel analyzer for plasma detection. Tests were carried out to determine optimum conditions for the DC sputter-cleaning
process with iron. Here, the tested parameters are plasma voltage, sputtering time, and impurity content of the gas phase. The
observations of this work indicated nitriding of the surface at high plasma voltages. As suggested for works, it is possible to examine
the contamination of TiN coatings as a function of oxygen and water vapor content in the plasma atmosphere during film
deposition. Despite performing some works about the structure of titanium nitride coatings developed by PVD, no unified structure
model has yet been presented that considers all experimental observations. Several contributions to both macrostrain (macrostress)
and microstrain (microstress) were discussed as a function of the processing parameters (substrate bias, deposition rate, etc.) for
each of the PVD processes. This model can particularly account for the high lattice parameter of PVD-developed titanium nitride
coatings as well as the variation in unit cell dimensions of the nitride with deposition rate and substrate bias voltage (112).
Mubarak et al. applied cathodic-arc PVD (CAPVD) to synthesize titanium nitride films on high-speed steel (HSS) (32). However,
as the main shortcoming of this technique, one can name formation of macrodroplets (MDs) during deposition, which results in
the formation of the films with rougher morphology. During practical tooling applications, the presence of MDs in the CAPVD
process is considered a serious problem. The main objective of this work is to investigate the effect of ion etching in the presence and
absence of titanium and chromium on the properties of TiN coatings deposited on HSS. The coatings deposited with Cr ion etching
for 8 and 16 min indicated half of the hardness compared to the specimens etched with Ti for similar etching times. Both coating
thickness and indentation loads affected the hardness of the deposited coating. Moreover, Cr ion etching dramatically decreased the
surface roughness and hardness in comparison to Ti ion etching. Wolfe et al. applied EB-PVD to prepare titanium carbide and
chromium carbide multilayer coatings using the varying individual layer thicknesses by the co-evaporation of titanium, chromium,
and carbon (through tungsten) ingots (79). It was found that adhesion of the multilayer coatings is greater than 50 N. Besides, the
findings of this work indicated that hardness of the titanium carbide–chromium carbide multilayer coatings rises from 1302 to
2052 VHN0.050 by decreasing the thickness of the individual layer from 1.2 to 0.1 mm. Moreover, it was also found that the average
grain diameter decreases from 3.315 to 0.356 mm by decreasing the thickness of the individual layers. The fracture toughness of the
TiC–CrC multilayer coatings indicated a drop from 4.179 to 1.411 MPa-m with decreasing layer thickness. The amount of
compressive stress in both TiC and CrC layers within the multilayer coating decreases with the drop of individual layer thickness.
Stirniman et al. applied thermogravimetric analysis (TGA) to measure the evaporation rate as a function of temperature and
molecular weight for an alcohol-derivatized perfluoropolyether (PFPE), Fomblin Zdol (113). The researchers of this work presented
that it is possible to numerically simulate the bulk evaporation rate of a polydisperse Zdol solution during temperature-ramp TGA
through combining molecular-weight-dependent Arrhenius parameters, the initial molecular weight distribution (as determined by
size exclusion chromatography), and Raoult’s law of vapor pressures. The results indicated that the simulation well corresponds to
experiments for both a low-molecular-weight polydisperse Zdol and for a mixture of the low-molecular-weight Zdol with a heavier
Zdol fraction. However, it is known that the mixtures of Zdol with nonfunctionalized Z lubricants substantially deviate from ideality
in quantitative aspects. PVD is receiving renewed interest in the disc drive industry. This is owing to the fact that it can be considered
an alternative technique of applying PFPE lubricants commonly applied as topical coatings on thin-film magnetic environments.
Within a process involving vaporization of a polydisperse liquid phase lubricant, quantitative prediction of deposition rates and
vapor phase molecular weight distributions will generally be allowed only in the case of having precise knowledge of liquid phase
distributions, component evaporation rates, and the ideality of the solution.
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Xu et al. applied EB-PVD to prepare lanthanum–zirconium–cerium composite oxide (La2(Zr0.7Ce0.3)2O7, or LZ7C3) as

a candidate material for TBCs (24). Here, they examined the composition, crystal structure, thermophysical properties, surface and
cross-sectional morphologies, as well as cyclic oxidation behavior of the LZ7C3 coating. The findings of this work indicated that
LZ7C3 has a high phase stability that ranged from 298 to 1573 K. Besides, its linear thermal expansion coefficient was found to be
similar to that of zirconia containing 8 wt.% yttria (8YSZ). The thermal conductivity of LZ7C3 is 0.87 W m1 K1 at 1273 K, which is
almost 60% lower than that of 8YSZ. One potential solution to deal with deviation of coating composition from the ingot might be
the addition of an extra amount of CeO2 and ZrO2 during ingot preparation or through adjusting the process parameters. The failure
of the LZ7C3 coating can mainly be attributed to the occurrence of microcracks inside the ceramic topcoat, which, in turn, induces
the abnormal oxidation of bond coating. Slifka et al. measured the average thermal conductivity of PWA 266 over a temperature
range of around 100–900 C (114). The measurements at each temperature vary from 1.5–1.7 W m1 K1 with a relative uncertainty
range of 20%. These results are rather independent of temperature. Because of the fine microstructure and porosity of yttria-
stabilized EB-PVD coatings, it was expected that the thermal conductivity would be independent of temperature. Even though
EB-PVD coatings are formed in a directional manner, leading to a high degree of texture, they do not present thermal behavior
normally associated with texture. The fine structure of the EB-PVD coating promotes the geometric scattering of phonons. Based on
measurements of similar coatings, a three-level structure of porosity was observed that can result in a noticeable reduction of
thermal conductivity compared to that of sintered polycrystalline material. The substantial amount of scattering induced the
disorder of the stabilized zirconia lattice and, coupled with the geometric scattering (caused by a large population of other defects),
makes these coatings have a lattice thermal conductivity that is not sensitive to temperature.
It is possible to determine the changes detected in the performance of nickel alloys with corrosion-resistant MCrAlY–ZrO2 EB-
PVD coatings through the complex effects of various factors, including the test temperature, the technique applied for synthesis
and treatment of the coatings, the thickness ratio of the individual layer of the coating that determines the allowed stress level, and,
finally, the mechanical properties of the base metal. It must be noted that the latter factor can prevail in a number of cases. Rybnikov
et al. indicated that it is possible to considerably enhance the life of alloys when the metallic coating is synthesized through
deposition from the vapor phase in the form of a two-layer metallic composition (i.e., a plastic interlayer, then one MCrAlY layer)
and finally a 60–120 mm thick external ceramic layer (115). The endurance of the composite coatings of the metal–ceramic type can
also be considerably increased through optimizing the chemical composition of the intermediate interlayer and choosing the
optimum thickness ratio of the internal and the main heat-resisting layers of the coating. Here, the plastic interlayer has been an
important barrier that prevents the propagation of microcracks induced by thermomechanical conditions. Application of metal–
ceramic coatings, made of many functionally interconnected layers, permits one to simultaneously deal with the problems of
protecting the turbine parts from heat, corrosion, and the erosive action of high-velocity gas flow under conditions of cyclic changes
of the temperature. So, such coatings are applied in industrial turbines and in naval and aircraft engines in environmental
conditions of Ukraine and Russia.
The enhanced activated reactive evaporation (EARE) and electron shower (ES) techniques are among the tightly related hybrid
PVD processes reported as extremely flexible for thin-film growth. Activation of metal vapor and gas phases significantly promotes
component reactivity and facilitates synthesis of a variety of compounds with low-synthesis energies. LeClair et al. investigated
modifications to the ES and EARE processes for further enhancement of reactivity and flexibility to deposit TiN thin films with
improved optical properties and higher adhesion values (116). Through the previous works, it was proved that the synthesis of films
that are highly adhesive to glass with good optical and mechanical properties is a difficult task. Li et al. presented the synthesis of
a twin-structured YSZ coating using an advanced plasma spray PVD process with a high-power hybrid plasma-spraying system (46).
Completely different from those deposited by conventional atmospheric plasma spraying and EB-PVD, this as-deposited YSZ
structure is characterized by coarse grains larger than 5 mm throughout the coating, differently sized t0 -ZrO2 twins (which fill the
coarse grains), and micron-scaled lenticular t0 colonies (where the twins arrange on the submicron scale alternatively). Based on
indentation tests conducted, it was found that both the nanohardness and microhardness of the peculiar coating are noticeably
higher than those of the ordinary YSZ coatings. These values are even comparable with those of the sintered YSZ polycrystal bulks.
7.04.8.2 Characterization of Coatings

Avelar-Batista et al. characterized electron beam evaporation plasma-assisted PVD Cr–N coatings formed on AISI M2 steel and hard-
metal (K10) substrates in two various Pristine (i.e., coated) and Recoated (i.e., stripped and recoated) conditions (77). It was found
that both Pristine and Recoated coatings consist of a mixture of hexagonal Cr2N and cubic CrN, regardless of the substrate type. For
the M2 steel substrate, only slight differences were observed in terms of coating phases, microstructure, adhesion, and friction, as
well as wear coefficients between the Pristine and Recoated techniques. Recoated on WC–Co (K10) demonstrated a less dense
microstructure and significant inferior adhesion compared to Pristine on WC–Co (K10). The wear coefficient of Recoated on
WC–Co was 100 times greater than that of those exhibited by all other specimens. The stripping process has no negative effect on the
Cr–N properties in the case of depositing this coating on M2 steel substrates. However, the fulfilling tribological performance of
Recoated on WC–Co implies that the stripping process is not efficient for hard-metal substrates. Figure 16 shows surface and
fracture cross-section SEM images of Cr–N coatings.
Ensinger explained a coating device that combines two material modification techniques, including PVD of a thin film and
plasma immersion ion implantation (PIII) (80). The plasma was prepared using an electron cyclotron resonance (ECR) microwave
plasma source. The plasma is confined in a magnetic field through a solenoid in the upper part of the vacuum chamber, whereas in
the lower part a magnetron sputter cathode and a resistively heated evaporator are mounted to deposit thin films on the sample.
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Figure 16 Surface (a, c, e, and g) and fracture (b, d, f, and h) cross-section SEM images of Cr–N coatings on (a and b) Pristine M2 steel; (c and d)
Recoated M2 steel; (e and f) Pristine WC–Co (K10); and (g and h) Recoated WC–Co (K10). Reproduced from Avelar-Batista, J. C.; Spain, E.; Housden, J.;
Fuentes, G. G.; RebolÉ, R.; Rodriguez, R.; Montalá, F.; Carreras, L. J.; Tate, T. J. Characterisation of Pristine and Recoated Electron Beam
Evaporation Plasma-assisted Physical Vapour Deposition Cr-N Coatings on AISI M2 Steel and WC-Co Substrates. Thin Solid Films 2005, 491, 177–183.
The specimen is clamped on a water-cooled sample holder that can be moved in the vertical direction. The holder, in turn, is
connected to a novel semiconductor-based high-voltage pulse generator that supplies negative voltage pulses. The characteristic
features of this device (i.e., technical data on the plasma source, pulse generator, and deposition devices) are described. Further-
more, the results on plasma characterization, including the ion density dependence on microwave power and gas pressure, were
discussed. Results on the formation of TiN films via deposition of titanium and following nitrogen PIII are also presented.
Quaeyhaegens et al. applied glancing angle XRD to investigate the interface between an austenitic stainless steel AISI 304
substrate surface and a TiN or Ti–TiN coating (117). Based on the deposition conditions, the presence of g0 -Fe4N can be noticed in
cases where no titanium intermediate layer is formed. The influence of the interface on the adhesion of the TiN coating is inves-
tigated through the scratch test method. The findings of this study indicated that formation of a g0 -Fe4N layer adversely affects the
adhesion, and much better adhesion is obtained once formation of such a layer is avoided, even in the absence of a titanium
intermediate layer. These results are consistent with adhesion measurements of the coatings performed through the scratch test
method. Kazmanli et al. deposited TiN–Sb nanocomposite coatings using a hybrid system consisting of cathodic-arc and
magnetron-sputtering sources (47). The magnetron-sputtering source in the hybrid system allowed incorporation of the low-
melting-point Sb into the high energetic arc plasma of Ti. This hybrid system configuration made it possible to adjust dopant
contents within the composite coatings. Antimony in TiN coatings indicated very broad and low-intensity diffraction peaks. Besides,
it involves an amorphous or nanocomposite structure. The critical antimony content, for the nanosized crystal formation (below
10 nm) and for the structural morphology variation from columnar to shapeless, was determined as 5.5 at.%. When a nanosized
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crystal was developed, the hardness of the coatings indicated a decrease to a minimum of 7.7 GPa for 12.6 at.% Sb containing
coating. TiN coating (synthesized using the CAPVD technique) demonstrated crystal size and hardness of 186 nm and 31 GPa,
respectively. Here, the integration of antimony into TiN reduced the crystal size of the TiN matrix. Furthermore, a small amount of
Sb (1.8 at.%) in TiN caused the crystal size to drop to 86 nm and provided maximum hardness of 38 GPa. Through adding a further
amount of antimony (5.5 at.% Sb and more) into the coating, the matrix crystal was transformed into a nanosized state (z5 nm),
whereas this nanocrystal formation, in turn, reduced the hardness of the coatings down to 18 GPa. It was found that the critical
antimony content is 1.8 at.% for the maximum hardness and 5.5 at.% for the formation of nanosized grains (below 10 nm).
Tribology test results initially indicated that Sb addition provided lower friction coefficients. In contrast, TiN coating against an
Al2O3 ball yielded a friction coefficient between 0.5 and 0.6; the friction coefficient of Sb-doped TiN (1.8 at.% Sb) coating was
between 0.17 and 0.35.
Mohite et al. deposited thin films of silicon oxynitride (SiOxNy) on silicon wafer substrates using the EB-PVD technique (118).
To do so, they applied a varying substrate temperature (T ¼ 100–450 C) and deposition time (t ¼ 0.5–2.5 min). The observations
indicated that the minimum reflectivity R ¼ 1.72% is obtained for the films deposited under the conditions of T ¼ 350 C, t ¼ 1.5 min
at k ¼ 548 nm. Besides, the characterization results demonstrated that the refractive index (RI) of the films rises with the increase in
the substrate temperature because of the increase in silicon nitride content. The findings of this work indicated that the refractive
index and the thickness of the films are n ¼ 1.72–1.90 and d ¼ 40–138 nm, respectively. Besides, the values n ¼ 1.88 and d ¼ 79 nm
observed, corresponding to the minimum reflectivity R ¼ 1.72%, meet the required condition of near-quarter-wavelength single-
layer antireflection coating. Therefore, the above films might involve great potentials for the future antireflective coating applications.
Giolli et al. prepared titanium dioxide coatings on various substrates through a modified electric-arc PVD (EA-PVD) technique
(48). The coatings were characterized by chemical and structural aspects. The deposition variables were changed during preparation
of the coatings with TiO2 in the anatase form. This might indicate good photocatalytic properties. The characteristics of the coatings
are controlled by both substrate type and deposition parameters. The crystal structure is mainly affected by substrate composition
(copper (anatase), stainless steel (rutile), and glass (anatase)) and the variation of substrate type. It also seems to affect the crys-
talline size of the coating grains. In addition, the crystalline structure might be influenced by the deposition rate, with lower rates
that tend to favor the anatase formation. The deposition rate of the coatings appears to be affected by many deposition variables
(e.g., gas composition, gas pressure, bias, and EMCAS configuration). Here, the substrate heating does not seem to alter the
characteristics of the coating like the other parameters. The homogeneity and adhesion of the coatings is controlled by the surface
uniformity of the substrates. Based on the photochemical experiments performed on some of the most promising samples, it was
observed that the crystalline form of the TiO2 coating is a main factor in determining photoactivity. The anatase coatings can rapidly
degrade photocatalytically by phenol solution compared to rutile coatings. The effect of coating thickness was another parameter
that was studied. The result indicated that the increase in thickness above about 700 nm does not result in any improvement of the
photocatalytic action.
Meng et al. synthesized two types of NiO–YSZ coatings with uniform and gradient distributions of NiO content along the
coating thickness direction (29). To do so, they applied an EB-PVD by adjusting electron beam currents. Then, after a reduction
treatment, the uniform and graded Ni–YSZ coatings were produced through the corresponding NiO–YSZ coatings. The composition
and porosity distributions along the coating thickness were uniform for a uniform Ni–YSZ coating. In addition, the specific surface
area and total pore volume for this coating could enhance up to 4.330 m2 g1 and 0.0346 cm3 g1, respectively. The area-specific
resistance (ASR) of this coating was constantly increasing with the increase in temperature, and an ASR of 2.1 105 U cm2
obtained at 600 C. For graded Ni–YSZ coating, a gradient in Ni content and porosity was obtained along the coating thickness.
Moreover, porosity values of as high as 33% and as low as 10% were achieved in the part of the coating close to the substrate and
close to the coating surface, respectively. Wolfe et al. synthesized polycrystalline 4 mm and 14 mm thick multilayer TiB2 and TiC
coatings using a varying number of total layers (2–20) (119). They applied the techniques, including ion beam assisted (IBA) EB-
PVD, on substrates of WC, 6 wt.% Co, and 0.3 wt.% TaC (see Figure 17). Average Vicker’s hardness numbers rose with the increasing
total number of layers; they range from 3215 to 3726 VHN0.050 and from 3294 to 3991 VHN0.050 for the 4 mm and 14 mm thick
multilayer TiB2–TiC coatings, respectively. The adhesion of the multilayer coatings is greater than 50 N for a 4 mm thick film and
below 30 N for the thicker films. The degree of crystallographic texture varies with the varying total number of layers, plus the
orientation of both materials within the multilayer system. The grain size and amount of residual compressive stress decrease with
the increasing number of layers. The fracture toughness reduces with an increased total number of layers.
Wolfe et al. successfully deposited TiC, TiB2, and superhard TiBCN coatings through IBA, EB-PVD (78). Here, titanium, titanium
diboride, and carbon (through tungsten) were coevaporated through the energetic electron beams. In the same time, the substrates
were bombarded using the varying ionized gas ratios of nitrogen and argon to obtain superhard TiBCN coatings. The findings of this
work indicated that the hardness of the TiBCN coating is equivalent to that of a soft diamond-like carbon film. Besides, adhesion
was determined as high as 50 N. It is worth mentioning that the authors are not aware of previous TiBCN coatings being deposited
using this approach. Kato et al. deposited YSZ film on a metal substrate through EB-PVD at 850 C (64). The YSZ film mainly
contains a tetragonal phase with a little amount of a monoclinic phase. Moreover, the film was composed of inverted triangular-
based pyramidal grains (T-grains) and inverted diamond-based pyramidal grains (D-grains). The T-grains were aligned in the
<111> direction and D-grains in the <110> direction. In addition, striated lines of nanopores, which were significantly associated
with the thermal conductivity of the film, were observed in each YSZ grain. The pores are aligned in the <110> direction in the
(111) plane and distributed across {114} planes in T-grains; besides, they are aligned in the [110] and the [001] directions in the
(110) plane and distributed across the (001) and (110) planes in D-grains.
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Figure 17 Schematic diagram of the ion beam assisted, EB-PVD chamber. Reproduced from Wolfe, D. E.; Singh, J.; Narasimhan, K. Synthesis and
Characterization of Multilayered TiC/TiB2 Coatings Deposited by Ion Beam Assisted, Electron Beam-physical Vapor Deposition (EB-PVD). Surf. Coat.
Technol. 2003, 165, 8–25.
7.04.8.3 Properties of PVD-Coated Samples

Fancey improved a coating thickness uniformity model for PVD in low-pressure gas (120). Through the original model, coating
uniformity is discussed in terms of the front-to-back thickness ratio, R, of coatings on thin flat substrates. Here, the terms front and
back indicate surfaces facing toward and away from the vapor source, respectively. By exploration of the principles used for
developing the original model, an equation is derived and verified empirically for the front-face fall-off in coating thickness with
source-to substrate distance, s. The equation neglects the effect of the progressive dilution of vapor flux that can be induced in
vacuum (the y function) from gas-scattering effects. Accordingly, it was found that the y function estimates are based on an inverse
square law with s; however, the level of approximation is controlled by the emission properties of the vapor source and associated
virtual source effects. The information obtained from the y function allows for further development of the original model for R. The
expressions were presented for the source–substrate configurations, including a thin substrate at an angle to the vapor source, a thick
substrate, and two vapor sources at different values of s.
Fancey et al. developed a model that concerns the ratio between the coating thicknesses on sample faces toward and away from
the vapor source (121). The model indicates that this ratio is an explicit hyperbolic cotangent function of (s/2l) in which s is the
source-to-substrate distance, while l is a mean free path related to the distance traveled by a vapor particle before it becomes
thermalized. It can be stated that the model is valid under gas evaporation and simple diode ion-plating conditions. However, these
investigations were generally limited to deposition by electron beam evaporation. The validity of the model was proved for TiN
coatings produced by reactive ion plating through discharge improvement and for metallic coatings deposited by resistive evap-
oration, magnetron sputtering, and cathodic-arc evaporation. The findings exhibit how thickness uniformity can be affected by the
type of source used. The authors believe that this is primarily because of the initial energy of the vapor flux as well as the effects of
source geometry. In addition, the changes in the vapor emission properties of EB gun sources are found to have a significant effect.
Fancey describes a coating thickness uniformity model for PVD in low-pressure gas (122). The model originates from a study of the
proportions of nonthermalized and thermalized vapor fluxes induced by the front and back surfaces of thin fiat substrates, where
front and back show the surfaces facing toward and away from the vapor source, respectively. It was found that R ¼ coth(s/2l), where
R is the front-to-back coating thickness ratio, s is the source-to-substrate distance, and l is related to the mean free path for vapor
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thermalization. An experimental step was conducted to evaluate the validity of the model under different deposition conditions.
The findings of this research indicated that the model can be successfully used in a PVD process through thermal evaporation
(through resistive or electron beam heating), and in plasma-based systems that employ magnetron sputtering or cathodic-arc
evaporation sources, or that operate under ion-plating conditions. The information obtained from this model might be useful for
predictive objectives or to provide knowledge about phenomena such as vapor particle thermalization and virtual source impacts.
7.04.8.3.1 Electrochemical Behavior

The thin-film coatings synthesized by PVD methods typically demonstrate porosity. Such local defects can result in local and rapid
corrosion of the base material. Here, the porosity is a parameter that is difficult to measure. Besides, electrochemical techniques are
most suitable for evaluating the corrosion resistance of the coated material. This work compares the corrosion resistance of TiN,
Ti(B,N), and (Ti,Al)N- and TiB2-coated ASP 23 high-speed steel. The corrosion performance of TiB2-coated samples was poor for
these materials. Ti(B,N) coatings produced through two different methods were completely similar. However, it must be noted that
the measured porosity of the coating produced by magnetron sputtering was lower than that of the coatings produced by the
electron beam technique. These coatings had more or less higher corrosion resistance compared to (Ti,Al)N coatings with a high
aluminum-to-titanium ratio. In addition, (Ti,Al)N coatings with a low aluminum-to-titanium ratio were better than those with
a high aluminum-to-titanium ratio. TiN coatings were determined as better in comparison to the other types, expect for (Ti,Al)
N þ AlN layer coatings, which performed best. (Ti,Al)N þ AlN coatings have an insulating layer on top of the coating, which
enhances their polarization resistance and reduces their corrosion current density (123). Milogev et al. investigated 2.8 mm thick TiN
coatings deposited on various substrates through PVD using electrochemical techniques (124). Three different substrates were
utilized: stainless-steel AISI 304, high-speed steel ASP 30, and stabilized iron CK45. To evaluate the microporosity of the coatings,
multisweep cyclic voltammetry experiments were performed in acetate buffer solution. In addition, an auger depth analysis carried
out on TiN coatings polarized at potentials more positive than 1.3 V in 0.5 M H2SO4 verified growth of an oxidized layer, which
implies the partial transformation of titanium nitride to a titanium oxynitride layer. A change in the corrosion behavior related to
the presence of the TiN coating was observed in 0.5 M NaCl. By contrast, the uncoated iron experiences general corrosion, and the
localized corrosion (which results from the microdefects present in the coating) takes place on the TiN-coated iron.
Titanium nitride coatings possibly promote the corrosion behavior of dental alloys. To evaluate this possibility, rest potential
and potentiodynamic polarization measurements were conducted on six nonprecious and precious metal reduced dental alloys. To
deposit TiN, 10 different coating methods were tried on the alloys. The findings of this work revealed that the corrosion resistance is
strongly controlled by the base material, the structure of the deposited titanium nitride, and the coating method. In several cases, the
coatings are permeable to the surrounding electrolyte. Hence, electrochemical reactions can take place with the base material and
provoke microscopic and, occasionally, even macroscopic lesions of the deposits. Through recording of the rest potential of the
untreated material in comparison with the coated material, the values in the region of passivity of the base alloy were obtained.
Therefore, the coatings do not hamper corrosion behavior. Current density versus potential measurements indicates a noticeably
lower corrosion current in comparison to the base metal even for coatings that are permeable to the electrolyte. The applied
electrochemical examination could be used as an easy quality assurance for thin-film coatings. To prove the biocompatibility of the
coatings, biological tests were conducted on impermeable specimens. No harmful effect was detected on cell growth and cell life, so
the TiN surface can be efficiently used in biological applications (125). Figure 18 shows current density–potential curves for
WironiumTM as a base material coated by various methods, while Figure 19 presents current density–potential curves for some
titanium materials and various surface modification techniques.
Performance of PVD TiN- and CrN-coated mild steel can be promoted through applying multiple layers. Although the overall
dissolution rate is decreased by the single-layer coatings, the relatively rapid local dissolution of the substrate at through-coating
pinholes still controls the corrosion process of the coated mild steel. In comparison to single-layer coatings, the four-layer coat-
ings drastically decrease the corrosion rate. Moreover, in comparison to either single-layer coatings or the bare mild steel, the PVD
four-layer coated mild steel is subjected to a much shorter period of dissolution, followed by a ‘passive’ regime. Corrosion products
can fully block the limited number of developed pinholes. Besides, four-layer CrN-coated mild steel exhibited a considerable
secondary dissolution within the polarization bandwidth. This might occur preferentially in certain phases within the coating. It is
worth mentioning that this was not observed to any significant degree for TiN. Figures 20 and 21 show cross-sectional SEM
micrographs of single- and four-layer (a) TiN and (b) CrN coatings. The improvement of the corrosion resistance by CrN coatings is
greater than that by TiN coatings owing to the following reasons: (1) The limited number of within-coating defects (e.g., pinholes),
with the compacted structure and fine equiaxed crystallites, makes the CrN coatings less permeable to the corrosive environment;
(2) a lack of direct diffusion channels due to the noncolumnar structure in which the oxygen diffusion rate is significantly decreased;
(3) redistribution of current flow because of the interphase corrosion within the coating, which reduces the current concentration at
small pinholes; and (4) less delamination along the coating–steel interface since the coatings are less permeable (see Figure 22).
There is promising scope to adjust the nitrogen content in the CrN binary phase system to synthesize mixtures of nitride and
metallic phases or produce wear-resistant metallic coatings that are functionally modulated in nitrogen content. More research is
needed to determine the optimum balance between mechanical and corrosion properties for specific application areas (126).
Generation of the pinholes is among the most important factors in coating corrosion-resistant films. Munemasa et al. proposed
a carbon tool steel, SK5(JIS), for substrates finished to various kinds of surface roughness (Rmax ¼ 0.2–17 mm) (127). This device
allows investigation of the relationship between the surface roughness and the birth of pinholes. Here, the magnetron-sputtering
technique was applied to deposit titanium and TiN on these substrates. Here, ferroxyl tests were performed for pinhole detection.
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Figure 18 Current density–potential curves for WironiumTM as a base material coated by various methods. Reproduced from Brauner, H. Corrosion
Resistance and Biocompatibility of Physical Vapour Deposition Coatings for Dental Applications. Surf. Coat. Technol. 1993, 62, 618–625.
Figure 19 Current density–potential curves for some titanium materials and various surface modification techniques. All layers are impermeable to
the electrolyte, as proved by the missing H2 rise. Note the better corrosion resistance of titanium materials as compared with the other alloys.
Reproduced from Brauner, H. Corrosion Resistance and Biocompatibility of Physical Vapour Deposition Coatings for Dental Applications. Surf. Coat.
Technol. 1993, 62, 618–625.
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Figure 20 Cross-sectional SEM micrographs of single-layer (a) TiN and (b) CrN coatings. Reproduced from Liu, C.; Leyland, A.; Bi, Q.; Matthews, A.
Corrosion Resistance of Multi-layered Plasma-assisted Physical Vapour Deposition TiN and CrN Coatings. Surf. Coat. Technol. 2001, 141, 164–173.
Figure 21 Cross-sectional SEM micrographs of four-layer (a) TiN and (b) CrN coatings. Reproduced from Liu, C.; Leyland, A.; Bi, Q.; Matthews, A.
Corrosion Resistance of Multi-layered Plasma-assisted Physical Vapour Deposition TiN and CrN Coatings. Surf. Coat. Technol. 2001, 141, 164–173.
Figure 22 Potentiodynamic polarization curves for the bare mild steel substrate and single-layer or four-layer TiN and CrN coated mild steel in 0.5 N
NaCl solution. Reproduced from Liu, C.; Leyland, A.; Bi, Q.; Matthews, A. Corrosion Resistance of Multi-layered Plasma-assisted Physical Vapour
Deposition TiN and CrN Coatings. Surf. Coat. Technol. 2001, 141, 164–173.
Besides, an image analyzer was utilized to count the number of pinholes based on a quantitative measurements approach. Addi-
tionally, the effects of total film thickness and multilayer coatings on the reduction in the number of pinholes were studied. The
number of pinholes was considerably reduced by increasing the number of layers to 10 in multilayer coatings. Wiiala et al. examined
several techniques, such as pulsing the nitrogen flow and rotating the substrates during deposition, to improve the corrosion
resistance of triode-ion-plated coatings (128). Moreover, they investigated the effects of a separate sputtering period during
deposition and the subsequent passivating treatment and vacuum annealing. Pulsing the nitrogen flow considerably enhanced the
corrosion resistance of a coating through reducing the number of pinholes. For a layered coating made of mostly TiN, the optimum
corrosion resistance was obtained once using a coating with a dense fine-grained TiN structure with a thin intermediate e-Ti2N layer.
The corrosion resistance of those layered coatings in the presence of pure titanium was slightly worse than that of those coatings with
no titanium content. Besides, in the case of ZrN, the best corrosion resistance was reached using a coating consisting of alternating
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thick zirconium and ZrN layers. The findings of this work indicated that the influence of both a separate sputtering period and
rotation of the substrates is beneficial for corrosion resistance. Annealing and chemical passivation were investigated as post-
deposition treatments. The chemical passivation of TiN-coated AISI 316 in HNO3–Na2Cr2O7 solution resulted in an enhanced
corrosion resistance. The improvement can be mainly attributed to the formation of TiO2 at the bottom of the pinholes. It was also
revealed that annealing enhanced the corrosion resistance of the coatings, although the mechanism was determined.
7.04.8.3.2 Tribological Behavior

Residual stresses are generated in coatings during deposition and can significantly affect the mechanical properties and durability of
the coating. Johnson et al. characterized in-plane residual stresses in EB-PVD TBCs (129). They measured the change in substrate
curvature upon coating removal, and in-plane elastic moduli using the resonant frequency of the coating–substrate system. It was
observed that changes in deposition conditions produce in PVD TBCs a wide range of stress levels, varying from 270 to 20 MPa. The
findings of this work indicated that the residual stress is strongly correlated with the in-plane elastic modulus. In addition,
a significant difference in the in-plane elastic modulus was determined along different directions of PVD TBC samples synthesized
through rotating the samples over the evaporation source. It was also found that the elastic modulus in the direction perpendicular
to the axis of rotation was always noticeably lower than the modulus measured along the axis of rotation. Moreover, the elastic
modulus measured perpendicular to the axis of rotation was related to compliant microstructural features formed through the
rotation of the substrate over the melt pool. Here, strain tolerance was directly measured using a new mechanical test. The test
measures the strain at delamination of a coating from an edge-initiated crack from a compressively loaded substrate. Furthermore,
the strain tolerance of the coating was reduced with increasing residual stress.
Perry et al. investigated the residual stress, lattice parameters, and strain broadening of diffraction peaks in a couple of TiN films
deposited on a C3 cemented carbide substrate by reactive magnetron sputtering (130). The substrate bias voltage and the sputter
target input power were varied. The findings of this work indicated that complex residual stress situations might exist where, for
example, (220) planes could indicate high compressive and shear stress, (422) planes could indicate simple low tensile stress, and
(333)-(511) planes could mean simple low-compressive stress conditions in a given film. Based on deposition conditions, it is
possible to classify the observed residual stress behavioral patterns into three categories. Moreover, the lattice variables and peak
broadening presented positive or negative deviations from the average values of the remaining planes, which are specific within each
behavioral pattern range. The authors believe that these effects are related to the significant rise in the defect and stacking fault
concentration observed with increasing bias, and to the ultramicrocracking on (220) planes.
Cernuschi et al. applied thermal barrier coatings (TBCs) to protect hot path components of gas turbines against hot combustion
gases (4). In the case of aero engines, TBCs have been deposited through the EB-PVD for a number of decades. EB-PVD coatings
indicate a columnar microstructure that ensures high strain compliance and better solid particle erosion compared to plasma-
sprayed TBCs. The main shortcoming of EB-PVD coating is that its deposition cost is higher than that of air plasma-sprayed (APS)
TBC. One standard porous APS, two segmented APS, one EB-PVD, and one plasma-sprayed PS-PVDTM were tested at 700 C in
a solid particle erosion jet tester. Here, EB-PVD and standard porous APS were applied as two reference systems. Tests were carried
out at contact angles of 30 and 90 , which are representative for particle contact on the trailing and leading edges of gas turbine
blades and vanes, respectively. Moreover, microquartz (as one of the main constituents of sand and fly volcanic ashes) was selected
as the erodent agent. Once completing the tests, the TBC microstructure was examined using electron microscopy for character-
ization of the failure mechanisms that happened in the TBC.
Nicholls et al. applied TBC technology in the hot sections of gas turbines to extend component life (131). To optimize these
advantages, the TBC is required to remain intact throughout the turbine life. High-velocity ballistic damage can result in overall
thermal barrier removal, while erosion might cause progressive loss of thickness during an operation. Here, a unique high-velocity
gas gun was designed. The gun had the capability of impacting TBCs at particle velocities up to 300 mrs and at test temperatures up
to 920 C. Using this equipment, it was found that at both room temperature and 910 C, EB-PVD ZrO2–8 wt.% Y2O3 thermal
barriers involve considerably higher erosion resistance compared to the equivalent plasma spray coating when impacted with either
alumina or silica in the particle size range of 40–100 mm. Examination of tested equipment indicated that cracking takes place
within the near-surface region of the columns for EB-PVD ceramic and that erosion occurs by elimination of these small blocks of
material. As a contrast, material elimination for plasma-sprayed ceramic happens through the poorly bonded splat boundaries. This
difference in material removal mechanisms is noticeable for the 7–10-fold improvement of the erosion resistance seen for EB-PVD
TBCs over those synthesized by plasma spraying. Either at room temperature or at 910 C, erosion rates were linear with velocity for
both types of coating. In the case of being impacted with hard particles (alumina at room temperature and 910 C and silica at room
temperature), peak erosion rates exist for normal impact, where the impact angle of scaling is similarly dependent for the air plasma-
sprayed and EB-PVD coatings. At high temperatures, erosion rates increased compared to those measured at room temperature,
which corresponds to the higher test velocities achieved at 910 C.
Wilson et al. compared duplex systems of plasma nitriding followed by plasma-assisted PVD (PAPVD) of TiN deposited on
Ti–6Al–4V and PAPVD of TiN and CrN alone (132). Since conventional surface modifications can often negatively affect fatigue
resistance, the fatigue resistance was also studied. A rubber-wheel-type abrasion tester and pin-on-disc sliding wear tester were
utilized to evaluate the wear resistance of the coatings and the load-bearing capacity of the substrate, respectively. In addition,
a Wohler-type rotating tester was utilized to examine the fatigue properties. Through applying the smooth rotating-bending fatigue
specimens tested in air at 5700 rev mm 1 for 10wcycles or until rupture, it was found that TiN, CrN, and the duplex coating did not
negatively affect the fatigue resistance; rather, they actually improved the S–N curves and increased the endurance limit. Based on
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wear results, it was found that although TiN and CrN do noticeably promote the wear resistance of Ti–6Al–4V, the duplex coating
has a greater load-bearing capacity on the titanium substrate and results in a considerable improvement on PAPVD TiN or CrN
coatings in sliding and abrasive wear conditions.
Cholvy et al. deposited the coatings in the Cr–C–N ternary system through the reactive vapor deposition applying an arc
discharge (133). The structure and microhardness of the films are closely connected to the experimental parameters. Chromium
films possess a microhardness ranging from 800 to 1000 HV0.01. The following phases are deposited for chromium nitride coatings:
doped chromium, CrN, CrzN, CrN, and Cr2N. The microhardness is in the range of 1500–2000 HV0.01. The nature of the chromium
carbide deposit is controlled by a large number of parameters. The microhardness was between 2000 and 3000 HV0.01. The
composition of chromium carbonitride deposits is mainly controlled by the temperature and the pressure ratio of the reactive gases.
Moreover, X-ray analysis indicated the presence of Cr2(C,N), CrN, Cr2(C,N) plus CrTC3, Cr2(C,N) plus CrN, and doped chromium.
Batchelor et al. applied surface alloying and thin coatings to roping wire to suppress fretting wear and friction (134). To do so,
the wires were treated through PVD, electroplating, as well as laser surface alloying (LSA). Here, a high-frequency wear test rig was
applied to measure wear and friction levels of the treated wires under dry fretting. Considering the information discussed here about
fretting resistance, corrosion resistance, and possible strengthening of steel wire, chromium and zirconium were chosen as coating
materials. Using the PVD technique, a solid lubricant, molybdenum disulfide, was also deposited. LSA offers a more durable friction
reduction compared to PVD coatings. Moreover, the friction of the molybdenum disulfide coating was controlled by coating
thickness; in other words, a thin coating failed rapidly after an initially low friction, while thicker films provided a gradual friction
increase from a similarly low initial friction coefficient. LSA led to both increase and decrease of friction. Also, it must be noted that
laser treatment without alloying had little effect on friction. In the case of using high levels of zirconium in LSA, a considerable wear
reduction was observed. The laser hardening alone also caused a decrease in wear.
Su et al. tested different potential surface-treated materials paired with multiple cathodic-arc plasma deposition (CAPD) TiN
coating specimens under reciprocating wear conditions using an SRV wear machine (135). Figure 23 shows a metallograph of
tufftrided and carburized treated specimens with PVD coating TiN. One application of these coatings is for screws and rollers. Before
performing the wear testing, the processing parameters of the TiN coatings (i.e., bias voltage, arc current, and partial pressure of N)
were optimized. The polishing pretreatment of the substrate resulted in the maximum wear resistance. According to the indentation
test, it was found that the adhesive strength drops with increasing coating thickness. In the case of excessively thin films, they were
easily worn through. Here, the optimum coating thickness was 3 mm. Under water-based cutting fluid, the self-mated TiN and TiN-
surface-treated specimen pairs indicated no measurable wear, except for surface polishing on the TiN surface. There are both
potential sliding pairs for TiN coating in machine element applications. The wear mechanisms of TiN involve the local flaking of the
coating layer at the edge of the wear scar as well as the surface polishing and surface pitting under oil-lubricated wear conditions. The
wear mechanisms under dry wear led to a residual TiN unworn layer in the presence or absence of a transferred layer, and the
exposed substrate region covered with a transferred layer. Suitable sliding pairs are self-mated TiN and TiN-surface-treated samples
under cutting fluid lubrication, and carburized samples paired with TiN coated samples under base oil lubrication.
TiAlN is among the most commonly evaluated hard coatings in laboratory and real-life applications. However, recently a novel
ternary nitride AlCrN with a high percentage of aluminum and better properties has been ever-increasingly noticed by researchers.
Thus, it would be a useful project to examine the tribological behaviors of AlCrN versus TiAlN coatings with focus on their wear
mechanisms. Mo et al. deposited AlCrN and TiAlN coatings on cemented carbide using the arc PVD (45). The AlCrN coating
indicated lower friction coefficient and wear rate compared to those of the TiAlN coating under same testing condition. The
dominant wear mechanism for the AlCrN and TiAlN coatings in both types of the sliding wear tests was a combination of abrasive
and oxidative wear, where tribo-oxidation played a key role. Nevertheless, an extrathin transferring film was developed in the center
area of the wear track for the ball-on-disc testing. This might be because of the different wear debris behaviors resulting from the
different relative sliding modes. In comparison to the TiAlN coating, the AlCrN coating indicated superior performance of anti-
oxidation and antispalling (see Figure 24).
Özmen et al. coated DLC films using PVD on WC–Co substrate in the presence and absence of an Si interface (136). The films
were tested under low (w20%) and high (w80%) humidity conditions using the reciprocating friction and wear device. Wear
debris particles behave as an abrasive agent (i.e., they deposit into the film and lead to failure initiation). In both cases, there are
a large number of wear mechanisms (including fatigue, abrasion, etc.) that simultaneously exist in the wear of DLC film. Wear rate
inversely correlates with the total wear way. It is possible to apply a chemically activated process as the controlling step in microcrack
propagation during the generation of a wear debris particle. Various tribological behaviors of the DLC coatings under various
environmental conditions were presented. Picas et al. explain and compare the mechanical and tribological properties of CrN
coatings deposited by means of PVD–CAPD on three different substrates: steel, aluminum alloy, and reinforced aluminum alloy
(61). Their results indicated that measured coating hardness relies upon the indentation depth reached in the ultra-
microindentation tests. Moreover, the coating–substrate system was characterized, the hardness variation from the coating to the
substrate was analyzed by different indentation depths, and the experimental curve was modeled using a universally approved
mathematical approach. The CrN–steel system indicated the best performance, where the system hardness is close to the CrN
coating hardness. Besides, the CrN–AMC system outperforms the CrN–aluminum one; however, it had worse performance than the
CrN–steel system.
Polonsky et al. experimentally studied the effect of PVD of TiN coatings with various thicknesses on the rolling-contact fatigue
(RCF) life of coated samples (137). According to the results of conventional three-ball-on-rod testing, the optimum film thickness
was determined to be 0.75 mm. Here, the thinner coatings did not considerably affect the fatigue life, although much thicker ones
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Figure 23 (a) Metallograph of tufftrided TFl-treated specimen; (b) metallograph of carburized treated specimen; (c) metallograph of SKDll after vacuum
heat treatment; (d) surface morphology of PVD coating TiN (3 p.m.); (e) line scan of Ti element distribution in the particle; and (f) the TiN coating
(7 p.m.) showing columnar grains, which nucleate in the preferred orientation. Reproduced from Su, Y. L.; Lin, J. S.; Shiau, L. I.; Wu, J. D. A Tribological
Investigation of Physical Vapour Deposition TiN Coatings Paired with Surface Treated Steels for Machine Element Applications. Wear 1993, 167, 73–83.
Figure 24 SEM micrographs (a) of the wear scar, and EDX line analysis (b) along the line AB for the AlCrN coating under the reciprocating sliding
condition. Reproduced from Mo, J. L.; Zhu, M. H.; Lei, B.; Leng, Y. X.; Huang, N. Comparison of Tribological Behaviours of AlCrN and TiAlN
Coatings-Deposited by Physical Vapor Deposition. Wear 2007, 263, 1423–1429.
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negatively affected it. These trends are consistent with the findings of previous works. Using a progressive testing technique, the
mode of localized damage experienced through the thick TiN coatings under cyclic contact stress conditions was developed. In
addition, the fatigue life reduction observed with such coatings was described in comparison to the coated surface roughness in the
damaged and the intact portions of the rolling track. Progressive testing results all suggest that the stress-affected material volume
plays a key role in near-surface-initiated RCF. Through adjusting the fatigue test conditions, the fatigue life was enhanced in some
PVD TiN coatings because of polishing of the loading ball by the hard coating. Gibson applied sputtering techniques to deposit
thick refractory metal and alloy coatings inside rifled tubes (138). Applying an extended source, in the form of a negatively biased
coaxial central rod made of the coating material, guarantees the uniform coverage of the substrate. In addition, application of
a negative bias to the tube enhances the intensity of the source glow discharge. Based on examination of tungsten and tantalum
coatings, it was found that poor adhesion presents, mainly due to the development of a brittle iron oxide layer during sputter
cleaning. The reliance of the columnar coating morphology upon the intensity of the substrate glow discharge is demonstrated
through a variation in the grain dimension between the land and groove of the rifling.
The common limitation of almost all PVD techniques is in the creation of rather thin (107–104 m) layers. Owing to their abrasion
resistance and corrosion resistance benefits to the engineered pieces, such coatings are very important in engineering applications. In
addition, they have a wide market in electronic and optical devices, decorations, and architecture. For these reasons, various
advances have been made in all aspects, and since each application has its own requirements, different techniques are combined to
produce the new ones. The PVD process includes processes that indicate the main controlling factors of PVD and have wide
applications. The nature of created coating also corresponds with PVD processes. PVD coatings are produced by either evaporation
from a melting source or by atoms injection from a solid source bombarded with ionized gases (sputtering). Different properties
and newly achieved results were discussed throughout this chapter for the fabrication of micro- and nanocoatings.
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92. Lu, T. J.; Levi, C. G.; Wadley, H. N. G.; Evans, A. G. Distributed Porosity as a Control Parameter for Oxide Thermal Barriers Made by Physical Vapor Deposition. J. Am. Ceram.
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93. Taher, M. A.; Schmidt, W. F.; Naseem, H. A.; Brown, W. D.; Malshe, A. P.; Nasrazadani, S. Effect of Methane Concentration on Physical Properties of Diamond-coated
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94. Schäfer, E. Effect of Physical Vapor Deposition on Cutting Efficiency of Nickel-Titanium Files. J. Endodont. 2002, 28, 800–802.
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97. Toriz, F. C.; Thakker, A. B.; Gupta, S. K. Flight Service Evaluation of Thermal Barrier Coatings by Physical Vapor Deposition at 5200 H. Surf. Coat. Technol. 1989, 39–40,
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101. Quinto, D. T.; Wolfe, G. J.; Jindal, P. C. High Temperature Microhardness of Hard Coatings Produced by Physical and Chemical Vapor Deposition. Thin Solid Films 1987, 153,
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102. D’Haen, J.; Quaeyhaegens, C.; Stals, L. M.; Van Stappen, M. Interface Study of Physical Vapour Deposition TiN Coatings on Plasma-nitrided Steels. Surf. Coat. Technol. 1993,
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103. Bi, X.; Xu, H.; Gong, S. Investigation of the Failure Mechanism of Thermal Barrier Coatings Prepared by Electron Beam Physical Vapor Deposition. Surf. Coat. Technol. 2000,
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104. An, K.; Ravichandran, K. S.; Dutton, R. E.; Semiatin, S. L. Microstructure, Texture, and Thermal Conductivity of Single-layer and Multilayer Thermal Barrier Coatings of Y2O3-
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105. Hakansson, G.; Hultman, L.; Sundgren, J. E.; Greene, J. E.; Münz, W. D. Microstructures of TiN Films Grown by Various Physical Vapour Deposition Techniques. Surf. Coat.
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107. Laxman, S.; Franke, B.; Kempshall, B. W.; Sohn, Y. H.; Giannuzzi, L. A.; Murphy, K. S. Phase Transformations of Thermally Grown Oxide on (Ni, Pt)Al Bondcoat during Electron
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113. Stirniman, M. J.; Falcone, S. J. The Ideality of Polydisperse Perfluoropolyether Lubricants with Application to Physical Vapor Deposition. Tribol. Lett. 2000, 8, 171–177.
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116. Leclair, P.; Berera, G. P.; Moodera, J. S. Titanium Nitride Thin Films Obtained by a Modified Physical Vapor Deposition Process. Thin Solid Films 2000, 376, 9–15.
117. Quaeyhaegens, C.; Stals, L. M.; De Schepper, L.; Van Stappen, M.; Malliet, B. Characterization by Glancing Angle X-ray Diffraction of the Interface between Austenitic
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118. Mohite, K. C.; Khollam, Y. B.; Mandale, A. B.; Patil, K. R.; Takwale, M. G. Characterization of Silicon Oxynitride Thin Films Deposited by Electron Beam Physical Vapor
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119. Wolfe, D. E.; Singh, J.; Narasimhan, K. Synthesis and Characterization of Multilayered TiC/TiB2 Coatings Deposited by Ion Beam Assisted, Electron Beam-physical Vapor
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120. Fancey, K. S. A Coating Thickness Uniformity Model for Physical Vapour Deposition Systems: Further Analysis and Development. Surf. Coat. Technol. 1998, 105, 76–83.
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125. Brauner, H. Corrosion Resistance and Biocompatibility of Physical Vapour Deposition Coatings for Dental Applications. Surf. Coat. Technol. 1993, 62, 618–625.
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7.05 Fabrication of Micro/Nanostructured Coatings by CVD Techniques
7.05.2 Process Characteristics 86
7.05.3 Various Types of Reactions 86
7.05.3.1 Pyrolysis 86
7.05.3.2 Reduction to Metal 87
7.05.3.3 Unparalleled 87
7.05.3.4 Plasma-Assisted CVD 87
7.05.3.4.1 Methods and Materials 87
7.05.4 Coating Thickness 88
7.05.5 Coating Rate 88
7.05.6 Costs 88
7.05.7 General Suggestions 88
7.05.8 Design of CVD 91
7.05.8.1 General Considerations 91
7.05.8.2 Design Requirements 91
7.05.8.3 Surface Conditions 91
7.05.8.4 Required Information for the Coater 92
7.05.9 Applications of CVD in Fabrication of Micro- and Nanocoatings 93
7.05.9.1 Synthesis of Coatings 93
7.05.9.1.1 Diamond Coatings 93
7.05.9.1.2 Nitride, Carbide, and Boride Coatings 96
7.05.9.1.3 Oxide Coatings 102
7.05.9.1.4 Polymeric and Other Types of Coatings 106
7.05.9.2 Characterization of CVD Coatings 109
7.05.9.3 Properties of Coatings 110
7.05.9.3.1 Electrochemical Properties 110
7.05.9.3.2 Tribological Behavior 111
References 113
7.05.1 Introduction
Chemical vapor deposition (CVD) techniques have been utilized over the past century but not purely for coating purposes. For
instance, Moud is a nickel purification process performed through pyrolysis of volatile nickel carbonyl through a CVD process. As
a coating process, CVD played a customized, but very important, role, ever since the low melted halides of refractory metals were
investigated as a system. Today, the term ‘chemical vapor deposition’ involves a wide range of processes in all of which the applied
reagents are those that can tolerate chemical reactions at or near the heated surface. Generally, each CVD reaction consists of three
steps: first, creation of a carrier compound such as nickel carbonyl; second, transfer of the generated gas to the deposition spot
without its decomposition; and third, the required chemical reaction for coating creation on substrate. These steps can be performed
at separate time or take place simultaneously in a reaction chamber; like what occurs in compressed alumina or iodine-quartz lamp
in which the source (tungsten filament) is constantly recoated by its evaporated vapor. Requirements of these three steps impose
various limitations to the process; however, CVD process fills the gap in case the other techniques cannot coat effectively. The CVD
process is unique in terms of pyrolytic carbon and boron nitride generation (1–12).
Warnes conducted a research (1) to determine the potentials of CVD codeposition in the synthesis of hafnium-, zirconium-, and
silicon-modified platinum aluminide diffusion coatings; (2) to determine if the reactive element additions enhance oxidation
resistance; and (3) to indicate whether CVD codeposition removes the elements harmful to high-temperature oxidation resistance
(13). Based on the experimental findings, all objectives of this work were achieved. This means that, using CVD codeposition it is
possible to make controlled active element additions to diffusion platinum aluminide coatings. In addition, the combined
influences of tramp impurity removal and reactive element additions results in a fourfold greater oxidation resistance compared to
the one observed for traditional biphasic-type Pt aluminide coatings synthesized through high-activity pack cementation (LDC-2E)
or gas-phase (MDC-150) coating techniques. Here, it is necessary to note some facts associated with the results. First, the reports

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86 Fabrication of Micro/Nanostructured Coatings by CVD Techniques
show that application of platinum aluminide coatings modified with Hf and/or Zr and Si as the bond layer in a thermal barrier
coating (TBC) system results in higher performance compared to other patented TBC systems. Next, owing to the fact that CVD
utilizes different metal halide generators for each element added to the coating, and all process variables are controlled by computer,
the CVD codeposition process is more efficient and competent than pack cementation techniques. Finally, since separate gas
systems are applied for the internal and the external coatings on turbine airfoils, various coatings can be simultaneously used in two
surfaces. In particular, it is possible either to deposit a simple aluminide (such as MDC-210) or to codeposit an active element-
modified aluminide inside airfoil cooling routes, while an active element-modified platinum aluminide (such as MDC-151L) is
employed to its external surface. According to the findings of this work, controlled CVD codeposition of aluminum and one or more
reactive elements is possible. The CVD codeposition process has many advantages over the alternative techniques for producing Hf-,
Zr-, and Si-modified diffusion coatings. In addition, the CVD codeposited coatings indicated appropriate degradation resistance
either as the bond coating for a TBC system or as the only turbine airfoil coating used.
Warnes and Punola conducted an experimental program to identify diffusion coating impurities introduced by standard
aluminizing processes (14). They also evaluate the impact of these impurities on oxidation resistance of the obtained Pt
aluminide coating. Here, the IN-738 tabs and foils were platinum-electroplated and then aluminized through three different
processes including high-activity pack cementation, high-activity CVD, and low-activity CVD. The obtained results indicated that
aluminizing processes can contaminate the diffusion coating during deposition process. However, applying CVD low-activity
aluminizing process, in which coating gas was generated at low temperature outside the coating chamber from 99.999% Al,
did not result in any coating impurities. Furthermore, it was found that the harmful impurities from the IN-738 substrate (sulfur,
boron, and tungsten) and the electroplating process (phosphorus) were eliminated from the coating during deposition. Finally,
the CVD low-activity Pt aluminide coating was the ‘cleanest’ method and demonstrated the best high-temperature oxidation
resistance of the studied coatings. As conclusion it can be claimed that the trace elements in diffusion coatings from the superalloy
substrate and/or the aluminizing process can have a negative effect on oxidation resistance of these coatings. Besides, CVD
low-activity aluminizing produces cleaner coatings compared to other commercially available aluminizing methods.
Sanjurjo et al. combined the techniques including CVD, fluidized bed technology, and subhalide chemistry for coating metallic
and ceramic substrates such as copper, steel, silica, and graphite with metallic and ceramic coatings of silicon, zirconium, TiN, and
Si3N4 (15). Here, subhalide and element-halide-hydrogen species serve as transport agents to carry the coating material from the
bed to the coating target. Since the coating target is in close contact with the bed, even very unstable short-lived species can play
a significant role in the coating process, owing to the fact that they provide a low-temperature path for the transport of mass. By
applying the reactive vapors such as HBr, it is possible to develop these transport species at much lower temperature. To do so, it is
required to use fully halogenated species such as TiCl4 which are much more stable in thermodynamic and kinetic aspects.
According to this work, it can be concluded that it is possible to perform deposition process at atmospheric pressure and at lower
temperatures than with conventional CVD. Moreover, the technique is required to be applicable to the coating process with other
materials such as carbides, borides, and sulfides.
7.05.2 Process Characteristics
Unlike physical vapor deposition (PVD) processes, high temperature and reaction nature do not require complete cleaning of the
substrate before its coating in CVD process. Besides, high temperature ensures effective density and cohesion of the coating. The
coatings are typically rougher than the substrate and the underlying coating. One explanation for this is the greater thickness of
the coating in this technique, which ranges from 10 mm to 1 mm. Throw power and coating’s surface uniformity is excellent in
CVD coating since the applied gas has a pressure equal to the ambient pressure. This implies that it is possible to use various
materials with different particle size and shape in this process. The technique is efficient for, particularly, coating of the sintered
carbides (4,10,16–26).
7.05.3 Various Types of Reactions

7.05.3.1 Pyrolysis
Element coatings are mainly fabricated through simple pyrolysis of the volatile components from refractory metals. The most
commonly used compounds in this class are carbonyls such as Ni(CO)4, halides such as WF6, hydrides such as B2H6, and specific
metallo-organic compounds such as copper acetylacetonate. Carbonyls are decomposed to the metal and carbon monoxide
typically below 200 C, but if it is required to synthesize an adhesive and consolidated coating, the substrate has to be hotter than
this temperature; however, substrate temperature is generally maintained below 600 C. The main disadvantage of carbonyls is their
high toxicity. Halides and hydrides tend to be decomposed at high temperatures (above 500 C), although in this state the
requirements for recoating have to be considered. Also, the temperatures above 1000 C are not very common. Due to the accessory
reactions between decomposition products, the organic components are not widely applied for coating purposes but since these
compounds are decomposed at temperatures lower than those of halides they are widely used in the synthesis of pyrolyzed carbon
either as coating or as delicate parts. Simple hydrocarbons such as paraffin are used to produce pyrolyzed carbon in case the
temperature is above 1500 C (9,27–36).
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Fabrication of Micro/Nanostructured Coatings by CVD Techniques 87
7.05.3.2 Reduction to Metal

One of the commercial applications of CVD is cemented carbide coatings (such as TiC) on cutting tools’ head, which is obtained
through the reaction between titanium tetrachloride, methane, and hydrogen. Once reaction pressure is below ambient pressure,
reaction temperature can reduce to 700 C. Also, a TiC layer with thickness of 5 mm leads to a 5 times increase in tools’ life. Titanium
carbonitride can be synthesized at slightly higher temperatures but provides higher endurance. Compared to chloride, nitrogen, and
hydrogen, titanium nitride involves excellent abrasion resistance and has an attractive golden color. Now, this compound has wider
range of application compared to the carbide and is utilized in different parts varying from cutting tools’ head to watch frame.
Today, above 60% of carbide cutting tools in the United States through CVD technique are fabricated using TiC or TiN, while HfN,
HfC, or Al2O3 are produced in lower amounts where their cost is estimated as 5–50% of the initial equipment costs.
In addition to the mentioned cases, many nitrides, carbides, oxides, silicides, and borides are also fabricated as abrasion-resistant
coatings through CVD technique but the reagents are toxic and require temperatures above 1000 C. Here, an exception is W2C,
which can be efficiently produced at temperatures below 700 C and then involves considerable potentials to coating pyrolyzed
frames without requiring any further pyrolysis (37–49).
7.05.3.3 Unparalleled
There are few reactions placed in this category among which compressed aluminizing is the most important. However, regarding the
other metals such as germanium and gold (producible through this technique) there is no insistence to use them as engineering
coatings.
7.05.3.4 Plasma-Assisted CVD

The most noticeable improvement in PVD processes is ionization of active compounds (similar to CVD approach) where a radi-
ation discharge reduces reaction temperature up to several hundred degrees centigrade. Since vapor deposition of SiO2 from tet-
raethoxysilane requires temperatures of 700 C, application of radio frequency (RF) in plasma-assisted CVD (PACVD) reduces
reaction temperature down to 200–300 C and then allows deposition of thin quartz layers on semiconductor materials. However,
reaction pressure has to be decreased to 100 Pa to avoid arching. For this reason, coating rate reduces compared to that of inactive
reactions and might reach 0.3 mm h1.
Both DC plasma and RF (with frequencies in the microwave range) have been applied and it was found that quartz reaction is
effectively activated by ultraviolet (UV) light. Today, microwave plasmas are an interest for many researchers to synthesize diamond
layers. Layer deposition is performed from a mix of hydrogen and organic gases containing methyl radicals with growth rate of
10 mm h1, but it was reported that Russian workers have fabricated some bushes with thickness above 1 mm. Diamond layers are
adequate abrasion-resistant coatings and have various applications in semiconductor technology, although it is their first experience
as commercial product. The Japanese company, SONY, produced a high-frequency speaker with tweeter sound based on physio-
electric properties using thin diamond layers. Here, the light tough layer responds well to high sonic frequencies (3,50–61).
7.05.3.4.1 Methods and Materials

The metallic coatings produced by CVD process (e.g., chromium or nickel coatings) are very pure and flexible and deposited by
approximate density of 100%. However, CVD is a more expensive process compared to electrodeposition and thus is only applied
in metals that cannot be electrodeposited like refractory metals such as W, Mo, Rh, Nb, Zr, Hf, etc., and some of their alloys. Coating
rate depends on reaction temperature and varies between 3 mm h1 and 3 mm h1. The main advantage of using this technique for
metals is the excellent throwing power for the synthesis of delicate coatings and parts at temperatures below those required for the
ordinary processes. Here, some products are crucibles, missile nozzles, and other high-temperature linens for chemical tanks and the
coating for electronic parts.
Thermally treated carbon is completely neutral and involves excellent thermal conductivity and is applied in chemical tanks,
high-temperature crucibles, nuclear fuels covers, and (in a less toxic application) as the linen for deep part of pipe. Also, thermally
treated boron nitride is mainly used as crucibles to synthesize specific electro-optic materials and coating of cutting tools. The
general application of CVD is synthesis of thin layers of TiN, TiC, and other components on shaping and metalwork tools and on
pieces such as blades, valves, nozzles, etc., which are susceptible to corrosion and abrasion. Application of CVD coatings where high
abrasion resistance is required like dentation crucibles is very limited for TiC, but in the cases such as head or carbide, drills, rods,
etc., where lubrication and resistance to scaling is important, TiN is widely utilized. On a smaller scale, alumina that serves as
a thermal barrier and cobalt glue protection can be used for carbide tools at uncommon turning rotation speeds. CVD techniques
maybe the only option for depositing diamondlike layers up to the thickness of several micrometers; however, some other processes
are also used in this regard. Now, application of diamond coatings for abrasion resistance or electronic and some optic purposes are
in the verge of an explosion.
The other deposited components, particularly those deposited by PACVD, like quartz, silicon, silicon nitride, and titanium
nitride are mainly applied in electronic applications as thin substrates and insolent layers. Despite having higher coating rates in
single-load and high-temperature processes, longer times are required compared to the slower coating processes. Besides, this high
coating temperature makes alloy steels tolerable to further thermal treatment after coating process. Lower temperatures are possible
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whenever the reactions are activated by the plasma, but the rate of PACVD coatings is commonly lower due to lower gas pressure.
Such factors lead to complexity and difficulty in comparing and selecting the best approach. However, CVD techniques involve
some noticeable characteristics that are vital for some applications (1,8,62–73).
The considerable overlaps between characteristics of various processes make their comparison a difficult task. Since many
processes are in their revolutionary period, allocation of a given approach to a particular application is not always possible and
might change through the modifications in the given technique. Although it can be generally claimed that ion implantation involves
various limitations for abrasion-resistant applications, CVD is specific for substrates that are safe when heating up to 300 C and
creation of adequate thickness for delicate parts and thick layers of thermally treated materials is only possible by this process.
7.05.4 Coating Thickness
Thickness range is not necessarily true for all available materials and processes, is not utilized for all processes, and indeed, does not
imply the actual limitations. It must be noted that coating thickness is determined by its application and not process capability.
The mentioned explanations are not true for ion implantation. A unique property of nitrogen implantation in steels is inward
migration of the nitrogen as it disappears in the surface. Although the main concentration of implantation is limited to subsurface
thin layer thinner than 1 mm, abrasion resistance remains up to a very larger depth (5,74–83).
7.05.5 Coating Rate
Considering the fact that various processes are applied to reduce the distance from various sources, the comparison between coating
rate of the processes gets complicated in a given material. Except ion implantation, coating vapor flow is in the form of a cone and
even fills reaction chamber. Hence, coating rates are complicatedly different considering the coating distance. Reaction rate rises by
adding the sources and, less effectively, by increasing the applied power; however, on applying a very high rate, the coating is
subjected to be damaged. It is expected that this output increase continues thanks to the developed dispersion supplies. This increase
in magnetron dispersion rate has made it competent with commercial vapor deposition techniques and there is yet no sign indi-
cating limitation of this technique. Ion implantation rates cannot be considered similar to coating rates. Here, the total dose amount
(3 107 nitrogen ions per cm2) is a key factor. Operation rate is the time consumed for surface unit implantation with the required
amount. Now, it is possible to achieve operation rates up to 5 cm2 min1 and it is not clear as if there is a limitation to it (2,84–92).
7.05.6 Costs
Typically, it is not possible to directly compare coating costs but one can estimate it in a rough manner. Probably, vacuum
evaporation by resistance heating is the cheapest technique in all aspects, while electron bombardment heating or RF power can
seriously affect investment cost and the current costs. Ion implantation and the associated techniques, compared to vacuum
evaporation, requires rather expensive equipment since it involves less coating efficiency and many factors are required to be
controlled. Investment cost of the dispersion equipment is high and they are also very complicated. However, thanks to the
electronics industry, considerable advances are about to be made while keeping the costs low. A cost comparison between ion
implantation and other techniques is soon to occur since this process is newly applied in economic scales. The direct operational
costs of ion implantation are average, but the investment costs are high. Also here, the advances in machining tools are in progress
and are about to give fruit. Compared to the traditional approaches, CVD is considered a cheap technique to shape some refractory
metals. Although its unique potentials in synthesis of thermally treated materials have reduced its costs, the indirect costs associated
to toxicity of many applied pieces can strongly enhance investment and current costs (93–106).
7.05.7 General Suggestions
As conclusion, it is worth to remind that apart from the mentioned points the dominance boundaries of the introduced technique
are not clear. Undoubtedly, by experiencing various applications it is possible to have a clearer image about their future; never-
theless, there is always a wide range of overlap for the applications and some particular features determine superiority of each
technique.
Gordon conducted a review on CVD. Now CVD is applied to deposit films of a large number of materials (74). A particular group
of materials including silicon, titanium nitride, and the oxides of silicon, aluminum, tin, zinc, and transition metals, are important
in glass industry and can add very useful electrical and optical properties to glass. There are several different chemical sources and
reactions applied for deposition of these materials. These processes can be compared in terms of ease of use of the precursors,
attainable deposition rates, and safety and cost of the precursors. Various tools have been developed for deposition of these
materials with excellent thickness uniformity over large areas of glass. Fluorine-doped tin oxide and zinc oxide appropriately reflect
infrared (IR) heat (low emissivity); so, they enhances the insulating ability of the windows. Since these materials are electrically
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conductive, they open up a variety of applications, including solar cells, flat-panel displays, touch control panels, and static
dissipation. Titanium nitride provides near-IR reflectivity, which can provide high-performance rejection of solar heat (solar control
glass). Besides, silicon/silicon dioxide/silicon trilayers create durable mirror coatings with high reflectivity to visible light. Amor-
phous aluminum oxide films are excellent barriers to diffusion of sodium out of soda-lime glass.
Hack et al. described specially designed, large-scale equipment for uniform coating of carbon short fibers with thin layers of SiC
and TiN in a continuous CVD process (107). The layer thickness for TiN was about 70 nm. Because of the low deposition temperature,
the thickness of the SiC layer (15 nm) deposited at 950 C was relatively low. Raman spectroscopy revealed an amorphous SiC
microstructure. Higher deposition temperatures are applied in order to enhance the layer thickness and the crystallinity of the SiC
coatings. Carbon short fibers coated with thin ceramic layers can be applied in fiber-reinforced composites. The coatings act as
reaction barriers and provide an excellent fiber–matrix bonding, which in turn results in improved composite performances. Kwok
and Chiu deposited carbon films on fused quartz substrates through CO laser-induced chemical vapor deposition (LCVD) in which
a novel open-air coating system was utilized (61). They used methane, propane, and butane as hydrocarbon precursor gases.
By measuring the mass of the carbon film deposited at constant temperature, the deposition rates of the three hydrocarbon gases were
determined and then validated by film thickness measurements obtained using an environmental scanning electron microscope.
According to the findings of this work, butane and propane indicated significant deposition at 1375–1500 K, while deposition
initiates at 1550 K for methane. Here, an exponential increase in deposition rate was observed for all three hydrocarbons. Deposition
rates obtained with butane and propane show a much stronger influence of temperature compared to methane. According to the
Raman spectra of the deposited carbon films, the surface consists of glasslike or nanocrystalline carbon. By increase of deposition
temperature, the ratio of D-peak to G-peak Raman band intensities decreases; this might be attributed to the self-annealing and
additional surface reaction during high-temperature deposition. Based on this finding, one can claim that the carbon film indicates
higher structural order at high deposition temperatures, which, in turn, can highly enhance the film’s hermeticity and mechanical
properties for use as an optical fiber coating. Figure 1 shows open-air laser-induced chemical vapor deposition system.
Mitterer et al. tested several commercial hard coatings developed by PACVD in aluminum die-casting applications including TiN,
Ti(C,N), Ti(B,N), and (Ti,Al)(C,N) (see Figure 2) (108). A considerable increase in lifetime was observed for all coatings tested on
die-casting cores. In order to improve the coating performance and to perceive their various behaviors in die casting, the soldering
tendency was characterized by applying an immersion test in liquid aluminum; then, oxidation resistance was studied by ther-
mogravimetric analysis; and finally, the influence of thermal cycling on film stresses was investigated using a cantilever technique.
Moreover, coating topography was examined using atomic force microscopy. According to the findings of this work, by reducing the
soldering tendency of the coatings and adjusting a suitable level of low compressive stress optimization, it is possible to consid-
erably achieve the performance of hard coatings in aluminum pressure die casting.
Quinto et al. measured microhardness values of hard coatings of TiN and HfN prepared by CVD and those of TiN, HfN, ZrN, and
TiAlN prepared using PVD between ambient temperature and 1000 C (35). The results of this work indicated that microhardness of
the PVD coatings is markedly higher than that of the CVD counterparts at room temperature; however, all microhardness values
tended to converge at 1000 C. Compared to CVD TiN, higher N:Ti ratios were found for PVD TiN. Based on X-ray diffraction (XRD)
Figure 1 Open-air laser-induced chemical vapor deposition system. Reproduced from Kwok, K. H.; Chiu, W. K. S. Open-air Carbon Coatings on Fused
Quartz by Laser-induced Chemical Vapor Deposition. Carbon 2003, 41, 673–680.
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Figure 2 Scanning electron microscopic (SEM) images of different PACVD hard coatings deposited onto ground and polished H11 steel
substrates after 1 h immersion into an AlSi7Mg melt at 700 C. (a) TiN coating scanning backscatter electron micrograph. (b) Ti(C,N) coating
scanning backscatter electron micrograph. (c) (Ti,Al)(C,N) coating. Reproduced from Mitterer, C.; Holler, F.; Lugmair, C.; Nobauer, R.; Kullmer, R.;
Teichert, C. Optimization of Plasma-assisted Chemical Vapour Deposition Hard Coatings for Their Application in Aluminium Die-casting.
measurements, the PVD involves high residual compressive growth stresses (because of lattice distortion and very fine grain size),
confirmed also by applying transmission electron microscopy (TEM). Besides, the thermal expansion mismatch between coating
and substrate resulted in residual stresses in high-temperature CVD coatings. Furthermore, the changing applied conditions of
energetic bombardment and deposition temperature in the several PVD methods resulted in differences in grain morphology and
crystal texture. The faster decrease in microhardness with temperature in PVD coatings can be attributed to the high residual energy
and finer grain size.
Bouyer et al. conducted thermal plasma chemical vapor deposition (TPCVD) of Si-based ceramic coatings from liquid precursors
(109). The process allows synthesis of SiC (and/or Si3N4) through control of both the a/b phases and coating microstructure using
a low-cost liquid precursor. Using the process parameters (i.e., substrate temperature, plasma gas nature, spray distance, and spray
characteristics), it is possible to control crystallite size. Besides, phase content is mainly controlled by the nature of the precursor
(i.e., molar C/Si ratio or N/Si ratio), plasma gas content (nitrogen for nitride or oxygen for oxide), and heat transfer efficiency
between the plasma and the disilane microdroplet precursor. It was found that the precursor droplet size is a critical parameter and
that the finer droplets favor a better treatment in the plasma. Regarding the obtained phases, the two disilane precursors employed
yielded different results. Considering the C/Si ratio of these precursors, a C/Si ratio of almost 1 is advantageous to b-SiC formation,
while a higher C/Si ratio involves formation of a-SiC with extra amount of graphite. Furthermore, the presence of nitrogen either in
the precursor or in the plasma gas (in small quantity) seems to make a contribution to the synthesis of the a-SiC. It has been verified
that the TPCVD process applied to Si-base ceramics synthesis is a very compatible technique in terms of the phases that can be
synthesized. Also, it is a very efficient technique since it involves high deposition rate (up to 20 mm min1), which is two orders of
magnitude higher than the one obtained through the conventional CVD methods.
Elkasabi et al. indicated efficiency and activity of carbonyl-functionalized poly(p-xylylenes) polymerized from functionalized
paracyclophanes (PCPs) (98). Using Fourier transform infrared spectroscopy (FTIR) spectroscopy and X-ray photoelectron spec-
troscopy (XPS), compositions of these polymers were verified both within the bulk coating and at the surface. Also, the carbonyl-
functionalized polymers indicated remarkable differences in crystallinity, owing to the compositional changes of the functional
group. Besides, these slight changes result in modified cellular morphologies on surfaces coated with the CVD polymers. Moreover,
carbonyl-functionalized PCPs were copolymerized with amine-functionalized molecules. The obtained copolymers involved
mechanical integrity and were dually reactive because of their amine and carbonyl groups. According to the FTIR spectra, control of
the copolymer compositions was indicated – where they were relatively homogeneous over several inches. It was also observed that
the copolymer composition is directly associated with the monomer sublimation temperatures, whose variations affected the
relative sublimation rates. The findings of this work indicated that these copolymers have potential use as biomedical coatings such
as protein adsorption, cell adhesion, biocompatibility, and immobilization of model drugs. To have a successful CVD polymeri-
zation, initiation and propagation steps must be helpful for producing robust, functional polymer coatings. Less-than-optimum
polymer films will be obtained, for example, when the monomer pyrolysis is incomplete. These effects are generally applied to CVD
polymerization, in general, but are even more noticeable for CVD copolymerization. For the polymer combinations used, the
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parameters were optimized to yield controlled polymer compositions. Nevertheless, optimization must be performed on a case-
by-case basis and limitations are required to be explored considering the obtainable CVD copolymers as novel CVD coatings.
Walther et al. introduced a new coating system for diffusion-barrier applications on polymer substrates such as polyethylene
terephthalate (PET) and polycarbonate (PC) (54). The barrier system is designed as a multilayer coating, made of oxidelike
barrier layers embedded in ‘soft’ polymerlike material. This system serves as a highly stable unit, which indicates excellent
adhesion to the substrate. The system has also been verified to be stable up to 121 C for 30 min without development of any
microcracks. This barrier system is deposited through plasma-impulse CVD technique, which employs a pulsed microwave
plasma working at very low substrate temperatures and high coating rates. This technology incorporates the advantages of the
CVD process, to coating three-dimensional substrate geometries with high-quality and nearly pinhole-free films. On PC with
thickness of 1 mm, the oxygen permeation was decreased by a factor of 360–0.375 cm3 m2 bar1 day1. Besides, the water
permeability was measured as low as 0.23 g m2 day1. This allows its application in highly sensitive packaging products, such
as medical applications.
Wang et al. developed in situ smooth, epitaxial cerium dioxide thin films in the 450–650 C temperature range on (001) yttria-
stabilized zirconia (YSZ) substrates (110). To do so, they applied metal–organic chemical vapor deposition (MOCVD) using a novel
fluorine-free liquid Ce precursor. The epitaxial films indicated a columnar microstructure with atomically abrupt film–substrate
interfaces and with only little bending of the crystal plane parallel to the substrate surface near the interface and at the column
boundaries. Applying the constant precursor temperature and gas flow rate, the CeO2 growth rate decreases from w10 Å min1 at
450 C to w6.5 Å min1 at 540 C. Also, it was found that the root mean square roughness of the films reduces from 15.5 Å at
450 C to 4.3 Å at 540 C. Moreover, high-quality, epitaxial YBa2C3O7x films were successfully deposited on these
MOCVD-derived CeO2 films, which in turn are grown at temperatures as low as 540 C.
7.05.8 Design of CVD

7.05.8.1 General Considerations
Physical vapor deposition techniques, which comprises warm or hot in vacuum techniques, are very wide and diverse, while CVD
techniques are limited to two active gases and do not produce coating through high-temperature reaction or gas phase on the
substrate. Here, the details of various processes were investigated; however, the designer needs to pay attention to some basic
considerations. The total piece or some part of it that constitutes the substrate has to be compatible with the process. Hence,
substrate temperature for PVD equals the ambient temperature or is slightly higher, while the temperature rarely rises above 500 C
for CVD techniques. It means that the temperature range for CVD process is 500–1200 C or, occasionally, slightly higher.
The vacuum requirements in PVD process and the high operation temperature in CVD process results in selection of the
considered part as there is no vapor pressure under deposition conditions – like solder containing Cd and Zn. Nevertheless, the
plastics can be coated under particular conditions. Since both CVD and PVD techniques use active gases, to prevent these gases from
leaking on uncoated spots, it is required to take necessary actions. The coating targets should be freely available for both discharge and
deposition; for instance, the recesses are not easily discharged and show some problems during radiation discharge cleaning. On the
whole, design considerations applied for electrodeposition are simultaneously applied for PVD and CVD techniques (107,111–119).
7.05.8.2 Design Requirements

1. The design should lack any deep and blind holes and cavities.
2. Small holes are difficult to plate. The piece has to be preferably designed in a dividable manner.
3. The holes or cavities have to be coated with a width to depth ratio of 1:1, although the wider ratios are preferable.
4. It is required to remove all surface cavities. The piece is not allowed to be porous or with slots or openings.
5. No chip is allowed to be in the edges of the coated surface.
6. The components have to be montaged by their bolting or contraction interdispersion.
7. Large surface section difference leads to temperature difference in the process and has to be avoided.
8. Coating has to be performed in a mechanical manner and since it has to be very strong and adhesive during the installation,
design accuracy and maybe consulting with the contractor is necessary.
9. Some accessory devices might be required to hold the piece. Here, it is required to consult with minor contractor.
7.05.8.3 Surface Conditions

1. The surface of pieces has to be polished and subjected to no surface operation.
2. Suitable polishing techniques are machining, delicate spark, polishing, and spray. Abraded or sputtered machining disks are not
allowed to be used since they lead to cold boils.
3. The polished products have to be removed through a suitable solvent.
4. For corrosion protection, the pieces have to be slightly oily or immediately coated with a plating material after machining or
cleaning.
5. No chips and foreign objects are allowed to be in the piece, particularly in closed spaces.
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6. The coating target has to be free from any surface operation or plating such as electrical deposition, carbon plating, nitrogen
plating, or chromium and aluminum plating.
7. The coating is not allowed to be burnt.
8. No stain or color is allowed to be in the surface.
7.05.8.4 Required Information for the Coater

1. Materials type and characteristics, if available.
2. Return temperature and any thermal treatment to which the piece is subjected.
3. Maps indicating dimensions and characteristics of coating targets or surface that should be avoided during coating.
4. Details of polish process, if it is required to be performed.
5. Tool type and properties of the turning machine.
6. Hardness in the point that is required to be measured.
7. Detection signs/digits that have to be kept.
Preparation defects in an SiC coating on C/C substrates are believed to be among the controlling factor reducing the oxidation
protection life at preparation temperature. To reduce the number of such defects, Cheng et al. conducted a low-pressure chemical
vapor deposition (LPCVD) technique, instead of the general CVD (67). Besides, the substrates were suspended, rather than their
application in supported state. They performed a multideposition process to seal the preparation defects at the edges of the substrates
produced by the suspension. SiC coating, which involves high quality, had a smaller crack width and a better interfacial binding. The
layers developed in the multilayer coating were all in uniform and smooth state, where their thickness could be easily controlled.
Since the gaps between the multilayers serve as channels for oxygen diffusion toward the defects in the inner layer, oxidation tests
showed that the preparation defects in the coating could not be sealed by multideposition technique. It was also found that the weight
loss decreases with increase of the multideposition times. An analysis showed that, disregarding the number of constituting layers of
the coating, failure always initiates from the preparation defects in the inner layer located at the edges of substrates. Besides, a cavity
can be developed under the inner layer by direct oxidation of the C/C. The oxidation process in C/C substrates with a multilayer
coating was controlled through oxygen diffusion rate along the interlayer gaps that were thinner and longer than the defects. The
longer the multideposition times, the larger would be the length of the gaps and the smaller will be the oxygen transport rate.
CVD of films and coatings involves a set of chemical reactions of gaseous reactants on or near a heated substrate surface. It is
possible to obtain highly pure materials with structural control at atomic or nanometer scale through this atomistic deposition
method. Besides, this technique allows producing single layer, multilayer, composite, nanostructured, and functionally graded
coating materials with well-controlled dimension and unique structure at low temperatures. In addition, the unique properties of
CVD compared to other deposition techniques such as non-line-of-sight-deposition capability enables coating complex-shaped
engineering components and fabrication of nanodevices, carbon–carbon (C–C) composites, ceramic matrix composites, as well as
free-standing shape components. Various capabilities of CVD have rapid growth and now it is among the main processing methods
for deposition of thin films and coatings in a large number of applications, e.g., semiconductors (e.g., Si, Ge, Si1xGex, III–V, II–VI)
for microelectronics, optoelectronics, and energy conversion devices; dielectrics (e.g., SiO2, AlN, Si3N4) for microelectronic-
refractory ceramic materials (e.g., SiC, TiN, TiB2, Al2O3, BN, MoSi2, ZrO2) utilized for hard coatings, protection against corrosion
and oxidation or as diffusion barriers; as well as metallic films (e.g., W, Mo, Al, Au, Cu, Pt) for microelectronics and for protective
coatings, fiber production (e.g., B and SiC monofilament fibers), and fiber coating. Choy et al. presented a summary of CVD
applications for synthesis of films and coatings (120). Also, the fundamental aspects of CVD including process principles, depo-
sition mechanism, reaction chemistry, thermodynamics, and kinetic and transport phenomena are presented. In addition, the
practical aspects of CVD such as the CVD system and applied apparatus, CVD process parameters, process control techniques, range
of films synthesized, characterization, and corelationships of structures and properties are discussed.
This study was conducted by Oguri to evaluate the effect of the N2-to-TiCl4 flow rate ratio on TiN coating properties developed on
M2 steel and pure iron (23). To do their experiments, they applied a temperature of 550 C by a DC glow discharge method from
mixed gases of TiCl4N2, H2, and argon. Besides, deposition rate of the coatings was saturated at an N2-to-TiCl4 flow rate ratio of 8–9.
According to the results of this work, no change in composition and hardness of the coatings was reported with the applied N2-to-TiCl4
flow rate ratio except for the maximum ratio of 14.3. On the other hand, the preferred orientation and microstructure had a noticeable
shift from (111) to (200) and from columnar to nonoriented. Moreover, the coatings deposited at an N2-to-TiCl4 flow rate ratio of 3–6
(produced in the (200) preferred orientation and fine-grained dense structure) exhibited a higher adhesion strength.
Sung Kim et al. developed titanium nitride deposits on TiC-coated 94 wt.% WC–6 wt.% Co substrates by CVD with a TiCl4, H2,
and N2 gas mixture (121). They evaluated the influence of deposition temperature, total flow rate of the reactant gases, partial
pressure of TiCl4 on the deposition rate, the preferred orientation, and the surface morphology of the TiN deposit. They also
discussed the dominant mechanism of the TiN deposition reaction as well as its relationship with deposition temperature and the
total flow rate of the reactant gases. Deposition rate and TiN crystal growth along the (220) preferred orientation rises with an
increase in the deposition temperature and partial pressure of TiCl4 at a total flow rate below 700 cm3 min1. Moreover, particle size
of TiN deposit decreases with increase of the partial pressure of TiCl4, while it increases with an increase in the deposition
temperature at a total flow rate of less than 700 cm3 min1. Once the total flow rate exceeds 700 cm3 min1, the deposition rate, the
TiN crystal growth along the (220) preferred orientation, as well as the particle size of the TiN deposit no longer change. Besides,
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once decreasing the temperature below or exceeding 1000 C, the TiN deposition reaction is controlled by the surface reaction or
mass transport, respectively. Furthermore, in the case the total flow rate is below or greater than 700 cm3 min1, the deposition
reaction is controlled by mass transport or surface reaction, respectively.
7.05.9 Applications of CVD in Fabrication of Micro- and Nanocoatings

7.05.9.1 Synthesis of Coatings
7.05.9.1.1 Diamond Coatings
A simple process has been perfected by De Barros et al. for deposition of smooth fine-grained diamond coatings at 600 C on
titanium alloys or titanium-coated surfaces (122). The process involves a two-step microwave plasma-assisted chemical vapor
deposition (PACVD) procedure. The procedure itself involves, first, deposition of a sacrificial sp2-carbon with layer from a methane-
rich CH4–H2 mixture and then diamond growth from a CO2–CH4 inlet mixture. The coatings were smooth and mainly composed of
crystalline diamond with a fine-grained morphology. The findings of this work were compared to those obtained from classical rough
polycrystalline coatings deposited from 8% CO–H2. Furthermore, the optical emission spectroscopy indicated important differences
between the plasma species produced for the deposition of these smooth coatings and the plasma species produced for the depo-
sition of both polycrystalline coatings from 1% CH4–H2 or 8% CO–H2 mixture and nanocrystalline films from Ar–CH4(-H2).
Bareiss et al. deposited adhesive, polycrystalline diamond films on various steel substrates by applying diffusion chromium
carbide interlayers (22). The employed interlayers indicated appropriate barrier properties for the diffusion of iron atoms from the
steel substrate to the surface as well as that of the carbon atoms from the gas phase into the bulk material (see Figure 3). Chromizing
and diamond deposition resulted in remarkable microstructural changes at the steel–chromium carbide interface and in the bulk
material. In general, the findings of this work indicated three essential mechanisms for the deposition of adherent diamond films on
steel substrates with a chromium carbide interlayer.
Figure 3 SEM picture of the layer compound and glow discharge optical emission spectroscopy spectrum of a diamond-coated steel sample
(X46Cr13) with a chromium carbide interlayer. Reproduced from Bareiss, C.; Perle, M.; Rosiwal, S. M.; Singer, R. F. Diamond Coating of Steel at High
Temperatures in Hot Filament Chemical Vapour Deposition (HFCVD) Employing Chromium Interlayers. Diamond Relat. Mater. 2006, 15, 754–760.
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1. An irregular surface is developed for compressive stress reduction on geometrical reversal points through microstructuring by
sandblasting.
2. Transformation of the chromium carbide phases at the surface results in creation of new covalent bonds between diamond and
chromium carbide and produces a great adhesion of the diamond layer. Thus, a reaction takes places between the former Cr23C6
phase and the carbon from the gas phase and a Cr3C2 layer between diamond layer and chromium carbide interlayer is
developed (see Figure 4).
3. The residual stresses can be decreased by deposition at high temperatures in the austenite field (>800 C), which leads to a g–a
transformation in the steel sample, as well as volume expansion during cooling down. Since this phenomenon takes place for
a certain number of steels, the probability of stress reduction is controlled by the following steel specifications: (a) temper-
ature at the beginning and end of the g–a transformation (depending on the cooling rate) and (b) grade of volume
expansion/contraction in the g þ a field.
Figure 4 XRD spectra and SEM pictures of a chromized surface and after diamond deposition in a low temperature (LT, left) and a high temper-
ature (HT, right) process on a 41Cr4 substrate. In the LT process, the Cr23C6 carbide is formed during chromizing and remains at the interface during
diamond deposition. In the HT process, Cr23C6 carbide reacts with carbon from the gas phase in the diamond process and forms the carbon-rich
Cr3C2 phase. This phase transformation indicates a much better chemical bonding of the diamond film to the carbide phase. For better illustration, the
ongoing reactions are shown schematically as well. Reproduced from Bareiss, C.; Perle, M.; Rosiwal, S. M.; Singer, R. F. Diamond Coating of Steel
at High Temperatures in Hot Filament Chemical Vapour Deposition (HFCVD) Employing Chromium Interlayers. Diamond Relat. Mater. 2006, 15, 754–760.
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Obtaining excellent adhesion of diamond films on steel substrates is among highly focused subjects since reaching such a goal
produces a large number of applications in the cutting and drilling industry. However, an important drawback in diamond
deposition on steel is high diffusion of carbon on steel at CVD temperatures. This results in very low nucleation density and
cementite (Fe3C) formation. Accordingly, although the study of the nucleation and growth processes is a time-consuming task, it
yields data that can be used to understand how to improve adhesion. Polini et al. evaluated adhesion of thin diamond films on
high-speed steel (HSS), which are previously coated with various interlayers like ZrN, ZrC, TiC, and TiC/Ti(C,N)/TiN (123). This
study mainly deals with TiC interlayer, proved for the first time to be a suitable layer for diamond CVD on HSS. Compared to other
interlayer materials investigated, no delamination was observed even after 3 h of CVD at 650 C in the case of applying only TiC.
Nevertheless, an increase in diamond film thickness on TiC-coated HSS substrates resulted in delamination of the small areas in
various regions of the substrate. This implies presence of a distribution of adhesive toughness values at the diamond–TiC interface
with stress development that depends on film thickness. Fu et al. investigated nucleation and growth of diamond coatings on pure
Ti substrate via microwave plasma-assisted chemical vapor deposition (MW-PACVD) method (17). They also investigated the
effects of hydrogen plasma, plasma power, gas pressure, and gas ratio of CH4 and H2 on the microstructure and mechanical
properties of the deposited diamond coatings. Based on the findings of this work, nucleation and growth of diamond crystals on Ti
substrate can be divided into several steps: (1) surface etching by hydrogen plasma and hydride development; (2) competition
between the formation of carbide, diffusion of carbon atoms, and diamond nucleation; and (3) growth of diamond crystals and
coatings on TiC layer. Once deposition of diamond coatings occurs, hydrogen diffuses into Ti substrate, forms titanium hydride,
and then results in an essential microstructural change as well as a severe loss in impact strength. The findings of this work also
indicate that nuclei density of diamond crystals is considerably enhanced through short-term pre-etching of titanium substrate with
hydrogen plasma. The surface morphology and mechanical properties of the deposited diamond coatings are significantly influ-
enced by plasma power. Another work carried out was study of the effects of gas pressure and gas ratio of CH4 and H2 on the
nucleation, growth, and properties of diamond coatings. The higher ratio of CH4 within deposition process enhanced nuclei density
of diamond crystals, although it led to a poor and cauliflower coating morphology. On the other hand, a lower ratio of CH4 in the
gas mixture resulted in high-quality diamond crystals; however, the nuclei density and the growth rate indicated a significant
reduction.
Although having excellent mechanical properties, titanium alloys have poor wear characteristics. Here, it seems that diamond
coatings serve as an efficient solution for the wear problem. Heinrich et al. applied standard deposition parameters for silicon
(diamond-scratched surface, microwave CVD, 500 W, 800 C for 4 h, 50 mbar with an atmosphere of 1% CH4 þ 99% H2) and
obtained excellent coatings on pure titanium (124). The processing temperature and gas atmosphere are the two key factors strongly
influencing mechanical properties of the titanium. Because of hydrogen adsorption, grain coarsening and creation of titanium
hydride occur and, as a result, the low cycle fatigue strength decreases by an order of magnitude. Nevertheless, hydrogen can be
removed again and it is almost possible to restore all the initial mechanical properties through annealing in vacuum (800 C for 2 h,
furnace cooled). Here, the surface can be considered as a five-zone structure (including diamond layer/nucleation zone/reaction
layer/gradient layer/affected substrate) created during the deposition process.
Sikder et al. applied CVD to improve the bonding of diamond particles to the metal matrix in the Ni–diamond-composite-
coated stainless-steel (SS) substrate (84). They coated the substrates using different combinations of Ni–diamond composite
coatings prior to CVD in order to suppress the diffusion of Fe on the deposition surface. Then, they applied two CVD processes for
the growth of metal–diamond composite and continuous diamond films on these buffer-layered substrates. It was found that high-
quality diamond films are grown on the substrates. In addition, energy-dispersive X-ray analysis indicates almost zero Fe content at
the surface after CVD treatment. To grow well-adhered and improved crystalline diamond on SS, it is advisable to use a modified
Ni–diamond composite layer since it provides the most suitable base. Vanhulsel et al. applied a 13.56-MHz magnetically confined
inductively coupled plasma (ICP) system to deposit diamondlike carbon (DLC) coatings from a methane plasma (125).
A noticeable advantage of applying a remote plasma source over the conventional capacitively coupled parallel plate system is the
possibility of decoupling the discharge power absorption and the substrate bias. This, in turn, allows for independent control of ion
flux and energy. Five deposition parameters of this process are the bias voltage, the RF power in the ICP source, the methane flow,
the distance between the source and the substrate, and the cooling of the substrates. The mechanical properties of the coatings
(hardness and Young’s modulus) were measured through nanoindentation. Besides, the structural properties were detected using
FTIR and Raman spectroscopy. Furthermore, mass spectrometry was applied to determine dissociation degree of the precursor gas in
the plasma. One solution for obtaining higher deposition rates and slightly better quality of the coatings is utilizing an efficient
system for substrate cooling. According to the findings of this work, deposition rate can be substantially increased compared with
the conventional capacitively coupled system, without any decrease in the quality of the coatings. A major disadvantage of the ICP
technique is the fraction of capacitive coupling from the RF coil to the plasma, which in turn results in sputtering of the dielectric
window leading to contamination of the coatings and deterioration of their properties. However, this problem was rather
diminished by installing a Faraday shield between the coil and the dielectric window.
Murakawa et al. examined diamond coating of a tungsten carbide alloy through hot filament CVD process for application to tool
manufacture (126). Previously, it was believed that it is not possible to deposit diamond on a cobalt-rich tungsten carbide alloy
using this technique. But now, it is known that a good diamond coating layer can be obtained when applying ethanol as the carbon
source. In addition, no abrasion of the diamond coating and adhesion of chips of the sheared material to the tip of the tool were
observed even after 5 104 punchings in the case of applying a diamond-coated tool to the shearing of an aluminum plate with
thickness of 2.5 mm. This clearly indicates the excellent hard coating effect as well as reasonably good adhesion of the coated
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diamond layer. Through low-pressure synthesis of diamond, it is possible to produce in situ diamond coatings that can highly
enhance the technical performance of cutting devices. However, diamond deposition on cemented carbide tools faces a major
problem: the presence of cobalt on the tool surface, which can interrupt diamond nucleation and growth, which in turn results in
poor adhesion. Pan et al. obtained optimal diamond deposition and excellent adhesion through development of etching and low-
temperature deposition conditions (127). Besides, the surface preparation of the inserts, the deposition method (hot filament),
a simple characterization test for the coatings, and industrial cutting tests are among the topics discussed. The restricted numbers of
cutting tests indicated the quality of the diamond layers and their adhesion compared to the conventional polycrystalline diamond
tools. The findings of this work demonstrated that the performance of low-pressure diamond coatings, at least for turning tests of
short duration, can compete with the level of polycrystalline diamond.
7.05.9.1.2 Nitride, Carbide, and Boride Coatings

It is known that application of the thin titanium interlayer significantly promotes the adhesion of titanium nitride coatings
produced by PVD. Such a belief has emerged from two factors, i.e., dissolution of weak native oxide layers by titanium (a chemical
gettering effect) and compliance of the rather soft interlayer, which decreases shear stresses across the coating–substrate interface.
Bull et al. investigated the effects of a titanium interlayer on adhesion values of titanium nitride deposited by PACVD (37).
According to PVD coating observations, the critical load for coating detachment enhances by increase of interlayer thickness;
however, in contrast with PVD coatings, no peak was observed in the range of investigated interlayer thickness. According to
secondary ion mass spectrometry depth profiles, interlayer has a significant influence in PVD coatings on titanium. Nevertheless, the
improved adhesion with increasing interlayer thickness is highly attributed to its compliance in PACVD coatings, since it involves
more effective precleaning stage. Application of a graded interface enhances adhesion in comparison to the case where no interlayer
is applied. However, as previously mentioned, a titanium interlayer of comparable thickness offers a much greater increase in
measured adhesion. There was a maximum in Weibull parameter (as a function of interlayer thickness) for both PVD and PACVD
films. This has a key effect on wear lifetime. Hence, it should be possible to improve coating performance in tribological appli-
cations through careful control of interlayer thickness and composition.
A new technique was developed by Dasgupta et al. to deposit hard nanocrystalline chromium nitride (CrN) thin films
on metallic and ceramic substrates by plasma-assisted metal–organic chemical vapor deposition (PAMOCVD) technique (128).
A volatile mixture of chromium(III) acetylacetonate and either ammonium iodide or ammonium bifluoride were utilized as
precursors in this low-temperature and environment-friendly process where nitrogen and hydrogen were used as the gas precursors.
A maximum deposition rate of w0.9 mm h1 was obtained through processing conditions optimization. The globular particles were
detected in the microstructure of the CrN films deposited on well-polished SS, while a rather smooth surface morphology was
observed for coatings deposited on polished YSZ. Zhao et al. deposited TiN coatings on the glass substrates by atmospheric pressure
chemical vapor deposition (APCVD) using titanium tetrachloride (TiCl4) and ammonia (NH3) as precursors, to examine the
possibility for TiN coatings to be low emissivity (6). Crystal concentration enhances with substrate temperature rise and TiCl4 flow,
which in turn results in the electrical resistivity reduction. They also showed that the optical transmittance of TiN thin films is
strongly controlled by gas flow and substrate temperature. In the presence of the optimum conditions, continuous polycrystalline
TiN coatings with face-centered crystalline (fcc) structure were obtained with an approximate electrical conductivity of 34.5 U h1,
optical transmittance around 50% in the visible range, and IR reflectance higher than 50% above 3000 nm. This illustrates that TiN-
coated glasses can be regarded as potential alternatives for high-IR-reflectance windows.
Holta et al. studied stoichiometry and hydrogen content of hot wire (HW)-grown silicon nitride as a function of SiH4/NH3 flow
ratio (129). Then, they examined the effect of postdeposition hydrogenation treatment on overall film hydrogen content. Also,
characterization of hydrogen release properties in Si-rich and N-rich nitride layers was performed through annealing treatments.
HW nitride layers were deposited on diffused emitter String Ribbon silicon substrates, which resulted in the formation of cells with
values of short circuit current density, open circuit voltage, fill factor, and efficiency comparable to those of substrates fabricated
using plasma CVD nitride. According to the findings of this work, changing SiH4/NH3 ratio from 0.01 to 0.08 yielded silicon nitride
films with refractive index ranging from 1.8 to 2.5, with hydrogen content ranging from 9 to 18 at.%. Based on FTIR transmission
measurements, a transition in the bonding of H (N–H to Si–H) was observed by increase of flow ratio beyond 0.06. Besides,
annealing studies indicated different kinetics for H release from Si versus N. The appearance of PtH complexes with a concentration
of w1014 cm3 in Pt-diffused Si samples, at annealing temperatures consistent with H release from the nitride top layer, implies that
a tiny share of H diffuses into the Si from the SiNx layer. Finally, ribbon silicon solar cells developed with HW-grown silicon nitride
layers indicated electrical properties comparable to those formed with plasma nitride layers.
Masuda et al. reviewed multiple applications of silicon nitride (SiNx) films prepared through catalytic chemical vapor deposition
(Cat-CVD) as coating, passivation, and insulating films (106). Using Cat-CVD technique, it was found that SiNx films are dense (low
hydrogen content) and have low wet etch rate, low oxygen, low water vapor transmission rate (even when prepared at temperatures
below 300 C), and low stress. Accordingly, SiNx films prepared by Cat-CVD can be appropriately used as coating and passivation
films for electronic devices, mechanical parts, and plastic films. Clearly, SiNx films prepared by Cat-CVD can also be utilized as
insulating films used in ultralarge-scale integrated circuits and thin-film transistors.
Moene et al. investigated coating process of activated carbon with silicon carbide through CVD (112). The main objective of their
work was to improve the oxidation resistance and the mechanical strength of the activated carbon extrudates. To analyze oxidation
resistance, thermal gravimetric analysis was performed in air. Besides, the temperature at the maximum rate of oxidation (Tmax) was
applied to compare the modified carbons. According to the findings of this work, it was not feasible to reach selective deposition of
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SiC by reacting SiCl4 with the carbon surface below 1400 K. In all cases, silicon deposition was encountered. The activated carbon
was coated by a CH/SiCl mixture and SiC deposition was developed at 1376 K. Then, oxidation resistance of this modified activated
carbon was improved by 150 K (Tmax ¼ 1025 K), while the side crushing strength improved by a factor 1.7. Here, the residual surface
area was calculated as 176 m2 g1. SiC coatings were also developed through decomposing CH3SiCl3 at temperatures above 1200 K.
In addition, side crushing strength of the extrudates was promoted by a factor of 1.4, while the resistance against oxidation remained
similar compared to the original carbon. The residual surface areas and pore volumes were 530 m2 g1 and 0.33 ml g1 on an
average, respectively. Using both methods of SiC deposition, the obtained surface areas were high enough for catalyst support
applications. Based on infiltration performance evaluation of this SiC-CVD process by CH3SiCl3, it was found that 20–95% of the
SiC has been deposited inside the extrudates. The residual porosity of the extrudates can be assessed by a general mathematically
developed chemical vapor infiltration design chart, which correlates initial Thiele moduli with the porosity after deposition.
Park and Kim deposited TiN-based hard coating layers on steel substrate at 500 C through a plasma-enhanced chemical vapor
deposition (PECVD) technique (111). They also conducted comparative evaluation of microhardness, microstructure, and oxidation
behavior among TiN, Ti–Al–N, and Ti–Si–N coating layers by PECVD. Adding even a small share of Al or Si to TiN highly affects
improvement in both microhardness and oxidation resistance of TiN film. Microhardness values of Ti–Al–N and Ti–Si–N, were
noticeably enhanced in comparison to those of TiN because of microstructural modification of TiN by adding Al or Si. These
microstructural modifications are mainly grain size refinement and the mixed crystallographic orientation of the grains. While TiN
film initiates to oxidize from 500 C, Ti–Al–N and Ti–Si–N coating layers indicated much improved oxidation resistance up to 700 C.
According to this work, amorphous aluminum oxide and silicon oxide phases developed at the initial oxidation stage for Ti–Al–N and
Ti–Si–N, respectively, highly retard their further oxidation. Compared to Ti–Al–N and Ti–Si–N, Ti–Si–N coating layer indicated more
desired mechanical properties at moderate temperature, while Ti–Al–N is highly advantageous in the resistance property against high-
temperature oxidation. Figure 5 shows plane view micrographs by TEM of different films with their electron diffraction patterns.
Kim et al. deposited a multilayer of TiN–TiC on mainly utilized die steels (D2) through pulsed DC plasma-assisted chemical
vapor deposition (see Figure 6) (72). They successfully deposited TiC layer at 580 C using a gas mixture of TiCl4, CH4, H2, and Ar.
Here, to minimize the excess carbon phases and chlorine content in the TiC-deposited layer, a minimum flow of TiCl4 (3.5 g h1)
and CH4 gas (18–20 sccm) was applied. To produce dense TiC films with minimum excess carbon phases and low chlorine content
(below 2.5 at.%), it is required to apply a gas volume ratio of TiCl4/CH4 in the range of 0.34–0.38. According to this work, Ti/C ratio
Figure 5 Plane view micrographs by transmission electron microscope of (A) TiN, (B) Ti–Al–N, and (C) Ti–Si–N films and their respective electron
diffraction patterns (a, b, c). Reproduced from Park, I. W.; Kim, K. H. Coating Materials of TiN, Ti-Al-N, and Ti-Si-N by Plasma-enhanced Chemical
Vapor Deposition for Mechanical Applications. J. Mater. Process. Technol. 2002, 130–131, 254–259.
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Figure 6 Schematic drawing of the PACVD system. Reproduced from Kim, D. J.; Cho, Y. R.; Lee, M. J.; Hong, J. M.; Kim, Y. K.; Lee, K. H. Properties of
TiN-TiC Multilayer Coatings Using Plasma-assisted Chemical Vapor Deposition. Surf. Coat. Technol. 1999, 116–119, 906–910.
of the densest film was measured as about 1.11. This value well corresponds to the substoichiometric carbon composition of
46 at.%, measured by Rutherford backscattering spectrometry (RBS) and Auger electron spectroscopy. This finding indicates that
a single phase of TiC can be developed near a substoichiometric composition, where no extra phases such as carbon and oxide
phases in the TiC layer is present. Moreover, using RBS measurement, the presence of the oxide phase in the TiC layer deposited with
low methane gas flow was proved.
Bertran et al. applied CVD using modulated RF plasma to obtain ceramic nanometric multilayer structures of nanostructured
particles of SiCx:H layers and amorphous Si films (130). This technique is broadly applied to produce ceramic Si-based nano-
particles (SiCxNy) with unique properties such as spherical morphology, composition, and controlled ultrafine particle size in the
range 2–100 nm. To investigate their structural, mechanical, and surface properties, hybrid multilayer nanostructures of ceramic
coatings containing Si and SiC were prepared. Low densities of crystalline nanoparticles were embedded in a Si matrix during the
growth of these structures and they were, in turn, inserted between amorphous Si layers. High-resolution transmission electron
microscopy and selected area electron diffraction techniques were applied to examine the phase structure, microstructure, and
morphology of the hybrid multilayered films. Then, it was found that nanoparticles are distributed in the multilayered structure of
the films. Using the nanoindentation technique, hardness and Young’s modulus were measured. Besides, the wear properties were
examined through an improved pin-on-disk system. The mechanical properties of the films, hardness, friction, propagation of
cracks, and wear resistance were considerably increased by the presence of the nanoparticles. As some potential applications of these
coatings based on ceramic multilayers one can name production of tough and hard coatings; protective and wear-resistant coatings
for mechanical tools, gears and mechanical parts, optical surfaces, and fibers; corrosion and high temperature-resistant coatings;
plus inorganic membranes, buffer layers for heterogeneous coatings, and coatings with anisotropic properties.
Pierson and Mullendore described an experimental study of CVD of TiB2 through the hydrogen reduction of TiCl4 and BCl3 to
produce very thick (more than 100 mm) and uniform coatings (131). Here, the optimum deposition conditions were determined as
temperature, 900–950 C and source gas ratios, [Ti]/[B] ¼ 1/2 and [H]/[Cl] ¼ 6/1. Deposition rates greater than 25 mm h1 were
obtained under these conditions. Here a very uniform composition with an excess of boron over stoichiometry (probably in the
form of free boron) was obtained. A slight share of chlorine remained in the deposit probably as TiCl2 (0.05 wt.% at 950 C).
The coatings are very hard (about 3700 kgf mm2) and have uniform hardness through the thickness. Through the exact control of
the deposition parameters, it is possible to produce uniform CVD coatings with thickness of 1 mm or more. Kim et al. reported
deposition of titanium carbide (TiC) and titanium nitride (TiN) films on Si3N4–TiC composite cutting tools through CVD using
TiCl4–CH4–H2 and TiCl4–H2–N2 gas mixtures, respectively (132). To figure out the nonmetal to metal ratio of the coated layer at
various deposition conditions, an Auger electron spectroscopy survey was carried out. This ratio increases in the deposits with an
increased mC:Ti (mole ratio of CH4 to TiCl4 in the input) for TiC coatings and mN:Ti (mole ratio of N2 to TiCl4 in the input) for TiN
coatings. It is almost possible to synthesize stoichiometric films with mC:Ti ¼ 1.15–1.61 for TiC and with mN:Ti ¼ 25–28 for TiN.
In addition, it is possible to obtain the maximum microhardness of the coatings in these ranges. Using the Auger depth profile
analysis, an interfacial region was examined between the coated layer and the substrate. According to this analysis, the interfacial
region of TiC coatings on Si3N4–TiC ceramics is wider than that of TiN coatings, implying good interfacial bonding for TiC. Also,
the microstructure and thermal shock resistance of the coated layer were studied. According to the experimental results, TiC coatings
have an equiaxed structure, while TiN coatings involve a columnar structure with a (220) preferred orientation. Finally, TiC coatings
on Si3N4–TiC ceramics have higher resistance to thermal shock compared to the TiN coatings.
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Larsson and Ruppi examined Ti(C,N) coatings produced through moderate temperature chemical vapor deposition (MTCVD)
and then compared them with Ti(C,N) coatings produced by conventional CVD (50). The different Ti(C,N) coatings were studied in
terms of their mechanical properties. According to the findings of this work, the deposited Ti(C,N) coatings had a twinned columnar
microstructure with strong (112) texture. A rough and facetted surface is produced because of large {001} crystal faces. The results of
this work also indicated that MTCVD-coated tools involve higher transverse rupture strength values compared to CVD-coated ones,
because of reduced decarburization of the cemented carbide substrates as well as lower residual tensile stresses. Improved edge
strength was obtained because of the reduced decarburization and the absence of the reversible h-phase reaction.
Holzschuh investigated coatings in the systems Ti–B–N and Zr–B–N since they have high potential in metal cutting (19). Hence,
CVD was applied to deposit TiN, TiB2, TiBN, multilayers like [TiN–TiB2]x or [TiN–TiBN]x (x ¼ 3–100), ZrN, and ZrBN coatings on
cemented carbides. Once the boron content is maintained above 5 wt.% TiBN, the coatings resulted in mixtures of TiN and TiB.
Here, by varying deposition temperatures and gas flows in the CVD process, it was possible to control TiN/TiB2 ratio, microstructure,
hardness, and wear resistance of the coatings. In comparison to TiN and TiB2 coatings, deposition rates in TiBN coatings
were significantly higher. At moderate deposition temperatures (700–900 C), TiBN coatings indicated high hardness values (HV
3500–5000). Using deposition temperatures below 900 C, it was allowed to successfully suppress boron diffusion and formation
of a CoWB phase on the surface of the cemented carbide tool. Because of applying moderate deposition temperatures, TiBN coatings
indicated very good adhesion. Here, boron diffusion was detected as the factor responsible for poor adhesion in TiB2 coatings. To
perform milling tests in TiN, TiB2, TiBN, multilayer coatings like [TiN–TiB2]x or [TiN–TiBN]x with a TiB2 content of 10–95%, ZrN,
and ZrBN were investigated. All TiBN coatings indicated appropriate wear resistance against abrasion. According to the observations
of this work, the TiBN coatings suppressed thermal cracks at a certain level of the TiN/TiB2 ratio. Despite high resemblance between
Zr–B–N and Ti–B–N systems, the results demonstrated differences in deposition chemistry and properties.
Jarms et al. deposited wear-resistant Ti1xAlxN hard coatings using different compositions (0 x 1) through DC plasma-
assisted chemical vapor deposition on HSS (133). They used TiCl and AlCl as metal precursors and then examined the effect of
AlCl partial pressure on coating properties. According to the findings of this work, aluminum content rises in the coating in a linear
mode with AlCl partial pressure. Then, microhardness of the Ti1xAlxN coatings was estimated as 2000 HV0.01 for samples with low
aluminum contents (x < 0.5), while it decreased down to 1300 HV0.01 for samples with higher aluminum contents. According to the
scratch test, adhesion decreases once aluminum content increases. There is an fcc structure in the coatings up to an aluminum
content of x ¼ 0.8. For x > 0.8, a weak (201) peak of the hexagonal Wurtzite structure was observed. Nevertheless, the Wurtzite
structure is confirmed only for x ¼ 1. Also, oxidation tests were performed in air at 873 K. According to XPS depth profiles, a better
oxidation resistance of Ti1xAlxN compared to TiN was seen. Here, oxidation resistance enhances, while aluminum content rises.
During the oxidation process, the aluminum content indicates an increase near the surface of Ti1xAlxN coatings. Also, it was found
that the aluminum atoms diffuse up to the surface. Jayaraman et al. produced hard, dense, and conformal hafnium diboride (HfB2)
thin films through CVD technique from the precursor Hf(BH4)4 at deposition temperatures below 350 C (34). As-deposited films
were amorphous; then, they were transformed to a nanocrystalline structure after being annealed at 700 C. It was found that the
amorphous HfB2 films involve an appropriate hardness of 20 GPa and their hardness enhanced in the nanocrystalline state to
40 GPa. Also, ternary Hf–B–N films, consisting of a mixture of HfB2, HfN, and BN, were obtained by adding atomic nitrogen to the
growth flux (see Figure 7). Producing the softer a-BN phase resulted in a drop in the hardness and modulus values. Finally,
a multilayer HfB2/Hf–B–N indicated a proper combination of high hardness (33 GPa) and low elastic modulus (300 GPa).
Jedrzejowski et al. investigated the mechanical properties of nanocomposite TiN/SiN1.3 films, where the concentration of the SiN1.3
component was changing (134). According to the findings of this work, the TiN/SiN1.3 materials behave as a two-phase material. As
a matter of fact, such an alloying effect can be avoided, because the film properties, in particular H and E, do not follow the mixture
rule. Moreover, significant changes in the material’s performance are induced by a small change in the microstructure. The meth-
odology and the interpretation of the mechanical measurements, i.e., hardness and Young’s modulus, were investigated. Then,
a quantitative comparison between the results from depth-sensing indentation (DSI), using the Oliver and Pharr model, and those
who have taken into the account the work of plastic and elastic deformation and different models considering the indentation size
effect was done. As conclusion, it was found that once these approaches are applied correctly, they can yield comparable values within
approximately 10%. In the next part, the mechanical behavior and microstructure of the nanocrystalline (nc)-TiN/SiN1.3 films was
systematically studied. Here, for an optimum concentration of Si (5–10 at.%), high values of microhardness (25 and 45 GPa) and
Young’s modulus (270 and 350 GPa) were obtained for the films deposited at 300 and 500 C, respectively. For the individual TiN
(H w 22 GPa, E w 200 GPa) and SiN1.3 (H w 18 GPa, E w 160 GPa) materials, these values seem to be substantially higher. Here, the
film behavior was described by a phenomenological model based on a system in which TiN nanocrystals of a constant size (w8 nm)
are embedded in an SiN1.3 matrix. The highest values of H are obtained on optimizing the interparticle distance (1–2 nm); this in turn
coincides with a maximum in the film toughness and total compressive stress. Furthermore, it was found that the surface roughness
decreases from w5.2 nm for TiN to w2.0 nm for 50% TiN/50% SiN1.3. Since nc-TiNySiN1.3 films possess very attractive mechanical
properties, the authors of this work are now encouraged to concentrate on a detailed investigation of the tribological and optical
characteristics in terms of their metallurgical, protective, decorative (optical), and other applications.
Thanks to their microstructure and chemical bonding, the individual hard thin-film materials such as TiN, SiN1.3, SiC, and CNx
indicate very interesting mechanical, tribological, optical, and electronic properties. Jedrzejowski et al. studied the properties of
such materials (135). Quaternary thin films prepared by PECVD from TiCl4/SiH4/N2/CH4 mixtures with different concentrations
of CH4 were systematically studied. It can be claimed that a TiCxNy/SiCN nanocomposite structure is developed in the coatings.
Moreover, based on DSI, static indentation, and curvature measurements carried out on samples prepared under optimal
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Figure 7 XPS spectra of (a) Hf4f and B 1s peaks from the HfB2 and Hf–B–N films and (b) N 1s peak from the Hf–B–N film. See text for detailed
interpretation. Reproduced from Jayaraman, S.; Gerbi, J. E.; Yang, Y.; Kim, D. Y.; Chatterjee, A.; Bellon, P.; Girolami, G. S.; Chevalier, J. P.; Abelson, J. R.
HfB2 and Hf-B-N Hard Coatings by Chemical Vapor Deposition. Surf. Coat. Technol. 2006, 200, 6629–6633.
conditions, hardness of 55 GPa, reduced Young’s modulus of 302 GPa, compressive stress of 2.0 GPa, elastic rebound above 80%,
H3/Er2 coefficient of 1.8 GPa, and high toughness value was observed. Besides, the friction coefficient and the wear rate measured
against diamond were 0.13 106 and 12 106 mm3 Nm1, respectively. They compared the properties of these nano-
composite TiCxNy/SiCN coatings with the performance of PECVD films from their earlier studies and found that these include TiN/
SiN1.3 nanocomposites and SiCN, for which they obtained a hardness of 45 and 33 GPa and a reduced Young’s modulus of
350 and 200 GPa, respectively.
Karvankova et al. reproducibly deposited and characterized superhard nanocomposite nc-TiN/a-BN and nc-TiN/a-BN/a-TiB2
coatings with hardness of 40–50 GPa in terms of their phase composition, nanostructure, thermal stability, oxidation resistance,
and mechanical properties (71). They applied high-frequency plasma CVD at a total pressure of several millibars with TiCl4, BCl3,
N2, and H2 as reactants. In comparison to the earlier studied systems of nc-MnN/a-Si3N4 (M ¼ Ti, W, V) and nc-TiN/a-Si3N4/a- and
nc-TiSi2, the maximum hardness of the nc-TiN/a-BN and nc-TiN/a-BN/a-TiB2 coatings was obtained at the percolation threshold in
the presence of about one monolayer of thin continuous tissue of a-BN between the TiN nanocrystals. The thermal stability
and oxidation resistance of these coatings were found to be fairly high, although being lower than that of the nc-TiN/a-Si3N4 and
nc-TiN/a-Si3N4/a-TiSi2 coatings.
Now, boron nitride coatings deposited by CVD are increasingly utilized as an interface material for SiC/SiC composites. Nyutu
et al. examined CVD of BN through statistical design of experiments approach (136). Here, a two-level screening design (Plackett–
Burman) was employed to determine the most significant parameters for the process. The most significant controlling factors of
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coating thickness were found as deposition pressure, gas mixture dilution factor, deposition time, and the reaction gas flow ratios.
A three-level surface response design (Box–Behnken) was employed to optimize the deposition process, as well as to produce
a predictive mathematical model of the process. According to the generated response surface modeling, deposition time had the
greatest effect on coating thickness. Moreover, temperature–time and temperature–NH3/BCl3 interactions may be large at low/high
NH3/BCl3 ratios and high deposition time, respectively. Moreover, the tensile strength was strongly influenced by the deposition
temperature and deposition time. The response model indicated that tensile strength depends on the coating thickness, NH3/BCl3
gas flow ratios, and time. Based on model interaction plots, a very clear dependence of temperature–gas flow ratio on tensile
strengths of BN-coated SiC fibers can be observed.
Stanishevsky et al. deposited ternary B–C–N amorphous and crystalline coatings by applying microwave CVD using a mixture
of NH3, CH4, B2H6, and H2 gases at substrate temperatures in the range 800–13 508 C, as well as a gas pressure in the range
(9.012) 103 Pa (137). They studied the effect of deposition conditions – including gas composition, substrate temperature,
and material – on the coating structure, chemical composition, and surface morphology. They deposited both amorphous and
polycrystalline coatings. Here, the amorphous coatings were usually developed at lower substrate temperatures and were
nonhomogeneous across the coating thickness. In their study, the nanocrystalline inclusions of boron carbide, boron nitride, and
diamond were observed in amorphous B–C–N compounds. Polycrystalline coatings were noticeably represented by both dia-
mond and boron nitride phases. In one case, a polycrystalline coating with B2CN4 composition was synthesized. It is possible to
produce both amorphous and polycrystalline nonhomogeneous B–C–N deposits using microwave plasma-assisted chemical
vapor deposition through a mixture of B2H6–NH3–CH4–H2 gases. The chemical and phase composition of the coatings, as well as
their structure and surface morphology, are strongly controlled by deposition conditions and substrate position. Here, various
phases are typically present in the coatings, e.g., boron-doped diamond polycrystalline phase detected in several B–C–N coatings.
Through the higher substrate temperatures it is possible to obtain a larger amount of polycrystalline phase in the coatings. To date,
it has not been possible to prepare homogeneous polycrystalline B–C–N through this technique. However, now CVD allows
synthesis of rather uniform, amorphous B–C–N coatings of various chemical compositions.
Arai et al. deposited TiC coatings on M2 steel and pure iron at temperatures below 550 C by applying a DC glow discharge
method by a device similar to the conventional apparatus utilized for ion nitriding of steel (62). The micro-Vickers’ hardnesses of
the coatings with chlorine content below 5 wt.% were determined as 2000 and 3000 for TiN and TiC, respectively, where the
hardness reduced by increasing chlorine content. In addition, the hardness of the TiC coatings was reduced by the excess carbon.
The corresponding XRD patterns for the NH4Cl were observed for the TiN coatings in which the chlorine content exceeded about
10 wt.%. A rolling test with slip indicated that the adhesion strength of these hard coatings is higher than that of the TiN coatings
developed through ion plating technique. A comparison between these two kinds of coatings demonstrates that the TiC coatings are
more adherent compared to the TiN coatings. Besides, these coatings involve a remarkable resistance to wear and galling, as high as
that of other hard coatings produced by other methods such as ion plating, CVD, and salt bath immersion. Jung-Tae Ok et al.
synthesized Ti–B–C coatings on WC–Co and Si wafer substrates through PECVD technique using a gaseous mixture of TiCl4, BCl3,
CH4, Ar, and H2 (86). Figure 8 shows schematic diagram of the PECVD system used. Here, the boron content was varied in a wide
range from TiC to TiB2 and microstructure and then a systematic investigation was conducted to study mechanical properties of
synthesized Ti–B–C coatings. Through the instrumental analyses conducted, the synthesized Ti–B–C coatings were determined as
composites containing nanocrystallites TiC, quasi-amorphous TiB2, and amorphous carbon at low boron content; contrarily, they
consist of nanocrystallite TiB2, quasi-amorphous TiC, and amorphous carbon at relatively high boron content. As the boron content
rises, microhardness of the Ti–B–C coatings increased from w23 GPa of TiC to w38 GPa of Ti0.33B0.55C0.11 coatings. The
Ti0.33B0.55C0.11 coatings were found to have lower average friction coefficient (i.e., 0.45). However, they indicated relatively better
wear behavior compared to other binary coatings of TiB2 and TiC.
Figure 8 Schematic diagram of the PECVD experimental apparatus. Reproduced from Ok, J. T.; Park, I. W.; Moore, J. J.; Kang, M. C.; Kim, K. H.
Syntheses and Mechanical Properties of Ti-B-C Coatings by a Plasma-enhanced Chemical Vapor Deposition. Surf. Coat. Technol. 2005, 200, 1418–1423.
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Materials in the Si–C–N system indicate excellent properties for wear protection applications as well as an excellent thermal
shock resistance even at high temperatures. Since these materials have no melting point, coatings must be synthesized. Among the
commonly applied techniques, the conventional CVD processes involve the disadvantage of low deposition rates. Among the gas-
phase synthesis processes, thermal Plasmajet CVD processes with liquid feedstock demonstrate the highest deposition rates. Wilden
et al. successfully applied single and triple DC and HF torches with supersonic nozzles to produce Si–C(–N) coatings on various
steel, aluminum, titanium and, copper alloys, as well as on graphite (89). They also used chlorosilanes, hexamethyldisiloxane,
tetramethyldisiloxane, and hexamethyldisilazane as liquid single precursors. Deposition rates up to 1500 mm h1 were achieved.
The coatings indicated cauliflower, columnar, or dense morphology plus an amorphous or nanocrystalline structure. Application of
chlorosilanes always results in chlorine-containing coatings. The chlorine leads to severe to mild corrosion in the interface and
carbon steel substrates. The processes are compared, considering their characteristics related to the injection modes, gas temperature,
and velocity profiles calculated via enthalpy probe measurements. The process conditions are correlated to the coating micro-
structure and then the adhesion to the substrates and guidelines for the optimum synthesis of Si–C–N coatings by Plasmajet CVD
are deduced. Moreover, emission spectroscopy is utilized to determine coating-formation mechanisms. Finally, the evidences of full
dissociation of the liquid feedstock in the plasma jet were proved.
7.05.9.1.3 Oxide Coatings

Burriel et al. deposited cobalt oxide films through pulsed injection metal–organic chemical vapor deposition (PI-MOCVD)
(see Figure 9) (138). To do so, they used toluene-dissolved Co(acac)3 (acac ¼ acetylacetonate) precursor. Besides, they investigated
the structure, morphology, and growth rate of the layers deposited on silicon substrates as a function of deposition temperature.
They detected pure Co3O4 spinel structure as a good candidate for deposition temperatures ranging from 360 to 540 C. Here, the
optimum experimental parameters for dense layer preparation as well as a high growth rate was determined and applied to prepare
corrosion-protective coatings for Fe–22Cr metallic interconnects, utilized in intermediate-temperature solid oxide fuel cells. The
layers deposited at temperature range of 360–500 C have crystal quality and preferred orientation. Also, the dense films with more
than 1 Am h1 growth rate have been prepared on flat (silicon) and rough substrates (Fe–22Cr) at 500 C. Other studies are
underway to characterize the efficiency of the cobalt layer as protection against corrosion.
Dumitrescu et al. deposited Al coatings through MOCVD at 573 K. To do so, they used tri-isobutyl aluminum as precursor on
FeCrNi- and FeCr-type SS substrates (139). They investigated in situ surface treatments of the substrates by TiCl4 vapor prior to
MOCVD of Al to promote nucleation density of the Al films and, as a result, to improve their surface morphology and compactness.
Figure 9 Schematic representation of the PI-MOCVD setup. Reproduced from Burriel, M.; Garcia, G.; Santiso, J.; Hansson, A. N.; Linderoth, S.;
Figueras, A. Co3O4 Protective Coatings Prepared by Pulsed Injection Metal Organic Chemical Vapour Deposition. Thin Solid Films 2005, 473, 98–103.
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They synthesized the desired b-FeAl compound as a main layer on the substrates by further thermal treatment at 923 K of Al-coated
samples under inert atmosphere (He), while at lower temperature, the intermetallic phase Fe2Al5 is mainly created. Through
annealing in the CVD reactor at 923 K under oxygen atmosphere, Al2O3 was produced as an outer layer on the Fe–Al diffusion
coatings. Al2O3 films were dense, uniform, and adherent under such conditions and demonstrated the cubic structure of the low-
temperature alumina phases. Such protective coatings were characterized by various techniques and their structure is discussed as
a function of this combined process conditions. Nable et al. coated aluminum oxide thin films on nickel substrates through the CVD
(140). They synthesized aluminum oxide via pyrolysis of a metal acetylacetonate precursor. The reaction was carried out at rather
low temperatures, ranging from 435 to 550 C to produce a thin film of aluminum oxide. The created coating was resistant to
isothermal oxidation at high temperatures. This resistance to oxidation was true for all of the coated substrates. However, the surface
morphology varied when it was heated for a long time. The samples coated at temperatures of 500 C and 550 C were effective up
to 900 C, while those coated at 435 C were good up to 800 C.
Bertrand et al. presented a novel process of microwave PECVD to produce TBCs that contain yttria partially stabilized zirconia
(141). They designed and realized a reactor at Onera to provide an alternative technique to the currently applied processes for TBC
deposition on gas turbine airfoils. It was noticed that it is possible to deposit zirconia coatings with columnar structure at a high rate
(up to 5 mm min1) that meets production requirements. The plasma study through optical emission spectroscopy resulted in
identification of the reactive species and determination of plasma distribution and location regarding factors such as gas flow and
the reactor chamber geometry. Here, it is possible to conduct a systematic study to determine the effects of operating parameters on
the structure, morphology of the coatings, and deposition rate. Figure 10 shows schematic representation of the MPECVD reactor.
Experimental conditions were determined where they allowed deposition of columnar zirconia coatings with rather high growth
rates, in the order of 120–150 mm h1. Such rates are ideal for the envisaged industrial application. The substrate temperature can be
below 1073 K. Since the coatings were highly porous, they can present a low thermal conductivity, with a thin dense layer in contact
with the MCrAlY substrate. According to the plasma analysis, a reaction mechanism has been proposed for the development of
zirconia coatings. However, further work is required to confirm it, particularly through in situ analysis.
Over the past decade, an increase in number of bone fractures incidence was reported by increase of elderly population.
Therefore, the improvement of the implant–bone interface is considered as an open problem. Recently, MOCVD has been
proposed as a new approach for coating orthopedic and dental prostheses with metal nanostructured oxide films either via
decomposition of oxygenated compounds (single-source precursors) or the reaction between oxygen-free metal compounds and
oxygenating agents. Giavaresi et al. evaluated in vivo biocompatibility of commercially pure Ti control material: TI/MA implants
(þ2 mm–5 mm length), which are coated by nanostructured TiO2 films by MOCVD (Ti/MOCVD), and then inserted into rabbit
femoral cortical (mid-diaphysis) and cancellous (distal epiphysis) bone (142). Also, histomorphometric, ultrastructural, and
microhardness investigations were conducted (see Figure 11). A significant (p < .0005) increase in Al of Ti/MOCVD implants was
Figure 10 Schematic representation of the MPECVD reactor. Reproduced from Bertrand, G.; Mevrel, R. Zirconia Coatings Realized by Microwave
Plasma-enhanced Chemical Vapor Deposition. Thin Solid Films 1997, 292, 241–246.
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Figure 11 Histology of implants in the distal epiphysis ((a) Ti/MA and (b) Ti/MOCVD) and in the diaphysis ((c) Ti/MA and (d) Ti/MOCVD) of
rabbit femur at 4 weeks, showing bone apposition around the implants (fast green and acid fuchsin, original magnification 5). Regular
architectural pattern of the cancellous and cortical bone surrounding the implants without connective capsule or gaps. Reproduced from Giavaresi, G.;
Ambrosio, L.; Battiston, G. A.; Casellato, U.; Gerbasi, R.; Finia, M.; Aldini, N. N.; Martini, L.; Rimondini, L.; Giardino, R. Histomorphometric,
Ultrastructural and Microhardness Evaluation of the Osseointegration of a Nanostructured Titanium Oxide Coating by Metal-organic Chemical Vapour
Deposition: An In Vivo Study. Biomaterials 2004, 25, 5583–5591.
observed 4 and 12 weeks after surgery in comparison to Ti/MA implants. According to bone microhardness results, a significant rise
for the Ti/MOCVD versus Ti/MA implants at 200 mm in the femoral diaphysis (4 weeks ¼ 14.2, p < 0.05) and distal femoral
epiphysis (12 weeks ¼ 14.5, p < 0.01) at 4 and 12 weeks was shown, respectively. As conclusion, the current findings indicate that
the nanostructured TiO2 coating has a positive influence on the osseointegration rate of commercially pure Ti implants and bone
mineralization at the bone–biomaterial interface in both cortical and cancellous bone.
Goto and Kimura prepared oxide thick films, partially YSZ, and titania (TiO2) using LCVD (see Figure 12) (143). Using the laser
is a considerable contribution to increase the deposition rate for YSZ and TiO2 films up to 660 and 2500 Am h1, respectively. This
increase in the deposition rate is simultaneous with plasma formation around the deposition zone. Here, the plasma was observed
over critical values of laser power and substrate preheating temperature. Controlled by deposition conditions, a wide range of film
morphologies from featherlike columnar to dense microstructures were obtained. A large amount of nanopores at columnar
boundary and inside grains were observed in the columnar structure (see Figures 13 and 14). These columnar structure and
nanopores involve various benefits for applying YSZ films to thermal barrier coatings.
Martinet et al. deposited silicon dioxide and titanium dioxide films at low temperature (18). During deposition process,
the plasma reactor was equipped with an in situ spectroscopic ellipsometer in order to control the thickness and refractive index.
A double-film antireflection coating was prepared and then a UV–visible near-IR spectrometer was applied to measure reflectance
values. Deposition of SiO2 and TiO2 films at low temperature by PECVD can be considered as a promising technique to synthesize
antireflection coatings for solar cells. Nagel et al. introduced an innovative antireflection coating technology for photovoltaic
modules based on remote PECVD of porous SiO2 films (64). The proposed technology is potentially capable of significantly
improving the performance of photovoltaic modules through an effective reduction of the optical losses of the air/glass interface.
The findings of this work indicated an increase in transmission of a glass pane measured at a single wavelength from 91.7% to 100%
using a single-layer porous SiO2 antireflection coating on both sides of the glass pane. In addition, the transmission weighted with
the AM1.5G spectrum in the 400–1150 nm wavelength region was enhanced from 91.6% to the considerably high value of 99.4%
through a double-layer porous SiO2 antireflection coating on both sides of the glass pane.
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Figure 12 Schematic diagram of LCVD apparatus. Reproduced from Goto, T.; Kimura, T. High-speed Oxide Coating by Laser Chemical Vapor
Deposition and Their Nano-structure. Thin Solid Films 2006, 515, 46–52.
Figure 13 Cross-section of YSZ films prepared at (a) IL ¼ 2.04 105 W m2 and Tsub ¼ 893 K, (b) IL ¼ 3.06 105 W m2 and Tsub ¼ 953 K,
(c) IL ¼ 2.04 105 W m2 and Tsub ¼ 1123 K, and (d) IL ¼ 5.09 105 W m2 and Tsub ¼ 1213 K (IL, laser light intensity). Reproduced from
Goto, T.; Kimura, T. High-speed Oxide Coating by Laser Chemical Vapor Deposition and Their Nano-structure. Thin Solid Films 2006, 515, 46–52.
Duverneuil et al. deposited SnO2 coatings through MOCVD on Ti plates using SnEt4 and O2 as reactive gas mixture (144). Here,
the growth conditions were responsible for controlling the thickness, morphology, and microstructure of these coatings. They tested
the deposition process for Ti/IrOx/SnO2 electrode preparation and was also tested for the anodic oxidation of organic pollutants in
industrial wastewater. A remarkable overpotential for oxygen evolution and an appropriate efficiency for the elimination of total
organic carbon from wastewater were found for these electrodes. Moreover, the electrochemical impedance measurements were
carried out to specify the activity of the interface SnO2/aqueous media as a function of time during the oxidation process. Here, the
main drawback resulting in electrode failure is the irregularity of the IrOx underlayer. A good uniformity of CVD SnO2 coatings was
reported, indicating an appropriate conformal-coverage of the surface roughness. Nevertheless, the applied dip coating process for
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Figure 14 Nanostructure of YSZ film prepared at IL ¼ 4.07_105 W m2 and Tsub ¼ 1200 K (a) near the film surface, (b) at the middle of the film,
and (c) near the substrate. Reproduced from Goto, T.; Kimura, T. High-speed Oxide Coating by Laser Chemical Vapor Deposition and Their
Nano-structure. Thin Solid Films 2006, 515, 46–52.
IrOx deposition does not allow a uniform overage of the surface roughness. Accordingly, the IrOx underlayer can be preferentially
deposited in the pits and concave zones of the substrate surface, while the prominences and tips are left uncoated. In such uncoated
zones, TiO2 is formed by progressive chemical and anodic oxidation of the Ti substrate. The electrode is irreversibly deactivated by
this insulator oxide. No significant influence of SnO2 film thickness on electrode behavior was noticed. However, the optimal value
is in the range of 2–5 mm since microcracks were not observed for as-prepared thicker films, maybe due to thermal stresses.
In addition, it is worth to mention that SnO2 film deposition temperatures above 653 K are not suitable because the growth tends to
be columnar. This enhances the risk of open porosity toward the interface and, in turn, oxidation of the Ti substrate.
7.05.9.1.4 Polymeric and Other Types of Coatings

Ceramic coatings are excellent alternatives for protection of the metallic structures working at high temperatures. Mullite is
a suitable ceramic for this purpose due to the fact it offers very good mechanical properties, great corrosion resistance, high thermal
resistance, and high durability. Here, CVD deposition by fluidized bed reactor (CVD-FBR) is considered as an interesting approach
to develop thin and adherent protective films on metallic surfaces. Moreover, this technique involves low costs and is easy to apply.
As the first stage for mullite synthesis, the coatings are developed by codeposition of aluminum and silicon coatings through
CVD-FBR. Then, thermodynamic calculations are carried out before the experiments for system investigation and optimization of
the working conditions. These depositions are formed in a fluidized bed reactor. The base material applied for this purpose is
a commercial AISI 304 SS. This technique is based on the reaction between aluminum chloride (AlCl3 (g)) and silicon chloride
(SiCl4 (g)). Perez et al. studied optimization of the deposition conditions including deposition temperature, time, fluxes, etc (145).
Besides, further oxidation of these precursor coatings is made to achieve the definitive system of a protective ceramic layer. In order
to obtain the best mullite structure, the coated samples were oxidized at different temperatures and times. CVD-FBR is an efficient
tool to develop protective coatings for materials that operate at high temperatures. The initial results obtained for Al–Si codepo-
sition on AISI 304 SS substrates of mullite formation was possible only on carrying out the assays at high temperature. Accordingly,
there must be an optimum of fluxes/temperature/time that allows formation of a protective, effective coating. This initially
developed coating should be oxidized later to create the mullite film that provides better protection to the corrosion at high
temperatures and better mechanical resistance. Finally, the oxidation assays performed can produce the rough idea of the oxides
formed. However, it is required to perform a comprehensive study of this oxidation.
In order to develop aluminide diffusion coatings on iron, nickel, and cobalt through pack cementation and CVD, it is required to
perform a number of similar steps. Among these steps, the slowest ones are transport of aluminum-bearing species from the vapor
phase to the substrate using gas-phase diffusion process and solid-phase diffusion of aluminum into the substrate for formation of
the aluminide phases. The former process enhances surface concentration of aluminum in the coating, while the second one
decreases it. This process modeling is based on the observation that the surface composition of the coating is inclined to reach a steady
state value in a short time after process initiation. At this stage, these two processes have equal rates. However, once producing the
iron aluminide coatings by applying LPCVD, the transport rate of aluminum to the substrate is much faster compared to that of the
solid-phase diffusion of aluminum into the iron substrate. This is due to the fact that the diffusion coefficients of the vapor species are
inversely proportional to pressure; besides, the diffusion layer thickness noticeably decreases at low pressures. Under this condition,
the vapor transport no longer determines the rate and the aluminide coating composition is controlled by the kinetics of solid-phase
diffusion. John et al. developed a model that explains the kinetics of the process, surface composition, and concentration profile of
the coating (44). Figure 15 shows optical micrographs of the transverse sections of the CVD aluminide coatings produced at different
substrate temperatures. Coating thickness decreases with a decrease in substrate temperature, due to slower diffusion.
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Figure 15 Optical micrographs of the transverse sections of the CVD aluminide coatings produced at substrate temperatures of (a) 1323 K, (b) 1273 K,
(c) 1223 K, and (d) 1173 K. Reproduced from John, J. T.; Kale, G. B.; Bharadwaj, S. R.; Srinivasa, R. S.; De, P. K. A Kinetic Model for Iron
Aluminide Coating by Low Pressure Chemical Vapor Deposition: Part II. Model Formulation. Thin Solid Films 2004, 466, 331–338.
John et al. investigated kinetics of formation of iron aluminide diffusion coatings by CVD on pure iron in the temperature range
1173–1373 K (45). They used AlCl3 vapor, produced by the sublimation of anhydrous aluminum chloride, to transport aluminum
from an aluminum source (pure aluminum) in the CVD reactor to the substrate to produce the coating. In the first stage, they
developed a theoretical model for the coating process by establishing process kinetics through monitoring the weight gain and
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thickness as a function of time and temperature. The growth process was based on a parabolic rate law where the rate constant
(by weight gain) was steadily increasing with substrate temperature from 0.0114 mg2 cm4 s1 at 1198 K to 0.0836 mg2 cm4 s1 at
1348 K. The rate constants were 4.138 106 and 6.554 106 mm2 s1 (by thickness) at substrate temperatures 1273 and 1323 K,
respectively. Besides, activation energy for the coating process was determined as 211 8 kJ mol1.
Basu et al. deposited dense, uniform, mullite coatings through CVD on SiC substrates (146). The typical coating microstructure
involves a thin layer of nanocrystallites of Al2O3 in vitreous silica at the coating–substrate interface, with columnar mullite grains
above this interfacial layer. The composition of the coating was graded in a way that its outer surface was highly rich with alumina.
The variations in the coating microstructure with processing parameters were discussed. Also, mullite potentials to incorporate such
large composition variations was discussed using the vacancy formation; as the Al/Si ratio rises, these vacancies order, which results
in changes of lattice parameters. Domains’ formation was studied through measuring the distances between superlattice spots in
electron diffraction patterns. The growth rate of the coatings was the fastest when the stoichiometric Al/Si ratio of 3 was applied.
Once the annealing process was applied, nanocrystalline region were transformed into mullite. This process was accompanied by
a structural conversion from tetragonal to orthorhombic from. Also, the structure of the Al-rich mullite grains was evaluated by
electron diffraction. Because of oxygen vacancies ordering along the b-axis, the structure converted from orthorhombic to tetragonal
once the Al/Si ratio is increased. Furthermore, the superlattice spots were observed in the [010] diffraction pattern of mullite, which
implies formation of the domains. Some of the largest domain sizes ever reported can be attributed to the more efficient atomic
mobility by surface diffusion during coating growth.
Binions et al. performed APCVD of tin phosphide thin films on glass substrates (94). To do so, they used the reaction of SnCl4 or
SnBr4 with RxPH3x (R ¼ Cychex or phenyl) at 500/600 C. These coatings indicated appropriate uniformity and surface coverage.
Besides, they were reasonably adherent since they passed the Scotch tape test. The films were highly opaque and had regions of
birefringence. Besides, based on XRD tests the films were amorphous. The energy-dispersive X-ray analysis and electron probe
studies yielded elemental ratios that were consistent. They indicated ignorable tin-rich and stoichiometric films, with slight chlorine
or bromine incorporation (SnP1.33/SnP0.40). No Raman scattering was seen. Also, the measurements performed through sheet
resistance showed that the films are insulating. CVD is an excellent technique to coat complex substrates such as fibers or inner
surfaces of the tubes. Nevertheless, the main disadvantage of CVD is its need for high coating temperatures, which prevents applying
coating on temperature-sensitive materials such as polymers, namely, those with titanium-based layers. Breme et al. developed
a novel plasma-assisted process to coat polymers at very low temperatures with titanium-based layers (116). The coating
temperature could be lowered to approximately 60 C (140 F), so it was made possible to coat a variety of different polymers
without undesired damage. The researchers used PET, polyethersulfone, polyvinylchloride (PVC), polytetrafluoroethylene, poly-
ethylene, and polypropylene. Here, using the tensile tests, it was found that the very smooth (Ra ¼ 3 nm) and thin (5–100 nm)
layers have a very good adherence (>10 N mm2). It is possible to show that all kinds of geometries such as tubes or textile
structures are allowed to be coated by this technique. The coating involves significant potential to improve biocompatibility and
blood compatibility of polymers in medical apparatuses. An evidence for this claim might be the significant higher cell vitality and
growth of the cells on Ti(C,N)-coated polymers compared with uncoated polymers using fibroblasts and endothelial cells.
Moreover, the coagulation of blood is less affected if polymers are coated with the Ti(C,N) layers. Besides, it is possible to show that
Ti(C,N)-coating is an effective diffusion barrier to prevent leaching of plasticizers or additives, e.g., from PVC. This is an advantage
for various medical devices as well as many other applications where PVC is utilized. Moreover, many other improvements of
polymers are likely to occur by this new coating process, e.g., surfaces with a higher wettability, corrosion stability, or electrical
conductivity.
Liu et al. found that carbon content in sputter-coated iron catalyst is a key factor for successful growth of vertically aligned carbon
nanotubes (CNTs) on smooth silicon surfaces using CVD (26). The difference in the induction time for the growth of CNTs can be
significantly reduced through presaturation of iron catalyst nanoparticles with carbon. This enables the adjacent CNTs to support
each other from their initial growth phase and, as a result, effectively prevent them from growing into randomly oriented CNT
networks on smooth silicon substrates. According to the findings of this work, it was found that cast iron containing carbon is an
appropriate sputtering target to allow the growth of vertically aligned CNTs on smooth silicon surfaces. Contrarily, it was found that
the pure iron is an ineffective sputtering target. Based on correlation of in situ measured sheet resistance of sputter-coated iron
catalyst with the alignment of CNTs, it was found that there exists an optimal control of the amount of carbon-containing iron
catalyst coatings for the growth of vertically aligned CNTs on smooth silicon surfaces. Here, the optimal catalyst coating was
obtained once the in situ measured sheet resistance versus sputtering time was near the transition zone between rapidly and slowly
declining sheet resistance with respect to sputtering time. Also, cosputtering of an iron target partially covered by graphite sheets
plus sequential sputtering of pure iron and graphite were performed to confirm the efficiency of carbon content in iron coatings for
the growth of vertically aligned CNTs.
Martin et al. applied an antimicrobial polymer coating to fabric through initiated chemical vapour deposition (iCVD) technique,
which is an all-dry method for producing thin, conformal films of polymers on a wide range of substrates (38). The technique allows
preservation of functional groups of fragile monomers, which in turn allows the rapid, one-step, low-temperature synthesis of an
active antimicrobial polymer coating. The dyed nylon fabric was coated with no apparent change in the fabric’s color or feel.
According to the findings of this work, the coating was 499.9999% effective against both gram-negative Escherichia coli and gram-
positive Bacillus subtilis after 60 min. Additional experiments indicated that the coating is 499.99% effective against E. coli after just
2 min. Also, two leaching tests were performed, where none of them indicated that the antimicrobial polymer dissolves off the fabric
to kill bacteria in solution. iCVD antimicrobial coatings are considered in various applications. The process is particularly ideal for
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coating fragile materials, because of the complete lack of any solvent and low temperature of the substrate. Also, finished nylon
fabric, which is sensitive to organic solvents, was easily coated. It is also possible to extend the technique to medical devices, where
the use of solvents in applying a coating could be problematic. The coating is also nonleaching, because of which it reduces the
potential problems with its use in the body.
To deposit uniform coatings on relatively large-sized and/or complex-shaped pieces, it is required to use a generally isothermal
rather than cold-wall CVD reactor. Maury and Senocq deposited Ir thin films deposited on W substrates through thermal
decomposition of Ir(COD)(MeCp) in the presence of either H2 or O2 (43). To do so, first a review of the state of the art of Ir CVD
processes was performed to select the starting materials. To initiate growth process, a horizontal hot-wall MOCVD reactor under
reduced pressure and low temperature (573–673 K) was utilized. In the case of applying this CVD reactor, the process is more
difficult to control when using H2 rather than O2 as coreagent. Here, deposition conditions control properties such as uniformity,
purity, microstructure, growth rate, and thickness. Oxygen prevents carbon incorporation in the layers and noticeably enhances the
growth rate. However, using excessive amounts of O2, Ir, and IrO2, codeposition was observed. The polycrystalline, compact,
untextured, and pure Ir coatings were deposited with appropriate thickness uniformity over an approximate length of 15 cm and
a typical thickness of 1–2 mm. The various attractions of these coatings allow them to be used as oxidation barriers at high
temperature. Using the trends predicted by a kinetic model (which simulates the growth rate along the CVD reactor) the optimal
deposition conditions were determined. To obtain proper thickness uniformity along the reactor, it is required to have a very short
residence time of the reactive species. Consequently, the conversion rate is low and results in a poor efficiency of the process.
Seifert et al. performed plasma wind tunnel tests between 1623 and 1923 K and indicated that through a two-layer coating
system of LPPS yttrium silicates deposited on a CVD–SiC bond coating it is possible to obtain appropriate oxidation protection and
erosion resistance for C/C–SiC composites (147). According to this work, the relative mass loss was estimated as below 0.6% and no
apparent degradation of the surface material was detected up to 1923 K. At higher temperatures, it was observed that hot spots are
formed at the sample’s surface after coating spallation. These overheating effects and similar ones might imply catalytic interaction
between the sample’s surface and the plasma flow. Besides, regarding the numerous possible coating failure mechanisms, a defi-
ciency of mechanical or chemical compatibility between the coating materials and the substrate is discussed. Due to the difference in
the thermal expansion coefficients of Y2Si2O7 and the two modifications of Y2SiO5, the obtained mechanical strain may also control
the microscopic surface cracks and failure in the case of applying high temperatures. Based on thermodynamic calculations, an
appropriate chemical compatibility was determined between both layer materials including yttrium silicate and SiC. Nevertheless,
since a partial increase in pressures of oxygen interface reactions is expected at high temperatures from thermodynamic calculations,
experimental verifications were employed on the results. Based on the calculated isothermal potential phase diagrams, the partial
pressure of a developed gaseous phase, mainly consisting of CO and SiO, highly affects the interface stability. The formation of gas
bubbles and blisters within the silicate layer is clearly attributed to the significantly increasing equilibrium vapor pressure of the
system. Through these calculations, a critical surface temperature of 1903 K is predicted for atmospheric pressure.
Doppalapudi and Basu deposited the adherent mullite coatings on SiC and Si3N4 substrates through a CVD process (81). The
coatings were graded based on their composition with the Al:Si ratio increasing from 2 at the interface to a value of 8 at the top of the
coating. They believe that this is the first report of such a graded mullite within the same coating. The observations of this work
support the earlier reports that a critical Al:Si ratio is necessary for mullite nucleation. Also, evolution of nonstoichiometric mullite
structure from sillimanite, by atomic substitution and formation of oxygen vacancies, was discussed. According to the data ob-
tained, a pure alumina structure can be derived by extension of the same mechanism. Through the ordering of oxygen vacancies and
domain formation, the metastable mullite was stabilized in the coatings with high oxygen vacancy concentration. Based on electron
diffraction studies, ordering of oxygen vacancies in the mullite unit cell was deduced and was correlated with the observed changes
in lattice parameters and Al:Si ratio. Using the images of anti-phase boundaries observed in electron diffraction patterns, it was
inferred that two-dimensional domains are formed by long-range ordering of oxygen vacancies. It was found that the domain width
varies in a linear mode with oxygen vacancy concentration.
7.05.9.2 Characterization of CVD Coatings

Schuster et al. applied vapor deposition in the temperature range of 350–550 C (148). They used bis(benzene)chromium and NH3
or N2H4 as chromium and nitrogen vapor sources, respectively, and then demonstrated the chemical and structural characterization
of these coatings. The amorphous films were produced below 450 C, while at the higher temperatures, a different phase, i.e., Cr7C3,
Cr2(N,C), or CrN could be formed depending on the gas-phase composition. Based on the electron probe microanalysis and XPS, it
was found that the film is slightly contaminated with free carbon atoms. The experimental results well correspond to the ther-
modynamic calculation, which yielded useful information about the feasibility of producing chromium nitride phases under these
CVD conditions. Microhardness of the coating in each case was competitive with that of a similar material deposited using other
approaches.
Chevalier et al. developed thin oxide films of Cr2O3 and Nd2O3 by MOCVD technique (see Figure 16), to protect SS against
high-temperature corrosion (149). They investigated conditions of precursor volatilization by thermogravimetry technique. Here,
the kinetics of the deposited film is controlled by deposition parameters, particularly substrate temperature, gas flow rate, and
location of the substrate in the coating reactor. The effect of deposition parameters on deposition rate and uniformity of the films is
discussed. The main objective of this work is to optimize coating parameters to produce mixed Nd2O3–Cr2O3 films, which leads to
the most important protective characteristics under high-temperature corrosion conditions.
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Figure 16 Schematic figure of the MOCVD apparatus. Reproduced from Chevalier, S.; Bonnet, G.; Larpin, J. P. Metal-organic Chemical Vapor
Deposition of Cr2O3 and Nd2O3 Coatings. Oxide Growth Kinetics and Characterization. Appl. Surf. Sci. 2000, 167, 125–133.
7.05.9.3 Properties of Coatings

7.05.9.3.1 Electrochemical Properties
Haanappel et al. performed MOCVD of amorphous alumina films on steel in nitrogen at atmospheric pressure (150). The MOCVD
technique is based on thermal decomposition of aluminum-tri-sec-butoxide (ATSB). The effect of the deposition temperature, the
precursor vapor pressure, and the gas flow of the MOCVD process was investigated in relation to corrosion properties at high
temperatures. Here, the corrosion tests were performed at 450 C in a gas atmosphere with 1% H2S, 1% H2O, 19% H2, and balanced
Ar. The amount of corrosion products on an alumina film (0.20 0.05 mg cm2)-AISI 304 combination drops with increase of
deposition temperature of the coating. This was more highlighted for the products developed through the coating since they have
certain porosity values. The crack density was almost unaffected. The thin films of aluminum oxide can be produced by pyrolytic
decomposition of ATSB, where the activation energy for the heterogeneous reaction is 83 þ 5 kJ mol. Despite the fact that the coated
specimens are much less attacked than uncoated ones, the application of these layers for corrosion protection for the underlying
metallic materials still involves challenges induced by fast diffusion paths such as cracks and pores. Besides, corrosive gas
components can easily reach the underlying substrate and form, for example, sulfide products. Also, the higher deposition
temperatures, corresponding to the region of diffusion-limited film growth, result in a less-uniform but more protective behavior of
the alumina film owing to a denser structure.
Hubbard and Espinoza developed an organometallic CVD process to prepare protective erbium oxide coatings resistant to
corrosion through liquid plutonium (151). They used precursor the compound Er(tmhd) to deposit the coatings applying a stan-
dard hot-wall reactor. The substrates utilized for process development were 304 SS flats. Next, the coatings were deposited on the
internal surfaces of high-aspect-ratio tubular parts, as well as a number of curved samples. The coatings prepared involved the
correct oxygen/erbium ratio plus small concentrations of carbon and hydrogen impurities. The impurities were present in the form
of unreacted or partially reacted precursor molecules, which are probably concentrated at the grain boundaries of the material.
Moreover, the films were polycrystalline with a grain size of 40 50 nm and indicated good adhesion and mechanical toughness.
An explanation for such small grain size and the resultant favorable mechanical properties might be the presence of the organic
fragments at the grain boundaries. Although an erbia thickness threshold is observed, the coatings deposited on SS flats were
resistant to corrosion by liquid plutonium. The failure mechanism for samples with thickness below the threshold value can be
mainly attributed to the flaws in the film morphology, e.g., large pinholes rather than grain–boundary attack.
Sella et al. studied the properties and corrosion resistance of amorphous hydrogenated carbon and amorphous hydrogenated
SiC films (152). The films are deposited by RF-PECVD at low temperatures (below 200 C). To prepare the SiC coatings, the gaseous
mixture of SiH4–CH4 was used. The classical SiH4–CH4 mixtures were used to deposit hydrogenated DLC coatings and then the
effect of various deposition parameters was investigated. In addition, the microstructural and mechanical properties of the films
(density, hydrogen content, nanohardness, internal stress, critical load, and friction coefficient) were examined. Here, the corrosion
resistance and biocompatibility of SiC and DLC coatings deposited on metal implants (Ti alloy) was studied, where the corrosion
resistance is assessed using potentiodynamic polarization tests in biological media. Moreover, the biocompatibility of coated and
uncoated metals is compared through differentiated human cell cultures. Han et al. investigated electrochemical characteristics of
graphite coated with pyrolytic carbon materials for the active material of anodes in lithium ion secondary batteries through
tumbling CVD process (153). To coating pyrolytic carbons on the surface of graphite particles, tumbling in a rotating reactor tube,
the pyrolysis of liquid propane gas was carried out. Through tumbling CVD, it is possible to appropriately coat the surface of
graphite particles with pyrolytic carbon. It was found that the core part consists of highly ordered carbon, whereas the shell part
contains disordered carbon. According to the findings of this work, the new-type carbon obtained from tumbling CVD involves
a uniform core (graphite)–shell (pyrolytic carbon) structure. Here, a charge–discharge cycler was utilized to examine the electro-
chemical property of these new-type carbons. It is possible to efficiently reduce the initial irreversible capacity by 47.5% for the
coating of pyrolytic carbon on the surface of graphite. Compared to bare graphite, cyclability and rate capability of carbons with the
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core–shell structure are considerably higher. It was indicated that the coating of pyrolytic carbon on the surface of graphite induces
contact resistance reduction in the carbon electrodes; i.e., the formation of solid electrolyte interface layer is suppressed. It seems
that coating of pyrolytic carbon by tumbling CVD is an appropriate technique to improve the electrochemical properties of graphite
electrodes for lithium ion secondary batteries.
7.05.9.3.2 Tribological Behavior

When steel- and nickel-based alloys are applied as substrate materials for the CVD of hard wear-resistant and corrosion-protective
coatings, the standards for selecting the appropriate grade have to be considered since these materials involve high mechanical
strength. Hintermann discusses the friction and wear behavior of some refractory coatings, including TiC, TiN, SiC, Cr7C3, FexB, and
Al2O3, under various environmental conditions (100). Also, some industrial tribological applications are introduced at medium
temperatures (350 C in a helium atmosphere) or where the environment hinders applying fluid lubricants to demonstrate the
technical and economic feasibility and the efficiency of these coated machine elements and wear parts. Finally, a very special and
newly initiated application is dealt with: a multiple refractory compound coating to promote the protection of niobium tubes in the
core of a nuclear reactor from damage induced by the metallurgical corrosion created by liquid steel at high temperature (1600 C),
which in turn is the result of accidental failure of a fuel pin.
Ma et al. deposited a set of new quaternary Ti–Si–C–N nanocomposite coatings on HSS substrate at 550 C (51). To do so, they
applied an industrial setup of pulsed direct circuit PECVD equipment using a gas mixture of TiCl4/SiCl4/H2/N2/CH4/Ar. By
adjusting the CH4 flow rate and the mixing ratio of the chlorides, it is possible to control the coatings’ composition. It was found
that a Ti (C,N)/a-C/a-Si3N4 nanocomposite structure is formed. In addition, Ti(C,N) films indicate a (200) texture, which changes to
random orientation of the crystallites once the silicon content exceeds 9 at.%. These coatings were examined at room and elevated
temperatures in terms of their tribological behavior. The findings indicate that the nanocomposite Ti–Si–C–N coatings with low Si
and high C contents have a lower friction coefficient of 0.17–0.35 at room temperature. Oguri and Arai prepared a-C-Si–H coatings
through PACVD technique using reactive gases of CH4 and SiCl4 (102). Performing ball-on-disk tests demonstrated the tribological
properties of the coatings with no lubricant in ambient atmosphere. According to the results of this work, laser Raman spectroscopy
indicated that DLC–Si coatings can be obtained at a carbon content of 70–85 at.%, while amorphous SixC1x and GLC–Si are
obtained at a lower and a higher carbon content, respectively. In addition, the friction coefficient m of the a-C-Si–H coatings
noticeably varies with carbon content (composition excluding hydrogen). Here, m values dropped sharply from 0.43 to 0.16 for the
coatings with about 60 at.% C and reached a minimum value of 0.04 for the coatings with 75–85 at.% C, which consisted of DLC–
Si. Moreover, m values of the DLC–Si coatings were one-third to one-fifth of those of DLC coatings without silicon. Another
significant point observed was that the wear rate of the countersteel ball against DLC–Si is equal to or is smaller than that against
DLC, whereas the wear rate of the DLC–Si coating was greater than that of the DLC coating. Also SiO2 – which seems to play
important roles in the friction properties, especially at friction coefficient below 0.04 – was developed at the sliding surface between
DLC–Si and steel.
Le Huu et al. investigated the tribological behavior of steel probes with different DLC coatings in a vacuum shell and under
various environments against steel (101). The coatings were obtained through plasma-assisted chemical vapor deposition.
According to the experiments conducted, good adhesion of these coatings to the substrate and good resistance to high shear stresses
were obtained. Experimental results for various DLC coatings are presented. The findings of this work can be used to identify
tribological behavior of each coating structure. Coatings with a high electrical conductivity, which indicates the presence of graphite
within the DLC, involve favorable tribological properties including low friction coefficients and very low wear rates. Adsorbable
gaseous environments result in decrease of the friction coefficient. Diamondlike coatings without the graphite structure demonstrate
a very different tribological behavior. The presence of water vapor or other active gases such as oxygen leads to an increase in the
friction coefficient. Colmet et al. deposited alumina coatings from an AlCl3–H2–CO2 gas mixture on TiC-precoated cemented
carbide or sintered alumina cutting tool inserts by applying CVD (154). They examined the influence of both CVD conditions
(temperature, total pressure, and feed gas composition) and the nature of the heat treatments of the substrates on the morphology,
adherence, and wear resistance of the coatings. The deposits are often made of conducting nonstoichiometric a-Al2O3. The growth
rate of the coating rises with temperature and total pressure. They obtained the optimum results with deposits prepared at medium
temperature and low pressure. Heat treatment of the TiC-precoated cemented carbide inserts, before alumina deposition, results in
an increase in adherence of the products. Moreover, an alumina CVD deposit on sintered alumina inserts improved their wear
resistance. On heating the black a-Al2O3 deposits in the air, oxygen vacancies are eliminated and become insulators.
Holzschuh deposited the cubic Ti(BxCyNz) coatings on cemented carbides through CVD technique (155). By keeping the B
content below 5%, it was allowed to maintain Ti–B–C–N in the cubic phase. Besides, by changing the gas precursor flows in the
CVD process, the B:C:N ratio, microstructure, hardness, and wear resistance of the coatings were controlled. According to the
findings of this work, TiCN coatings containing B demonstrated higher hardness but lower critical loads for coating decohesion.
Besides, using microprobe measurements, it was found that B diffusion was responsible for inhomogeneous coating compositions
and formation of a CoWB phase on the surface of the cemented carbide tool. Finally, using milling tests, it was found that the
coatings had appropriate abrasion wear resistance – where the main wear mechanism in turning tests was cratering.
Keshri et al. applied CVD to prepare a homogeneous dispersion of CNTs on aluminum oxide (Al2O3) powder (87). The powder
was sprayed as plasma particles on a steel substrate to produce a 96% dense Al2O3 coating with CNT reinforcement. By adding
1.5 wt.% CNTs, a 24% increase in the relative fracture toughness of the composite coating was observed. The improvement in the
fracture toughness is obtained mainly because of the uniform dispersion of CNTs and toughening mechanism such as CNT
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bridging, crack deflection, as well as strong interaction between CNT/Al2O3 interfaces. Besides, the wear and friction behavior of the
CNT-reinforced Al2O3 coating was examined under dry sliding condition using ball-on-disk tribometer. With increase of the normal
loads from 10 to 50 N, the wear volume loss and coefficient of friction of the coating increased as a consequence of transition from
the mild to severe wear conditions. At load value of 50 N, the wear resistance of the Al2O3–CNT composite coating improved by
w27%. Finally, coefficient of friction at 50 N was controlled by the competing phenomena of wear debris generation and
graphitization induced by the pressure. Figures 17–19 show SEM and TEM images of obtained nanomaterials.
Feng et al. studied friction of diamond on diamond in air to understand the friction mechanisms (28). They also examined
friction of diamond on CVD diamond coatings. They utilized a reciprocating friction apparatus with a sliding configuration of
a stylus on a plate, which allowed estimation of contact area and pressure from Hertz theory. Also, the effects of temperature, the
number of sliding traversals, as well as environmental conditions were investigated. Adhesion is important in the friction process of
diamond sliding on diamond in air. Moreover, water plays a key role in adhesion decrease. For measuring friction of diamond on
CVD diamond coatings relatively low pressure values were employed due to the poor adhesion between the diamond coatings and
the substrates (silicon). Furthermore, the friction coefficient of diamond sliding on CVD diamond coating was greater than that of
diamond on diamond for the same experimental conditions. One explanation for this phenomenon might be the rougher surface
compared with that of a polished diamond. Nevertheless, the friction coefficient could be considerably lowered by applying water,
implying that adhesion was also present in the friction process. Hirata and Yoshioka investigated sliding friction properties of CNT
coatings catalytically deposited by microwave plasma CVD (78). They used a gaseous mixture of methane and hydrogen and then
applied ball-on-disk type friction testing. They deposited CNTs with different crystallinity levels by varying the microwave power
and bias voltage employed to a silicon substrate. Before the deposition process, nickel was utilized as a catalyst and coated on the
substrate by DC sputtering. Once CNT coatings are less defective and, in particular, in a water-free atmosphere such as a vacuum,
friction values indicated a reduction. Moreover, by improving the adhesion of CNT coatings on cemented carbide and silicon nitride
substrates, lower friction coefficients, below 0.1, are obtained; however, it depends on the density of the CNTs remaining on the
sliding surfaces.
Figure 17 SEM images showing (a) as-received dense, sintered, and crushed Al2O3 powder and (b) CVD-grown CNTs concentrated between the
ridges of the Al2O3 powder particle. Reproduced from Keshri, A. K.; Huang, J.; Singh, V.; Choi, W.; Seal, S.; Agarwal, A. Synthesis of Aluminum
Oxide Coating with Carbon Nanotube Reinforcement Produced by Chemical Vapor Deposition for Improved Fracture and Wear Resistance. Carbon 2010,
48, 431–442.
Figure 18 (a) Homogeneous dispersion of CVD-grown CNT on Al2O3 powder particle and (b) high-magnification SEM image of CVD-grown CNTs.
Length of CNTs is in the range of 0.6–2.0 lm. Reproduced from Keshri, A. K.; Huang, J.; Singh, V.; Choi, W.; Seal, S.; Agarwal, A. Synthesis of
Aluminum Oxide Coating with Carbon Nanotube Reinforcement Produced by Chemical Vapor Deposition for Improved Fracture and Wear Resistance.
Carbon 2010, 48, 431–442.
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Figure 19 (a) TEM image of CVD-grown CNTs and catalyst particles in ICP-1 powder and (b) HRTEM image of CVD-grown CNTs showing 19 4
walls of graphitized carbon. Inset shows inverse fast Fourier transformed image of CNT with an interlayer spacing of 3.81 Å for in situ grown
CNT. (c) Histogram showing the distribution in diameter of in situ grown CNTs. Reproduced from Keshri, A. K.; Huang, J.; Singh, V.; Choi, W.; Seal, S.;
Agarwal, A. Synthesis of Aluminum Oxide Coating with Carbon Nanotube Reinforcement Produced by Chemical Vapor Deposition for Improved
Fracture and Wear Resistance. Carbon 2010, 48, 431–442.
CVD techniques have been used successfully for many years in order to fabricate micro- and nanocoatings. As a coating process,
CVD played a customized, but very important role, ever since the low-melted halides of refractory metals were investigated as
a system. Today, the term ‘chemical vapor deposition’ involves a wide range of processes in all of which the applied reagents are
those that can tolerate chemical reactions at or near the heated surface. Different kinds of nanocoatings including diamonds,
carbides, nitrides, oxides, and polymeric materials can be deposited by the CVD method. Plasma and RF have been applied in CVD
process and many interesting results have been achieved. Today, microwave plasmas are an interest for many researchers to
synthesize diamond layers. Layer deposition is performed from a mix of hydrogen and organic gases containing methyl radicals
with growth rate of 10 mm h1, but as an example, it was reported that researchers have fabricated some bushes with thickness above
1 mm. Diamond layers are adequate abrasion-resistant coatings and have various applications in semiconductor technology.
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134. Jedrzejowski, P.; Klemberg-Sapieha, J. E.; Martinu, L. Relationship between the Mechanical Properties and the Microstructure of Nanocomposite TiN/SiN1.3 Coatings Prepared
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Thin Solid Films 2004, 466, 189–196.
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7.06 Fabrication and Properties of Micro- and Nanostructured Coatings
Using Electrochemical Depositions

7.06.2 General Principles 124
7.06.3 Coating in the Cell 124
7.06.3.1 Principles 124
7.06.3.2 Efficiency 124
7.06.3.3 Characteristics 125
7.06.4 Selective or Brush Coating 125
7.06.5 Chemical, Autocatalytic, and Electroless Deposition 125
7.06.6 Hard Anodization 126
7.06.7 Coating Materials 126
7.06.7.1 Chromium 126
7.06.7.1.1 Characteristics 127
7.06.7.1.2 Applications 128
7.06.7.2 Nickel 128
7.06.7.3 Chemically Deposited Ni 129
7.06.7.3.1 Characteristics: Ni–P 129
7.06.7.4 Characteristics: Ni–B 129
7.06.7.5 Copper 129
7.06.7.6 Cu–Sn Alloys 131
7.06.7.7 Iron 131
7.06.7.8 Cobalt 131
7.06.7.9 Pb 132
7.06.7.10 Sn 132
7.06.7.10.3 Characteristics: Sn–Ni (65/35) Alloy (Introduced in Standard BS 3597) 132
7.06.7.11 Sn-Based Diffusive Alloys 132
7.06.7.12 Ag 133
7.06.7.13 Au 133
Comprehensive Materials Processing, Volume 7 http://dx.doi.org/10.1016/B978-0-08-096532-1.00707-X 119

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120 Fabrication and Properties of Micro- and Nanostructured Coatings Using Electrochemical Depositions

7.06.7.14 Pt Group Metals 137
7.06.7.14.1 Pd 138
7.06.7.14.2 Pt 138
7.06.7.14.3 Rh 138
7.06.7.14.4 Ru 138
7.06.8 Composite Electrochemical Deposition 138
7.06.8.1 Characteristics: Co–CrC 138
7.06.8.2 Characteristics: Ni–SiC 138
7.06.9 Hard Anodizing 139
7.06.9.2 Applications 139
7.06.10 Selection 140
7.06.10.1 Design 140
7.06.10.2 Piece Design 140
7.06.11 Process Design for Cell Coating 141
7.06.11.1 Substrate Materials 141
7.06.11.2 Surface Preparation 142
7.06.11.3 Polishing 142
7.06.11.4 Technical and Inspection Characteristics and Quality Guarantee 142
7.06.12 Application of Electrochemical Deposition for Micro- and Nanocoatings 142
7.06.12.1 Metallic-Based Coatings 142
7.06.12.2 Ceramic-Based Coatings 145
7.06.12.3 Polymeric-Based Coatings 150
References 152
7.06.1 Introduction
Electrodeposition is a common process in the synthesis of metallic coatings improving surface properties in engineering oper-
ations. Although its principles are rather similar to the processes performed in relatively thin coating applications for aesthetic and
corrosion protection purposes, the surface engineering type of electrodeposition is considered a specialized process and is
different from the other ones in some aspects. In this chapter, the application of specific metallic coatings is elaborately discussed
through chemical reduction and anodic oxidization processes. Both these processes are performed in aqueous media and are
mainly applied in association with electroplating processes. Theoretically, there is no limitation to the coating thickness, because
various metals and alloys can be electrically deposited; however, the needed thickness for functional requirements is the main
criterion. Here, the economic aspects of the process are also important. It must be noted that electrical deposition can be slow and
expensive. So, although it is required to produce thick coatings, other surface operation techniques can be more effective in terms
of economic considerations. Regarding the thinner engineering coatings, electrical deposition offers a dramatic flexible view to the
process designer and is considered a key point for successful the operation of many parts (1–11).
It is known that samarium-based films are developed from aqueous solutions on the surfaces of metallic substrates like
steel or aluminum. Their presence has been reported to substantially reduce the corresponding corrosion rate of the under-
lying metallic substrate. Based on the previous studies about the deposition of oxides or hydroxides of a closely related
element, namely cerium, Ruiz et al. (12) indicated that samarium films are formed following a similar mechanism. As
a fundamental step, the mechanism involves an increase in interfacial pH induced by cathodic oxygen reduction or hydrogen
evolution reactions.
Sazou et al. (13) applied an electrodeposition technique to synthesize polyaniline (PAn) films on stainless steel 304 (SS) from
0.5 M H2SO4 solution containing 0.1 M aniline. In particular, PAn films were produced using the following approaches: through
cyclic potential sweep (CPS) deposition upon varying the upper potential limit (El) of the polymerization potential region between
0.8 and 1.1 V and the lower potential limit of 0.2 V; and via potentiostatic deposition, where the applied potential (Eappl) varies
between 0.8 and 1.1 V. The potential sweep rate (dE/dt) was also varied for the aniline polymerization during the CPS deposition.
Variation of the El, dE/dt, and Eappl influences the PAn growth and results in films with different electrochemical and structural
characteristics. Based on monitoring of the open circuit potential (EOC) of the PAn-coated SS electrode in 0.5 M H2SO4, it was
found that the SS remains in the passive state. PAn films can also provide protection to SS in chloride-containing 0.5 M H2SO4 for
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Fabrication and Properties of Micro- and Nanostructured Coatings Using Electrochemical Depositions 121
the studied period of time; however, pits were detected during prolonged immersion. It seems that the protection efficiency is
related to the parameters El, dE/dt, and Eappl, which are varied during polymerization.
Sisman et al. (14) used an acidic aqueous solution of CdSO4 and TeO2 to electrosynthesize size-quantized thin films of CdTe on
Au (111) substrates through underpotential deposition (UPD). Besides, a cyclic voltammetry test was carried out to evaluate the
electrodeposition mechanism and the codeposition potential of CdTe. Based on voltammetric analysis, it was found that the elec-
trodeposition of CdTe is a two-step codeposition process under the conditions of UPD. Moreover, morphological investigations
indicate that the film growth continues through the formation of a few layers, followed by the growth of spherical nanoparticles on
the overlayer, and then proceeds by growth to form smooth spherical crystallites of CdTe. The formation of films is highly preferential
with the (111) orientation. Also, optical investigations exhibited a blue shift in band gap energy because of quantum confinement.
Deng et al. (15) produced polypyrrole–graphene oxide (PPy–GO) composite films using a one-step electrochemical process. To
do so, they utilized the electrostatic interaction between positively charged pyrrole cation radicals and negatively charged graphene
oxide (GO) sheets (see Figure 1). Besides, the effects of the polymerization current density and the GO content in electrolyte were
examined on development of PPy–GO coatings on platinum neural microelectrode sites. Compared to the pure PPy film, PPy–GO
coatings indicated a rougher surface feature with micrometer-scale bulges. According to the findings of this work, the impedance of
the PPy–GO-coated Pt electrode is only about 10% of the bare Pt electrode at the biologically relevant 1 kHz. But the charge capacity
density is more than two orders of magnitude that of the bare Pt electrode. In addition, the PPy–GO-coated Pt electrodes indicated
better performance compared to the PPy-coated electrodes for the application of neural probe.
Tsybulskaya et al. (16) developed a polyligand alkaline bath for Zn–Ni alloy electrochemical deposition containing aminoacetic
acid (AAA) and triethanolamine (TEA) as the ligands to bind Ni(II) cations. The [Zn(II)]–[Ni(II)] ratios in the bath significantly
affected the alloy composition, where the nickel content in the obtained deposit changed in a wide range (from 8 to 75 at.%). It was
found that the alloys are composed of the g-phase (Ni5Zn21), solid solutions of Zn or Ni in the g-phase, or a mixture of the g-phase
and polycrystalline Ni or Zn. Here, the highest corrosion resistance in a saline environment was observed for high-quality coatings
with nickel content of 13–20 at.% having the g-phase or solid solution of Zn in the g-phase. Based on the findings of this work, the
optimal Ni(II):AAA:TEA molar ratio to obtain corrosion-resistant alloys was determined as 0.04:0.65:0.12. The microhardness of
these Zn–Ni alloy coatings (1.6–1.9 GPa) was twice greater than that of zinc coating.
Wang et al. (17) applied an electrochemical technique to deposit hydroxyapatite and fluoridated hydroxyapatite (FHA) coatings
on titanium substrates. Different concentrations of F ions were loaded to the apatite structure through adding NaF to the elec-
trolyte. After electrodeposition and subsequent posttreatment (i.e., alkaline immersion and vacuum calcination), the typical apatite
structures were obtained for all developed coatings. The coatings were uniform and dense, with a thickness of w5 mm. When the
F-concentration exceeds 0.012 M in the electrolyte, a saturation of F in the coating occurred, and the F:Ca ratio in the coatings
Figure 1 Conceptualized approach for electrochemical deposition of PPy–GO coating on the Pt electrode site. Reproduced from Deng, M.; Yang, X.;
Silke, M.; Qiu, W.; Xu, M.; Borghs, G.; Chen, H. Electrochemical Deposition of Polypyrrole/Graphene Oxide Composite on Microelectrodes towards
Tuning the Electrochemical Properties of Neural Probes. Sens. Actuators, B, 158, 176–184.
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became almost constant (F:Ca ratio ¼ 0.125). Higher bonding strength and lower dissolution rates were observed for FHA coatings
compared to hydroxyapatite coating, particularly for those with a fluoridation level of 0.5–0.625. In comparison to pure Ti, FHA
and hydroxyapatite coatings demonstrated higher biological affinity like cell proliferation and alkaline phosphatase activity.
Considering their clinical applications, it can be claimed that the moderate content of F, such as Ca5(PO4)3(OH)0.375–0.5F0.5–0.625, is
most appropriate as a compromise among cell attachment, cell proliferation, apatite deposition, and dissolution resistance.
Haseeb et al. (18) addressed the capability of electrochemical deposition as a production method for artificially structured
materials. In comparison to PVD, electrochemical deposition technology involves some distinct advantages such as low cost,
industrial applicability, and its ability to produce structural features with sizes ranging from nanometers to micrometers. Such
benefits have attracted many people to this technology for the synthesis of artificially structured materials. Several electrochemical
deposition methods are briefly reviewed. Moreover, some specific cases of artificially structured coatings produced by electro-
chemical deposition, such as epitaxial multilayered materials (Cu–Ni), amorphous materials in combination with crystalline
materials (NiPx–NiPy), and alternating hard and ductile materials (NiPx–Sn), are also highlighted (see Figures 2 and 3). According
to the findings of this work, by adequately controlling the electrochemical deposition conditions, it is possible to synthesize a wide
range of artificially structured materials considering their constituent elements and microstructural morphology.
Blackwood and Seah (19) used hydroxyapatite coatings to improve the biological performance of titanium and its alloys to the
surface. Although plasma spraying is as a technique currently accepted in clinical applications, it involves shortcomings such as
being a line-of-site method, which greatly limits its utilization to coating either irregular shapes or the low-elastic-moduli porous
materials and currently developed metallic sponges for implants. As an alternative, one can name the electrochemical cathodic
deposition technique, which also involves some disadvantages (crystallinity of the deposited hydroxyapatite and its adhesion to the
Figure 2 Cross-sectional scanning electron micrograph (SEM) of electrochemically deposited Cu–Ni multilayers with sublayers 100 nm thick by the
dual-bath technique. Deposition conditions: 2 A dm2 for both Cu and Ni depositions; 30 C; Cu bath: 90 g 1l CuSO4$5H2O, 200 g 11 H2SO4
and 10 ml l1 EX-10 (Harshaw); and Ni bath: 400 g l1 Ni(NH2SO3)2 and 30 g 11 H3BO3. Reproduced from Haseeb, A.; Blanpain, B.; Wouters, G.; Celis, J.
P.; Roos, J. R. Electrochemical Deposition: A Method for the Production of Artificially Structured Materials. Mater. Sci. Eng. A 1993, 168, 137–140.
Figure 3 Schematic diagram showing the range of microstructures obtainable by dual-bath electrochemical deposition. Reproduced from
Haseeb, A.; Blanpain, B.; Wouters, G.; Celis, J. P.; Roos, J. R. Electrochemical Deposition: A Method for the Production of Artificially Structured
Materials. Mater. Sci. Eng. A 1993, 168, 137–140.
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substrate). The enhanced adhesion and crystallinity are obtained through either pretreating of the Ti substrate with NaOH after
a heat treatment at 600 C or the addition of H2O2 to the electrolyte. Such an increased adhesion might lead to the former case from
the creation of a titanate binding layer. However, in the latter case, the local alkaline conditions needed for deposition are obtained
through reducing the peroxide, which in turn rules out the need to evolve hydrogen that can damage the film. Rotating the substrate
at low revolutions is also beneficial for adhesion. Nevertheless, bulk precipitation is preferred to film formation at high rotation
rates. Figure 4 illustrates high-resolution transmission electron microscopy (TEM) images of the as-prepared Ni–Al LDH–C
composite containing 17.8 Al% at different magnitudes.
Yan et al. (20) performed field emission studies on diamond-like carbon (DLC) and nitrogen-doped diamond-like carbon
(N-DLC) films deposited through an electrodeposition technique. The films were formed on Si (100) substrates through the
electrolysis of methanol–urea solution under high voltage, at atmospheric pressure, and at low temperature. Moreover, the field
emission measurements were carried out with a parallel plate configuration using the deposited DLC and N-DLC films as the
cathode and indium tin oxide (ITO)-coated glass as the anode. Based on these measurements, it was found that the electrodeposited
films demonstrate good field emission properties, and the nitrogen doping could raise the current density. These behaviors mainly
associate with changes in the microstructure of the samples, which in turn is controlled by the difference of surface morphology.
Coating porous titanium with calcium phosphate (Ca–P) is an efficient technique to promote osteoinduction capability of
titanium. The efficiency of two coating techniques (i.e., biomimetic deposition and electrochemical deposition) was examined in
aqueous solutions. Before applying a coating process, the titanium surfaces were modified by acidic etching and alkaline. Moreover,
the influence of the precoating treatments was evaluated on Ca–P coating. Both deposition techniques could create Ca–P coatings
on the inner pore surfaces of the titanium. Biomimetic deposited coatings were thicker and more uniform compared to the elec-
trochemical deposition coatings. Moreover, electrochemical deposition was less sensitive to the titanium surface condition and
Figure 4 High-resolution TEM images of the as-prepared Ni–Al LDH–C composite containing 17.8 Al% at different magnitudes: (a) 500 nm and
(b) 50 nm. Reproduced from Blackwood, D. J.; Seah, K. H. W. Electrochemical Cathodic Deposition of Hydroxyapatite: Improvements in Adhesion
and Crystallinity. Mater. Sci. Eng. C 2009, 29, 1233–1238.
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much faster in the coating deposition. Nevertheless, electrochemical deposition produces less uniform and thinner coating layers on
the inner pore surfaces of the titanium in comparison to the biomimetic deposition technique. Regardless of the applied deposition
method, the crystalline structure of the coating was octacalcium phosphate (OCP). Also, the morphology of flake-like OCP crystals
in the deposition layers was similar for both deposition methods, except that the crystal flakes rupture after electrochemical
deposition (21).
7.06.2 General Principles
Within electrical deposition or electroplating, the coating target is designed as a cathode (negative electrode) and placed in a liquid-
containing cell. Typically, this liquid (electrolyte) is a solution with salty metal (containing target deposit) kept at 60 C. The
electrical circuit is completed by an anode or positive electrode, which typically is made of a metal that performs deposition and
should be placed at a small distance from the cathode. In the case of applying DC current at low voltages, metallic ions are positively
charged and move toward the cathode in the electrolyte. Indeed, this place is part surface and is considered a spot where the ions are
subjected to the metallic atoms and are deposited on the cathode. The structure and properties of the deposited metal depend on the
chemical composition of the electrolyte, its temperature, as well as its acidity or alkalinity level (pH). These factors, especially the
electrical current density in the unit surface of the cathode, determine the deposition rate. The electrical current distribution in
lumps of cathodic surfaces are more than recesses, and this change in current density affects metal distribution, as the thickness of
coating deposition corresponds with the current density (22–33).
Evenness of thickness is a function of throwing power of the electrolyte, which can be considerably enhanced through designing
parts accurately and paying careful attention to deposition conditions. Since the electrical deposition coatings rarely involve unified
thickness throughout the surface, typically a share of the surface with a key role in piece performance and servicing is defined as the
effective surface and the minimum thickness (not the average one) is determined at this surface. Extensive electrodeposition is
utilized for both obtaining the desired surface properties and further repair and adjustment of the size in pieces highly abraded
during the service or those that are out of dimensional precisions (34–46).
Another application of this technique is fabrication of delicate structures through deposition on rods with various forms that can
be subsequently separated. This process, which is known as electroforming, is a simple technique for the fabrication of pieces with
delicate form through a monotonous load operation, where it is possible to reproduce the final shape and surface of the rod. For
electrodeposition of engineering coatings, there are two main processes. The main features of these two processes and the
complementary process of chemical deposition, including electrolysis, autocatalytic, and hard anodizing processes, will be intro-
duced in this chapter (47–56).
7.06.3 Coating in the Cell

7.06.3.1 Principles
Deposition for almost all engineering applications is performed in tanks or cells with capacity of several thousand liters. The tank
might be installed around the piece for some specific applications. Here, a large cylindrical piece with internal coating requirements
also calls for its specific tank. The electrolyte is agitated in a slow rate through the air jets or mechanical motions and kept at working
temperature through submerged electric ovens or vapor coils. It is also possible to apply a water-circulating system instead of that.
Here, the anodes are suspended at the distance of several centimeters with a worked piece (i.e., the current passes through them but
is not dissolved in the electrolyte process). Thus, the coating materials are totally obtained from the solution. The workpiece itself
is placed in a cage or vise and suspended in the electrolyte. A rectifier transformer supplies a coating current in the voltage range of
4–8 V in an adjusted manner. The applied current is recorded using an ammeter and deposition tome required for achieving the
desired thickness, and the expected efficiency is estimated in this way (16,19,57–64).
7.06.3.2 Efficiency
Efficiency of deposition involves the weight ratio of the metal that is actually deposited to the weight supposed to be deposited
through a current–time combination. Generally, a share of passed current is wasted due to unavoidable hydrogen emission in the
cathode. This will be discussed in detail in this chapter. Deposition efficiency varies with the applied electrolyte system, coating
conditions, and current density. By keeping nonmetallic particles in suspended form in the electrolyte, these particles can be present
in a deposit’s metal, such as silicon carbide (CSi) in nickel (Ni). The process was controlled through measuring the density and
acidity of the electrolyte and, in the long term, chemical composition. By modification of the coating cell, it is possible to coat
smaller pieces in a bulk manner. For instance, the pieces can be placed in a slotted cylindrical rubber barrel that is submerged in
coating solution and is constantly circulating. The workpiece is formed in a negative electrode of the barrel and keeps its electrical
contact by its sliding over each other. At the same time, fresh surfaces are provided for the electrolyte performance. Barrel plating is
used for pieces that are lighter than 500 g, involve simple form, and are able to slide over each other without any interlock. The
coating developed in this way is thin and is mainly applied in embellishment application; however, the engineering deposition
applications of Pt and Au metals are for corrosion and abrasion resistance (13,65–76).
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7.06.3.3 Characteristics
1. Considering that the operation temperature never goes over 100 C, no undesired metallurgic change or distortion occurs in the
sample.
2. Coating conditions can be adjusted in a way so that hardness, internal stresses, and mechanical properties of the deposit are adjusted.
3. The coatings are dense and adhesive to the substrate. The strength of the bond, which is of a molecular nature, reaches up to
1000 N mm2.
4. Deposits’ thickness is appropriate with the current density and depositing duration.
5. Since current density at the surface of a workpiece is rarely unified, the coating is thicker in the edges and corners, while it is
thinner in recesses and wide flat areas.
6. The deposition rate rarely exceeds 75 mm h1, but deliberate stirring of the electrolyte can accelerate it.
7. There is no technical restriction for deposits’ thickness. Metals such as Ni can have a thickness of 13 mm or higher during elec-
trolyte formation or repair operations, but in the majority of surface operation applications, it is required to use thinner coatings.
8. Coatings application is not limited to the current purposes. Although the restriction of throwing power – the ability to coating
round corners – might exist, for anodes (e.g., in coating of the thin tubes’ holes) there is a relative freedom.
9. Cell size limits the dimensions of the workpiece.
10. The process is not suitable for an automation process.
7.06.4 Selective or Brush Coating
The electrochemical reactions in selective or brush coating are the same as for cell coating. The main differentiation between these
two approaches is that selective (brush) coating can be manually performed on pieces such as molds, axes, or bearings in the specific
selected areas.
7.06.4.1 Principles
This process is considered complementary to cell coating and is applied for those electrodeposition processes that can be performed
with minimum coating or filling of the selective areas without piece submerging. Here, the principles are the same for as cell coating,
but the anode is installed in a brush handle and is surrounded by a moisture-absorbent pad soaked in the electrolyte. The workpiece is
attached to the negative pole of a direct current (DC) supply, and the circuit is completed by pad attachment to the workpiece and then
the deposition initiates. Generally, the operator manually moves the pad on the target coating areas. However, to do this, the operator
needs to be very skillful since motion speed is very effective in creating a clear homogenous deposit with no defect. In this process, the
anode is an insoluble carbon rod. Moisture absorbent pad is made of cotton wool or long fibers, although the plastics with resin
bonds are preferred. The electrolyte can be replaced in the pad by its submergence in a glass, drop feed, or solution pumping.
Workpiece cleaning before coating process guarantees polarity for workpiece anodization in the presence of specific solutions (42,77).
The first five characteristics of cell coating are also true for selective coating. The further features of this process are as follows:
1. The equipment is portable and can be carried toward the workpiece. Therefore, for example, the molds can be produced in an in
situ manner without the minimum coating time.
2. Typically, the overall coating is not necessary since only the coating target area is required to be in contact with the electrolyte.
3. The electrolyte has to be stronger than the coating electrolyte in the cell, so it could resist the severe variations of operation
temperature and current temperature.
4. The supply source, which operates at 8–30 V, consists of some fuses for minimizing the destruction imposed by short circuits and
a current–time gauge for coating trend monitoring.
5. Here, the deposition rate is typically higher than that of cell coating and can even reach 200–400 mm h1.
6. The electrolytes are expensive, but they are consumed in small quantities.
7. The manual operations demand high skills and are highly affected by the operator.
8. The process can be handled in an automated manner, for example, in cylindrical hole coating.
9. Selective coating is not suitable for mass production.
7.06.5 Chemical, Autocatalytic, and Electroless Deposition

7.06.5.1 Principles
Electrodeposition involves the reduction of metallic ions that are generated from the electrolyte and converted to the deposited
metallic ions in a cathode surface (workpiece). There is no need to supply reduction current from an external source; for instance, Cu
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can be deposited on Fe by a substitution process. The coatings are very thin and weakly adhesive, which limits their application in
the industry. Some metals, such as Ni, Cu, and Pd, can be deposited through chemical reduction from aqueous solution of their salts
as the initial layer accelerates the further depositing. Hard nickel alloys, which are deposited through the solutions containing
phosphor or boron components, are widely applied as reduction factors in engineering applications. Commonly, the process takes
place in polypropylene or stainless-steel tanks with polytetrafluoroethylene (PTFE) plating, where the solution is maintained at
90 C. These tanks are equipped with some devices for precise temperature control as well as solution stirring and filtering. As with
electrodeposition, the workpiece needs to be cleaned (9,10,29,56,71,74,78–83).
1. The equipment is simple and economical, as there is no need for anodes and DC electrical supply.
2. Deposit thickness is uniform, and it is possible for the solution to flow throughout the surface.
3. Deposition rate, which is controlled by temperature, is about 20 mm h1.
4. Through this process, it is possible to obtain a thickness of 125–200 mm.
5. Also, the places that are not supposed to be coated are coated in this process.
6. The tank size restricts workpiece dimensions.
7. Although the utilized chemical materials are expensive, this process can compete with electrodeposition, particularly when it is
required to deposit a limited number of pieces.
7.06.6 Hard Anodization

7.06.6.1 Principles
The main objective of hard anodization is to thicken and strengthen the adhesive oxide layer, which is typically developed on metals
such as Al and Ti. Hard anodization of Al and its alloys is a well-known and common commercial technique that guarantees
anodization of the workpiece in a tank containing acidic (normally 10–20% sulfuric acid) electrolyte. By applying a direct current at
high potential, the oxygen generated in the anode leaves aluminum, and then a balance between this action and dissolution process
is developed in the electrolyte. The operation at low temperatures (0–5 C) and high current density coupled with solution stirring
results in oxide formation, while it also hinders the dissolution effect. The coating developed through this technique involves high
strength, and then the required initiation voltage (which is 25 V) has to be increased up to 70 V. In some anodization processes,
alternative current (AC) is utilized as well as DC to improve abrasion strength of the coating (60).
1. It requires a larger amount of equipment, compared to electrodeposition, to maintain the required temperature; a coolant unit is
also needed.
2. Hard anodization is a conversion process where the coating is grown from the metal and then integrated with it.
3. Throwing power (i.e., evenness of the coating thickness) is excellent.
4. Hard anodization coatings can be applied for Al and its alloys through selective or brush techniques.
5. The insertion of hybrid metals such as steel must be coated to prevent its corrosion.
6. The process can be performed in an automated manner.
7.06.7 Coating Materials
The electrochemical principles control the electrodeposition process. The standards for electrode potentials are shown in Table 1.
The developed electrical potential between the metal and solution of one of these salts under standard conditions implies the
relative ease of metal deposition from aqueous solutions. Indeed, the actual potential of the electrodes depends on environmental
conditions, especially solution concentration. The binary and ternary alloys can be electrodeposited by the selection of coating
conditions in such a way that deposition potential of the constituting metals is the same. The metals with negative potentials below
1.2 V (Table 1) can be generally deposited from aqueous solutions. Therefore, only Al and Ti can be coated from solutions in
organic solvents or electrolytes of the melted salt since both of them require their own techniques and equipment. Nevertheless,
these processes are now available at commercial scales. Table 2 lists the mechanical and physical properties of the metals and alloys
typically used for engineering purposes of electrical deposition (12,20,21,84–112).
7.06.7.1 Chromium
Although its hardness in the electrical deposition state coordinates with its other surface operations, chromium (Cr) contains a set of
valuable unique properties in engineering operations. The corrosive nature of the electrolytes hinders deposition of Cr alloy, but
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Table 1 Electrical potentials of engineering metals
Metal E vs. SHE (V)
Al 1.66
Ti 1.63
Mn 1.18
Cr 0.74
Fe 0.44
Co 0.28
Ni 0.25
Sn 0.14
Pb 0.13
H2 0.0
Cu þ0.34
Ag þ0.80
Au þ1.68
Table 2 The mechanical and physical properties of some metals utilized for electrodeposition engineering and chemical deposition purposes
Linear expansion Electrical Resistance Relative Tensional Melting

coefficient conductance at 20 C lengthening strength Hardness Density temperature The common
(106/ C) (W m1 k1) (mUcm) (%) (N mm2) (HV) (kg m3) ( C) final thickness Coating type
7.5 67 14–67 <0.1 100–500 800–1000 6930 1878 Up to 0.13 Chromium (Cr)
(even 0.050)
13.5 94 7.4–11.5 3–30 340–1050 150–450 8907 1455 Up to 0.50 Electrodeposited Ni
(and even þ13)
13.0–14.5 60–80 (20a) 1–1.5 (0.2a) 758 (69a) 480 (1030a) 8000 (Almost) 890 0.013–0.05 Chemically
electrodeposited
Ni with 9% of
phosphor
16.5 403 17–4.9 Up to þ40 180–650 60–150 8933 1084 Up to 0.05 Cu
(and even 13þ)
650–700 8400 800þ 0.01–0.2 Sn–Ni (65:35)
(Almost) 21.0 (Almost) 427 1.6–1.9 12–19 240–340 60–120 10 500 961 Up to 0.13 Ag
a
After thermal operation; if not, the information implies as-deposited metal.
The sign ‘–’ indicates that the information is either incorrect or unavailable.
Reproduced from Stoychev, D.; Stefanov, P.; Nikolova, D.; Aleksandrova, A.; Atanasova, G.; Marinova, T. Preparation of Al2O3 Thin Films on Stainless Steel by Electrochemical
Deposition. Surf. Coat. Technol. 2004, 180–181, 441–445; Stefanov, P.; Atanasova, G.; Stoychev, D.; Marinova, T. Electrochemical Deposition of CeO2 on ZrO2 and Al2O3 Thin
Films Formed on Stainless Steel. Surf. Coat. Technol. 2004, 180–181, 446–449; Shpan’ko, S. P.; Grigor’ev, V. P.; Dymnikova, O. V.; Anisimova, V. A. The Effect of Surfactant
Mixtures of Several Reaction Series on Electrochemical Characteristics of Nickel Deposition and Properties of Nickel Coatings. Zashch. Met. 2004, 40, 365–369; Shpan’ko, S. P.;
Grigor’ev, V. P.; Dymnikova, O. V.; Anisimova, V. A. The Effect of Surfactant Mixtures of Several Reaction Series on Electrochemical Characteristics of Nickel Deposition and
Properties of Nickel Coatings. Prot. Met. 2004, 40, 326–330; Sewing, A.; Roessler, S.; Schamweber, D.; Nies, B.; Worch, H. Thin Biomimetic Hydroxyapatite and Mineralised
Collagen Coatings Prepared by Electrochemical Assisted Deposition. In Proceedings of Transactions – 7th World Biomaterials Congress; 2004; p 309; Sewing, A.; Lakatos, M.;
Scharnweber, D.; Roessler, S.; Born, R.; Dard, M.; Worch, H. Influence of Ca/P Ratio on Electrochemical Assisted Deposition of Hydroxyapatite on Titanium. Key Eng. Mater.
2004, 254–256, 419–422; Plieth, W. Electrochemical Deposition: The Concept of Residence Times in Structure Development. J. Solid State Electrochem. 2004, 8, 338–345;
Molina, J. M.; Saravanan, R. A.; Narciso, J.; Louis, E. Surface Modification of 2014 Aluminium Alloy-Al2O3 Particles Composites by Nickel Electrochemical Deposition. Mater.
Sci. Eng. A 2004, 383, 299–306; Malyshev, V. V. Electrochemical Deposition of Coating from Carbide, Boride and Silicide of IV via Group Metals in Ion Melts. Poverkhnost
Rentgenovskie Sinkhronnye i Nejtronnye Issledovaniya 2004, 68–78; Choi, W.; Ko, H. C.; Moon, B.; Lee, H. Electrochemical Deposition of a Pyrrole-1-yl Substituted Perylene
Diimide for Photoluminescence and Electrochromism. J. Electrochem. Soc. 2004, 151, E80–E83; Choi, H. H.; Park, J.; Singh, R. K. Nanosized CuO Encapsulated Silica Particles
Using an Electrochemical Deposition Coating. Electrochem. Solid-State Lett. 2004, 7, C10–C12; Chang, K. L.; Chung, S. C.; Lai, S. H.; Shih, H. C. The Electrochemical Behavior of
Thermally Oxidized CrN Coatings Deposited on Steel by Cathodic Arc Plasma Deposition. Appl. Surf. Sci. 2004, 236, 406–415; Xu, Q.; Zhang, L.; Zhu, J. Controlled Growth of
Composite Nanowires Based on Coating Ni on Carbon Nanotubes by Electrochemical Deposition Method. J. Phys. Chem. B 2003, 107, 8294–8296; Smith, A.; Belomoin, G.;
Nayfeh, M. H.; Nayfeh, T. Spatially Selective Electrochemical Deposition of Composite Films of Metal and Luminescent Si Nanoparticles. Chem. Phys. Lett. 2003, 372, 415–418;
Plieth, W. Electrochemical Alloy Deposition: New Properties by Formation of Intermetallic Compounds. Surf. Coat. Technol. 2003, 169–170, 96–99; Mendoza, L.; Albin, V.;
Cassir, M.; Galtayries, A. Electrochemical Deposition of Co3O4 Thin Layers in Order to Protect the Nickel-based Molten Carbonate Fuel Cell Cathode. J. Electroanal. Chem. 2003,
548, 95–107; Mehmood, M.; Kawaguchi, N.; Maekawa, H.; Sato, Y.; Yamamura, T.; Kawai, M.; Kikuchi, K. Electro-deposition of Tantalum on Tungsten and Nickel in LiF-NaF-
CaF2 Melt Containing K2TaF7: Electrochemical Study. Mater. Trans. 2003, 44, 259–267; Malyshev, V. V.; Uskova, N. N.; Solov’ev, V. V. Electrolytic Deposition of Boron
Powders, Silicon Coatings, and Electrochemical Synthesis of Chromium Borides and Silicides. Izvestiya Vysshikh Uchebnykh Zavedenij: Tsvetnaya Metallurgiya 2003, 52–59;
Lin, S.; LeGeros, R. Z.; LeGeros, J. P. Adherent Octacalciumphosphate Coating on Titanium Alloy Using Modulated Electrochemical Deposition Method. J. Biomed. Mater. Res.,
Part A 2003, 66, 819–828; Kuntyi, O. I.; Okhremchuk, E. V.; Khoma, M. S. Electrochemical Deposition of Nickel in Aprotic Solvents. Mater. Sci. 2003, 39, 885–888.
adding 1% of Mo to the system improves both mechanical abrasion strength and corrosion resistance in acidic environments. The
UK standards for engineering coatings of Cr are DEF GUIDE D G13 and BS 4641 DEF STAN 03-14/1 (110,113,114).
7.06.7.1.1 Characteristics
1. High level of hardness (800–1000 HV), which results in resistance to the abrasion-induced wear.
2. Low friction coefficient and resistance to adhesion, which serves against adhesion-induced abrasion.
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3. Corrosion and oxidization resistance up to 800 C.

4. Strength maintenance up to 300 C.
5. The coatings with thicknesses above 50 mm require grinding polish.
6. The thickness is commonly limited to 0.5 mm, but the thicker coatings for piece repair are fabricated on a Ni substrate.
7. The crack pattern expands until the development of a structure with open porosity to retain the lubricant.
8. Tensional stresses are that much high, which lead to crack development. Thus, to provide corrosion protection, coating thickness
is not allowed to drop below 50 mm.
9. Brittle and weak against the shock.
10. Low-deposition efficiency, so the process is sensitive to the energy.
11. The hydrogen emitted in a simultaneous manner can be dissolved in the workpiece.
7.06.7.1.2 Applications
1. Plastic molds
2. Shaping and stretching molds of the metals
3. Cutting tools
4. Gauges
5. Linen of the cylindrical pieces
6. Piston rings
7. Crank shafts
8. Hydraulic hammers
9. Repair of worn pieces
7.06.7.2 Nickel
Nickel is widely applied in engineering applications to cope with mechanical abrasion, corrosion, scratch, and spalling (which is
induced by heat). The range of its coating solutions is wider than the ones for Cr. Besides, it is more preferred for deposition in terms
of economic considerations. Standards including BS 4758 and DTD 905A present the UK features of Ni. The easy utilization and the
properties of the crated deposit have made Ni widely used in electrolyte shaping, such as mold and wiredraw manufacturing or foil
and metal wire products (16,56,80,95,96,109,112,115–122).
1. Average hardness (150–450 HV).
2. Softer and more flexible compared to Cr, so involving higher resistance to scratch corrosion.
3. Corrosion resistance at 125 mm, which guarantees corrosion in various chemical media.
4. Resistance against corrosion fatigue.
5. Resistance against spalling up to 600 C.
6. There are no technical limitations about coating thickness.
7. Deposit polishing can be performed by a turning process.
8. The internal stresses are usually controllable in the deposit.
9. Tendency to spalling, which serves against even some metals in a lubricated state.
1. Hydraulic equipment, especially in submarine applications.
2. Processing of sensitive products such as food materials and textiles to prevent contamination such as staining.
3. Worn parts repair.
4. Electrolyte shaping.
Lira-Cantu et al. (123) applied 316L stainless steel as substrate for the electrodeposition of black nickel solar absorber
coating. To do so, first they electrochemically coated the substrate with a bright metallic nickel film before applying the final
black nickel coating. Employing two different current densities with an intermediate drying step in nitrogen atmosphere was
found to be crucial for the solar absorber coating. The applied current densities were around 10 and 25 mA for the first and
second deposits, respectively. The solar absorption and thermal emittance values of the sample are not significantly affected by
the slight variation of the applied current density from the original value. However, it was observed that the deposition time is
a key parameter and must be carefully controlled. Deposition times greater than 60 and 90 s were formed in high solar
absorption but poor thermal emittance for the first and second electrodeposits, respectively. The optimum electrochemical
deposition parameters for the best performance were determined as follows: for the first coating, a current density of 12.6 mA
was applied for 60 s and followed by a drying step under nitrogen; while for the second coating, it was 23.6 mA for 90 s. It was
not possible to obtain emissivity values higher than 0.1, probably due to the limitation of the stainless-steel substrate. The
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absorptivity value of the sample was improved through an antireflection coating dried at 200 C based on TEOS made by the
dip-coating technique. Nevertheless, the absorptivity values are decreased because of sample heating at 300 C due to the
degradation of the black nickel surface. The thickness of the black nickel coating was determined as 1.3–1.7 mm where this
thickness is directly influenced by deposition time. The SiO2 antireflection coating from TEOS was found to have the thickness
of about 400 nm when dip-coated at constant speed of 30 cm min1.
7.06.7.3 Chemically Deposited Ni

Based on the utilized reduction agent, the obtained deposits are typically Ni alloys containing 6–12% of phosphor or 2–7% of
boron. Here, it is possible to synthesize ternary alloys such as Ni–P–Cu and composite coatings through nonmetallic particle
submergence in a deposition solution. The standard DEF STAN 03-5/1 introduces requirements for Ni–P deposition (124).
7.06.7.3.1 Characteristics: Ni–P

1. Thickness evenness.
2. The parts can be coated up to the desired dimensions without any need for polishing.
3. The hardness at the deposited state is 400–500 HV and can even reach 1000 HV by thermal treatment at 400 C. In this state, the
obtained properties are similar to those of hard chrome.
4. Corrosion and abrasion resistance are improved compared to electrically deposited Ni.
5. Low friction coefficient.
6. Keeping the strength up to 350 C. By cooling down from higher temperatures, some extra strength is gained.
7. Coating process of the high-alloyed steels is difficult since they require initial coating of the electrically deposited Ni.
8. The utilized materials are highly expensive compared to those used in electrodeposition.
9. Preprocessing and control of the solution are very critical compared to in electrodeposition.
7.06.7.3.1.1 Applications
1. Water pump parts
2. Hydraulic and pneumatic valves
3. Plastic molds
4. Worn parts repair
Lee (56) studied the microstructure, and the mechanical, electrochemical, and wear corrosion characteristics, of electroless
nickel–phosphorus coatings on carbon-fiber-reinforced plastic (CFRP) composites. These composites are typically applied in
aeronautical and astronautical applications since they possess preferable properties such as high specific strength and modulus.
According to the experimental results, it was found that a uniform nickel–phosphorus coating can be successfully deposited on
a CFRP substrate through electroless plating after appropriate sensitization, activation, and mechanical polishing pretreatments of
the CFRP substrate. The coating also indicates excellent protection from corrosion and wear corrosion for CFRP composites. The
findings of this work demonstrated a remarkable correlation between the prepolishing condition (the corresponding surface
roughness) of the CFRP substrate with microstructure, phosphorus content, thickness, and electrochemical and wear corrosion
properties of the nickel–phosphorus coatings. Furthermore, when the substrate surface roughness was 0.3 mm, high P content
(P > 7 wt.%), low microporosity, smooth morphology, high thickness, and hardness of nickel–phosphorus coatings on the CFRP
substrate were obtained. The obtained electrochemical behavior demonstrated a strong passivity that favors enhanced wear
corrosion resistance properties.
7.06.7.4 Characteristics: Ni–B

1. Almost similar to Ni–P, but with higher hardness (500–750 HV).
2. It can be thermally treated in cases needing higher hardness.
3. Less flexibility and higher internal stress compared to Ni–P deposits.
4. Higher wear strength compared to Ni–P deposits.
5. Higher operation costs compared to Ni–P deposits.
The applications of Ni–B systems are the same as those for Ni–P ones, and providing warm hardness is considered Ni–B is preferred
(e.g., for glass molds).
7.06.7.5 Copper
Copper deposits, which are typically harder than nickel deposits, can be easily obtained from some recognized electrolytes. Copper
can also be coated through chemical deposition and then used in a large scale in the electrolyte industry. To fabricate tools such as
attrition spark tools and signal detectors in radar technology, it is possible to form copper by the electrolyte (38,86,114,120,125–134).
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1. Soft and flexible; hardness of 60–150 HV
2. Suitable electrical conductance
3. Resistance to scratch corrosion
1. Filler insert in selective surface hardening of the steel
2. Printer rollers
3. Surface lubricant in metalworking
4. Electrolyte shaping
5. Abraded parts repair
Cejkova et al. (126) applied atomic force microscopy (AFM) and scanning electron microscopy (SEM) to characterize
copper surface-enhanced Raman scattering (SERS)-active substrates prepared by electrochemical deposition. Through these
methods, one may obtain complementary information about the arrangement and size of features on roughened metal
surfaces. The surface roughness can be evaluated quantitatively in AFM, so it is possible to obtain useful information for
further investigation of the SERS phenomenon. Here, different modes were applied to prepare copper SERS-active substrates
to determine the conditions for optimum SERS enhancement. Besides, according to Raman measurements, it was found that
an acidic bath is not particularly suitable for the preparation of copper SERS-active substrates or for obtaining a good SERS
enhancement. The measured Raman spectra indicated a low S–N ratio and low intensities, plus some missing characteristic
bands. Substrates prepared from ammoniac baths indicated higher improvement in all measured spectra of the selected probe
molecules, although it is required to optimize the preparation parameters. Applying short current steps leads to the creation
of irregular copper barb-like particles that imply a relatively low enhancement (C2c, C2d). It is probable that the short time
is not sufficient for the formation of more regular copper particles. Accordingly, the duration of individual steps is a crucial
parameter for preparing the nanoscale surface morphology. In the case of prolonged time steps, the formation of regular
spherical particles of various sizes (C3 procedures) occurs. According to the findings of this work, the final current is also
a critical parameter for surface morphology sine its value, and the duration of the step affects particles size (C3b vs. C3c). It
seems that in the case of ending a current sequence of short steps with one long step with a high current value (C1
procedures), barb-like particles become coated with spherical particles (cauliflower-like surface morphology). According to
the Raman spectra obtained from these substrates, a considerably high SERS enhancement, an extremely high S–N ratio, and
high spectral intensities were indicated; besides, all characteristic Raman bands required for proper spectral interpretation
were observed. It can be concluded that it is possible to obtain good Raman surface enhancement on copper SERS-active
substrates prepared by electrochemical deposition from ammoniac baths. Copper substrates developed from acidic baths
did not indicate any efficient Raman surface enhancement. It seems that the average surface roughness value does not have
a key role, but the shape of nanostructures is of great importance. Furthermore, it was found that the composite structures
consisting of fractal spear-shaped structures with superimposed spherulite features result in the optimum SERS enhancement
from all cases tested.
Solmaz et al. (63) deposited NiCu composite coatings through an electrochemical approach on a copper electrode (Cu–NiCu).
Cathodic current–potential curves and electrochemical impedance spectroscopy techniques were applied to investigate HER activity
of the prepared electrode 1 MKOH solution. Based on the findings of this work, the NiCu coating involves a porous structure and
good electrocatalytic activity for the HER in the alkaline medium. Besides, the HER activity of the Cu–NiCu electrode was higher
than that of the uncoated Cu- and Ni-coated (Cu–Ni) copper electrodes. Also, there was found a correlation between catalytic
activities and the porosity as well as synergistic interaction of Ni and Cu.
Solmaz et al. (50) applied the electrochemical deposition approach to develop nickel (Cu–Ni), iron (Cu–Fe), and nickel–
iron (Cu–NiFe) composite coatings through different chemical compositions on a copper electrode. Next, cathodic current–
potential curves and electrochemical impedance spectroscopy techniques were employed to examine the electrocatalytic
activity of the coatings for the HER in 1M KOH solution. In comparison to the case of nickel and iron coatings individually,
the presence of nickel along with iron enhances the electrocatalytic activity of the electrode for the HER. The HER activity of
the composite coatings is highly controlled by the chemical composition of the alloys. It was found that the Cu–NiFe-3
electrodes (with a molar concentration ratio of Ni2þ:Fe2þ of 4:6 in the plating bath) have the best suitable cathode material
for the HER in an alkaline medium under the studied experimental conditions. Moreover, the change in the electrocatalytic
activity of the electrode with operation time was investigated through examination of the electrocatalytic activity of the Cu–
NiFe-3 electrode for the HER for extended periods of time. The findings of this work indicated that the HER was activation
controlled and does not change after an electrolysis process. Also, a constant current density of 100 mA cm2 was applied to
the electrolysis system, and the corrosion behavior of the Cu–NiFe-3 electrode was evaluated after different operation times
using electrochemical impedance spectra (EIS) and linear polarization resistance (LPR) techniques. In contrast, the corrosion
behavior of a Cu–NiFe-3 electrode to which no current was applied was also studied. The results of corrosion tests exhibited
that the corrosion resistance of the Cu–NiFe-3 cathode varied in the case of applying a cathodic current to the electrolysis
system.
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7.06.7.6 Cu–Sn Alloys

Copper alloying with 10–15% of Sn produces components with hardness higher than both of them.
1. Hardness of 300–400 HV
2. Rather flexible
3. Resistance to corrosion and abrasion
4. Resistance to shock
1. Sparkproof coating for head of underground drilling tools
2. Substrate for hard chromium
3. Filling insert for selective nitrification of the stainless steel
7.06.7.7 Iron
Electrically coated iron has been applied from the beginning for repair of abraded tools; however, its serious utility was highlighted
when it was found that nickel resources are limited. It is possible to use electrolyte shaping to produce Fe foils as well as hollow
roller bearings in Fe–Ni alloys (50,94,135–137).
1. Strong and cheap
2. Thermally treatable
3. Susceptible to corrosion
4. Difficult deposition process due to the need for high temperatures and, as a result, oxidization of electrolyte components
1. Soldiering of Fe nozzles
2. Scratch-proof coatings in internal combustion (IC) engines
3. Repair of abraded parts
4 .Electrolyte shaping
7.06.7.8 Cobalt
Nonalloy cobalt is widely used in computer technology due to its magnetic properties. However, alloys with 20% of Mo or W have
important engineering applications, especially in the improvement of abrasion resistance of blacksmith metals and cold-pressing tools.
Since these pieces are typically massive and the operation time is also short, the brush method can be utilized for in situ coating (138,139).
1. Approximate hardness of 600 HV
2. Low friction coefficient
3. Resistance to oxidization
4. A deposit with thickness of 12 mm, resistant to wear and metallic particles adsorption
1. Cr metalwork molds
2. Cold press tools
3. Solid lubrication
Mendoza et al. (108) optimized a room temperature electrochemical deposition process to develop a protective cobalt oxide
layer on a nickel substrate. The main objective of this project was to avoid nickel dissolution, such as the modern cathode applied in
the molten carbonate fuel cell (MCFC). Various experimental deposition conditions (i.e., imposed potential, electrolysis duration,
pH, electrolyte, and preoxidation of the substrate) were investigated. According to the findings of this work, a nitrate medium at pH
7.4, using a previously oxidized nickel substrate, at a relatively low oxidation potential yields the optimum deposits in terms of
adherence and homogeneity. Since all developed deposits were amorphous, an annealing treatment is necessary to obtain a crys-
talline structure. It was found that there is a linear evolution of the thickness with the electrolysis time experimental framework of
this work. Moreover, the X-ray photoelectron spectroscopy (XPS) characterizations conducted on the cobalt oxide films deposited
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on nickel substrates revealed that the cobalt oxide has a Co3O4 form, disregarding the degree of oxidation of the nickel substrate and
electrochemical potential during the cobalt deposit. This oxide keeps its chemical properties in the surface layers after annealing at
500 C. Annealing at 700 C modifies the cobalt oxide component into a CoO-like oxide, with the presence of oxidized nickel in the
surface. After an annealing treatment at 500 C, the presence of cubic Co3O4 was confirmed.
7.06.7.9 Pb
Pb is very important in engineering applications since it facilitates bearings’ performance when applied as overlay. The alloys might
contain Sn (10%) and In (8%), or Sn (10%) and Cu (2%).
1. Soft and flexible (hardness of 8–15 HV)
3. High wear strength through lubricant greases
4. Approximate thickness of 25 mm
Its main application is the overlay for Cu and simple base Al bearings for providing strength against harsh beginning conditions and
for preventing machining motions and entrapment of small dust particles, which prevents potential damage to the bearing or axis.
Sirés et al. (140) synthesized highly crystalline, nanostructured, 3D b-PbO2 coatings through galvanostatic deposition from
baths containing aqueous lead(II) and methanesulfonic acid (CH3SO3H). Compared to plating of b-PbO2 in HNO3, this involves
a much more environmentally friendly methodology. The deposits indicated high quality and good adherence. The crystallite was in
the size range of 20–30 nm. Besides, AFM imaging revealed very uniform, rough deposits (i.e., 255–275 nm rms). Also, the elec-
trochemical advanced oxidation processes (EAOPs) were applied to study the oxidative destruction of Methyl Orange azo dye. An
electro-Fenton process with a high-surface-area carbon-felt cathode overweighed the performance of the single anodic oxidation.
Rapid and complete decolonization was achieved following pseudo-first-order kinetics.
7.06.7.10 Sn
Same as Pb, electroplated Sn is soft, and its engineering applications are limited to adhesion-induced wear. The standards, including
BS 1872 and DEF STAN 03-8/1, involve Sn deposition.
1. Soft and flexible (approximate hardness of 12 HV)
2. Low melt temperature
3. Low friction coefficient; scratch-proof
4. Suitable for hard soldering
5. Corrosion resistant
1. Filling insert in steel nitrification
2. Corrosion protection in the absence of mechanical wear
3. Thin flash coatings for facilitation of mobile pieces installation
7.06.7.10.3 Characteristics: Sn–Ni (65/35) Alloy (Introduced in Standard BS 3597)

1. High hardness (700 HV)
2. Low friction ration
3. Corrosion resistance
4. Retains thin oil layers
5. Brittle; low shock strength
6. Strength maintenance up to 300 C
7. Potentials for brazing
7.06.7.11 Sn-Based Diffusive Alloys

Through some recent works, Sn-rich steel-based alloys have been electrodeposited and then thermally treated to obtain diffusion
alloys that contain an Fe–Sn mixture as well as the other intermetallic components distributed in a support matrix (8,90,141).
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3. Corrosion resistance
4. Wear strength when lubrication conditions are weak
5. Very low drop in fatigue strength
1. Bearings and pump tubes
2. Shoulder guide in textile industry
3. Rods and molds for punching and stainless-steel cutting
Wu et al. (59) applied cathodic deposition to develop amorphous tin oxide (SnOx) on a graphite electrode in a bath containing
0.1 M stannous chloride (SnCl2), 0.5 M sodium nitrate (NaNO3), and 0.4 M nitric acid (HNO3) in an aqueous solution of 50%
(v/v) ethanol. Then, the grown SnOx coatings on graphite were characterized as representative capacitive behaviors by cyclic vol-
tammetry and chronopotentiometric (CP) in 0.5 M KCl. Specific capacitance (in millifarad per square centimeter, Ca) linearly varies
with the deposition charge up to 4.5 C cm2, and a maximum value of 355 mF cm2 was obtained with the SnOx coating formed at
around 5 C cm2. For the SnOx coating deposited at 0.2 C cm2, a maximum specific capacitance (in farad per gram, Cm) of 298 and
125 F g1 was obtained from CVs at a scan rate of 10 and 200 mV s1, respectively. Cm values significantly decrease from 265 to
around 95 F g1 as the deposition charge rises from 0.2 to around 6.0 C cm2. The long cycle life and stability of the SnOx coatings
on graphite via the presented cathodic deposition were indicated.
7.06.7.12 Ag
Electrodeposited Ag involves a set of mechanical, electrical, and chemical properties useful for many industries. Pb-, Pd-, or Cu-
based alloys of Ag enhance its deposition temperature. The standards BS 2816, DEF STAN 03-9/1, and DTD 939 contain the
requirements for Ag deposition.
2. Thickness range of 0.001–1 mm
3. Scratch and corrosion resistance
4. Desirable friction properties
5. Suitable electrical conductance
1. Specific bearings like those for a plane fuel system
2. Electrical joints
3. Resistance to seizure at high temperatures
He et al. (116) studied the activity and stability of the chemideposited palladium–nickel foam (Pd–Ni foam) electrode
applied in the electrochemical dechlorination process. Here, silver was electrochemically deposited on a nickel foam
substrate (Ag–Ni foam) before chemical deposition of palladium. The physicochemical properties of the resultant material
(Pd–Ag–Ni foam) were characterized. The silver coating was in the form of spherical apophyses, and the palladium was
dispersed finely on the surface of the Ag–Ni foam. To study the activity and stability of the palladium catalyst, dichloro-
acetic acid was chosen as the indicator. In comparison to the Pd–Ni foam electrode, the Pd–Ag–Ni foam electrode
consistently had a relatively higher dechlorination rate and current efficiency in the case of applying the current density
range of 1.5–10.5 mA cm2. Based on quantitative analysis of the main intermediates and final products, including
monochloroacetic acid, acetic acid, and chloride ion, the improvement of electrochemical dechlorination was clearly shown
by the presence of silver. In addition, after five cycles of dechlorination, the current efficiency for the Pd–Ni foam electrode
dramatically dropped from 67 to 13%. In contrast, for the Pd–Ag–Ni foam electrode, it decreased by much less, from 78 to
62%. Moreover, the palladium loss was clearly reduced through adding a silver coating between the Ni foam and the Pd
outer layer (see Figures 5 and 6).
7.06.7.13 Au
Owing to its unique mix of properties, electrodeposited gold has very wide applications in electronic, control, and communication
equipment. The relatively soft pure gold has a hardness of 70 HV and lacks any thin surface oxide layers. Thus, it is possible that
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Figure 5 Effect of current density on the current efficiency of dichloroacetic acid (DCAA) dechlorination on Pd–Ag–Ni foam (a and c) and Pd–Ni
foam (b and c) electrodes. Initial concentration of DCAA: 30 mM; palladium loading: 1.78 mg cm2; silver loading: 5.17 mg cm2. Reproduced from
He, Z.; Zhan, L.; Wang, Q.; Song, S.; Chen, J.; Zhu, K.; Xu, X.; Liu, W. Increasing the Activity and Stability of Chemi-deposited Palladium Catalysts
on Nickel Foam Substrate by Electrochemical Deposition of a Middle Coating of Silver. Sep. Purif. Technol. 2011, 80, 526–532.
spalling occurs in involved surfaces such as sliding joints. However, using slight amounts of base metals such as Ni and Co as alloy
elements promotes hardness up to 450 HV. This factor – coupled with simultaneous deposition of an organic polymer synthesized
in a coating solution – results in improvement of abrasion resistance and expands the application range of Au alloy coatings in
electrical connections fabrication (23,25,133,142–145).
1. Hardness of pure gold (70 HV) can be enhanced through alloying with base metals such as Ni and Co
2. Low resistance to electrical connection
3. Resistance to corrosion and oxidization in a wide temperature range
4. Appropriate capability for brazing, which is retained even after keeping for a long time in the stock
1. Edges connection in print circuits
2. Transformer parts
3. Connections in electrical and electronic equipment
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Figure 6 Effect of palladium loading on the current efficiency of DCAA dechlorination on Pd–Ag–Ni foam (a and c) and Pd–Ni foam (b and c)
electrodes. Initial concentration of DCAA: 30 mM; current density: 7.5 mA cm2; silver loading: 5.17 mg cm2. Reproduced from He, Z.; Zhan,
L.; Wang, Q.; Song, S.; Chen, J.; Zhu, K.; Xu, X.; Liu, W. Increasing the Activity and Stability of Chemi-deposited Palladium Catalysts on Nickel
Foam Substrate by Electrochemical Deposition of a Middle Coating of Silver. Sep. Purif. Technol. 2011, 80, 526–532.
Liu et al. (9) applied a simple strategy of electroless deposition for gold nanoparticle (Au NP) modification on conductive
substrate. The morphology of Au NP modified electrodes could be relatively controlled through choosing various solution
concentrations, deposition times, and so on. The Au NP modification highly enhanced the electrode surface area, and the surface
area after Au NP modification on the polyelectrolyte multilayer (PEM) assembled electrode was about 3.3 times greater than that of
the planar gold electrode. The enhancement of DNA immobilization and hybridization on the Au NP modified electrode was
characterized through cyclic voltammetry and differential pulse voltammetry through applying the Ru(NH3)3þ 6 as an electro-
chemical redox indicator. Applying this approach enables reaching the sensitivity of 1 1011 M for the Au NP modified PEM
electrode for target DNA. In comparison to the planar gold electrode, the detection limit was found to rise about three orders of
magnitude. Figure 7 shows SEM images of Au NPs obtained by electroless deposition onto a planar gold electrode and a PEM (three
bilayers of PSS and PAH) modified electrode in 1 mM HAuCl4.
Montes De Oca and Fermín (146), for the first time, reported the controlled electrochemical deposition of atomic layers of Te on
3D assemblies of Au nanoparticles in acid solution. Figure 8 shows a TEM image of nanometric citrate-stabilized Au nanoparticles.
Here, citrate-stabilized Au particles with a diameter of 19.3 1.2 nm were loaded into 2D and 3D networks through the electrostatic
layer-by-layer adsorption via applying the poly-L-lysine (PLL) on In-doped SnO2 (ITO) electrodes. Based on the atomic force
microscopy and electrochemical measurements performed, it was found that the 3D assemblies comprise an open network of
electrically interconnected nanoparticles. Moreover, the electrochemical studies in the presence of TeO2 indicated two distinct
features related to one and two atomic adlayers of Te – which were selectively deposited on the Au nanocrystals. Detailed analysis of
the electrochemical responses (which is in turn as a function of the surface corrugation) indicated that the average Te coverage on
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Figure 7 SEM images of Au NPs obtained by electroless deposition onto planar gold electrode (a, b) and a PEM (three bilayers of poly(sodium-
4-styrene sulfonate) (PSS) and poly(allylamine) hydrochloride (PAH)) modified electrode (c, d) for 6 min in 1 mM HAuCl4; (b) and (d) are the cor-
responding high magnification images of (a) and (c), respectively. Reproduced from Liu, S.; Liu, J.; Wang, L.; Zhao, F. Development of Electrochemical
DNA Biosensor Based on Gold Nanoparticle Modified Electrode by Electroless Deposition. Bioelectrochemistry, 79, 37–42.
Figure 8 TEM image of 19.3 1.2 nm citrate stabilized Au nanoparticles. The histogram in the inset shows the characteristic particle size
distribution obtained from this synthesis protocol. Reproduced from Montes De Oca, M. G.; Fermín, D. J. Electrochemical Deposition of Te
Adlayers onto 3D Networks of Gold Nanoparticles. Electrochim. Acta 2010, 55, 8986–8991.
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a single Au nanoparticle is close to those seen on extended Au surfaces. The findings of this work also indicate that the surface
composition of each individual particle in the 3D assembly can be electrochemically modified at the atomic level.
Song et al. (34) appropriately deposited gold–platinum (Au–Pt) hybrid nanoparticles (Au–PtNPs) on an ITO surface through
a direct electrochemical method. Based on the findings of this work, the size of the Au–PtNPs is controlled by the number of elec-
trodeposition cycles. Au–PtNPs obtained by 20 electrodeposition cycles indicated a cauliflower-shaped structure with an average
diameter of about 60 nm. These Au–PtNPs exhibited alloy properties. Based on electrochemical measurements, it was found that the
charge transfer resistivity was considerably decreased for the Au–PtNP–ITO electrode. Furthermore, the Au–PtNPs showed an elec-
trocatalytic activity for nitrite oxidation and oxygen reduction. The Au–PtNP–ITO electrodes could possibly be applied as electro-
catalysts and sensors.
Zhang et al. (147) presented a new enzymatic amplification approach for ultrasensitive electrochemical immunosensing. The
approach uses glucose oxidase for the enzymatic deposition of gold nanoparticles on an ITO electrode surface (see Figure 9). New
gold developer solution consisting of 20 mM of glucose, 20 mM of NaSCN, 0.5 mM of p-benzoquinone (PBQ), and 1 mM of
AuCl4 dissolved in 0.1 M of pH 7.5 phosphate buffer solution – was used. The amount of deposited gold was calculated
electrochemically through surveillance of the reduction of gold oxide in an aqueous solution of 0.5 M of H2SO4, which well
corresponds to the amount of antigens in the solution. The efficiency of this technique was experimentally shown via the
construction of an immunosensor for the detection of mouse IgG by a sandwich immunoassay in a linear dynamic range of
5 pg ml1 to 50 ng ml1. Over the entire linear dynamic range of the sensor response in the serum samples, a decent mean
apparent recovery was obtained in the range of 88–102%. This implies that the immunosensor would be beneficial for testing of
proteins in real clinical samples.
Vorobyova et al. (148) indicate that EG electrolytes on the base of Sn(IV) chloride and potassium tetracyanoaurate(III) can be
utilized for Au–Sn alloy electroplating at tin content of 27–54 at.%. The most tin-rich alloys were deposited using the solutions with
Au(III) concentration as low as 0.05 mol dm3, and while Sn(IV) concentration was between 0.75 and 2.8 mol dm3. Moreover, Au–
Sn alloy coatings were deposited from the EG solution containing AuSn2, AuSn, and Au5Sn phases and an amorphous gold-rich
phase. Also, the alloy containing both Au5Sn and AuSn crystalline phases were deposited from 1.4 M solution of Sn(IV) in EG at
a current density of 15–21 mA cm2 and a rate of 1.3–1.9 mm h1. Twice, diminution in Sn(IV) content in such an electrolyte
allows increasing the rate of an alloy deposition up to 2.6–5.2 mm h1 at a small current of density 5–21 mA cm2 and obtaining the
alloy on the base of a AuSn intermetallic compound. Based on voltammetric investigations performed, there was observed the
absence of the electrode passivation during Au(III) and Sn(IV) reduction in the EG electrolyte, the proportionality of the current
density to the set potential in a broad electrochemical window, and its high reliance on Au(III) and Sn(IV) concentration in the
solution. Applying this fact allowed determination of the conditions of Au and Sn alloying through the appropriate Au:Sn ratio
(28:1) in the coatings. It must be added that Au–Sn coatings deposited from the EG electrolyte were nonporous and fine grained and
consisted of tightly packed grains 0.2–0.8 mm in size forming agglomerates with mean sizes 2–4 mm.
7.06.7.14 Pt Group Metals

Electrically deposited coatings of Pd, Rh, and Ru have various engineering appeals due to their hardness and corrosion resistance.
Therefore, the thin coatings are utilized to protect the parts against abrasion, and corrosion occurred in electronic and electric
equipment (99,149,150). The main properties and applications of them are summarized in this section.
Figure 9 Schematic of a generic electrochemical immunosensor based on a novel gold developer solution for gold nanoparticle deposition.
Reproduced from Zhang, J.; Pearce, M. C.; Ting, B. P.; Ying, J. Y. Ultrasensitive Electrochemical Immunosensor Employing Glucose Oxidase
Catalyzed Deposition of Gold Nanoparticles for Signal Amplification. Biosens. Bioelectron. 2011, 27, 53–57.
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7.06.7.14.1 Pd
Palladium is synthesized by relatively low costs and involves a hardness of 300 HV, which makes it appropriate for electrical
connections with high battery life. Pd coatings are also used to protect refractory metals such as Mo against oxidization.
7.06.7.14.2 Pt
Platinum is very resistant to corrosion. Very thin coatings of Pt applied on Ti create electrodes that are widely used for cathodic
protection purposes and in the electrochemical industry.
7.06.7.14.3 Rh
Rhodium, which involves hardness of 800 HV, can be easily deposited. It is mainly used in rotating joints in very harsh wear
conditions, mercury protection against blurring, and joints utilized at high currents that are subjected to abrasion.
7.06.7.14.4 Ru
The appeal of ruthenium is constantly increasing, and it might substitute rhodium (Rh) in some specific applications.
7.06.8 Composite Electrochemical Deposition
Simultaneous deposition potential of the hard particles has widened the application range of wear-resistant coatings in the
electrodeposition process. The available processes are based on Co and Ni with 30 volumetric percent of fine (3 m) particles
such as chromium carbide and silicon carbide. Also, other matrix metals can be utilized and simultaneously deposit
softer materials (e.g., PTFE for lubrication purposes). Chemical deposition techniques are utilized to synthesize composite
coatings since they offer coatings with even thickness. The DTD 943 standard explains deposition of composite Co–CrC coatings
(15,26,27,49,56,61,73,100,106,115,128,151–157).
7.06.8.1 Characteristics: Co–CrC

2. Oxidization and scratch resistance up to the temperature of 800 C
1. Parts of jet plane engine
2. Textile machinery parts
7.06.8.2 Characteristics: Ni–SiC

2. Wear strength is not as high as that of Co–CrC
1. Rotary engines of the IC
2. Water membrane for operations in freshwater and seawater
3. Shaping glass molds
Hu et al. produced HA–COL composite coating through three chemical techniques on NiTi SMA in MSBF with high concentrations of
Ca and P ions and water-soluble type I COL. ELD coating had relatively flat and smooth surfaces, composed of strip-like crystals with
a length and width of 5–7 mm and 1 mm, respectively. Once ELD coating was resoaked in MSBF for several days, the newly developed EBG
coating was a denser, thicker, and more favorably crystallized HA–COL composite coating. In addition, the c-axis of HA oriented parallel
to the longitudinal direction of the COL fibril in BG and EBG coating, and this orientation was similar to the nanostructure of natural
bone tissue. According to the OCT-1 osteoblast-like cells culture test, it was found that the cells had a polygonal shape with filopodia on
BG coating, while the rather rounded and flat cells spread dispersedly on ELD and EBG coating. Based on the cell proliferation number, it
was deduced that the HA–COL composite coating prepared by the BG approach involve more favored properties in cell biocompatibility
since they have various surface roughness and crystal arrangements. According to the findings of this work, BG was a better technique
compared to ELD in preparing an active cell-responding HA–COL composite coating in acid MSBF (73).
Molina et al. (100) proposed a novel approach to modify the surface of aluminum matrix composites (AMCs) through elec-
trochemical nickel deposition. They performed a deposition process in a stirred standard Watt’s bath, where the potential and time
were adjusted to optimize coating characteristics. The method – which allowed one to cope with the serious problems associated with
electrochemical deposition of an inherently inhomogeneous material – was applied in nickel coating composites of 2014 aluminum
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alloy–15 vol.% Al2O3 particles. Coatings with a good adherence and thickness up to 60 mm were easily synthesized. To improve
surface properties, the coated composite was subjected to relatively long (from 10 to 47.5 h) heat treatments at a temperature of
520 C. This process improved the uniformity of the deposited layer and formation of Al–Ni intermetallics, namely, Al3Ni2.
Qiu et al. (26) used NiTi alloy as biomaterial because of its unique properties, but the high content of Ni (about 50 at.%) in
biomedical NiTi caused concern. Here, hydroxyapatite and hydroxyapatite–zirconia composite coatings were directly electro-
deposited on a NiTi alloy surface. In the case of adding ZrO2 into the electrolyte, the morphology of HAP was changed from thin
flake-flower-like crystals to needle-flower-like ones, and a denser coating was obtained. Moreover, HAP crystal grains in the coating
were preferentially arranged in the (001) direction. Addition of ZrO2 might enhance the bonding strength between the coating and
the substrate. Furthermore, the corrosion resistance of NiTi in the simulated body fluid was significantly improved at 37 C by
almost 60 times through the electrodeposition of the hydroxyapatite–zirconia composite coating.
Smith (106) presented a procedure for selective deposition of Si nanoparticles thorough applying an electrochemical process,
where a conducting substrate was soaked in alcohol in which the particles are suspended. Positive biasing of the substrate relative to
a platinum electrode draws the Si particles to the substrate. Based on a fluorescent spectroscopy test, it was indicated that the
deposited particles retain the high luminescence efficiency and spectral distribution properties of the dispersed state. The process is
employed to deposit composite thin films of metal and Si nanoparticles. Furthermore, dielectric masking enabled selective area
deposition. These processes can be useful for flat-panel or flexible particle-based displays.
Owing to the enhanced properties exhibited by metal matrix composite coatings reinforced with nanosized particles, they have
recently gained an appeal in science and technology. Ni–SiC composites have found a large number of applications for the
protection of friction parts in the automobile industry. The effects of parameters such as SiC content, current density, and stirring
speed are investigated in the microhardness of nanocomposite coatings. Here, a correlation was found between the improved
microhardness and the reduction in crystallite size determined by X-ray diffraction tests. The impact of nano-SiC incorporation in
a hardened Ni–Co alloy matrix was also studied. The findings of this work indicated that for 28 wt.% Co content in the matrix, the
microhardness was higher compared to 70 wt.% for a given nano-SiC content. This can be attributed to the crystal phase of
Ni–28Co–SiC being in the face-centered cubic (fcc) phase compared to the hexagonal close-packed (hcp) phase indicated
by Ni–70Co–SiC. In addition, a pin-on-disc wear tester under dry sliding conditions was applied to study the wear resistance of pure
Ni, Co, and nanocomposite coatings. Based on volumetric wear loss data, the wear resistance of Ni–SiC nanocomposites was found
to be better than that of pure nickel deposit. Moreover, the wear resistance of Ni–Co composites was found to be higher than that of
Ni composite. The wear behavior of Ni and Ni–28Co composites corresponded with Archard’s law. However, the higher wear
property displayed by the Ni–70Co–SiC composite followed the reverse of Archard’s behavior (158).
Wang et al. (152) synthesized fluoridated hydroxyapatite–titanium dioxide nanocomposite coating using a modified electro-
chemical deposition technique. To do so, F ions, nanoscale TiO2 particles, and 6% H2O2 were added into the electrolyte, and then
ultrasonication was performed to prepare this nanocomposite coating. Also, the microstructure, phase composition, dissolution
rate, bonding strength, and in vitro cellular responses of the composite coating were examined. The findings indicated that the
composite coating was uniform and dense because of the H2O2 and ultrasonication influences. The thickness of the composite
coating was w5 mm. It was shown that nanoscale TiO2 particles were imbedded uniformly between FHA crystals. The addition of F
and TiO2 decreased the crystallite size and increased the crystallinity level of HA in a FHA–TiO2 composite coating. In addition, the
composite coating indicated a higher bonding strength and lower dissolution rate compared to the pure HA coating. Also, the in
vitro bioactivity of the FHA–TiO2 composite coating was not affected compared to the pure HA coating.
7.06.9 Hard Anodizing
Aluminum alloys can be easily applied with, for example, Cr to improve wear strength of the coating, but hard anodizing
introduces a useful alternative technique. Although this technique is applicable for most alloys, those with greater than 3% Cu or
7% Si require further treating operations. The standards BS 5599 and DEF STAN 03-26/1 indicate UK characteristics for hard
anodizing.
2. Wear strength is not comparable to that of hard Cr
3. Thickness of 25–75 mm, and in some cases even up to 175 mm
4. Porosity can be sealed with lubricants
5. Brittle and irresistible to shock
6. It can be sealed to enhance corrosion resistance, although this reduces its wear strength
7.06.9.2 Applications
1. Transportation industry, especially aerospace
2. Hydraulic valves
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Table 3 Guidelines for selection of an engineering electrodeposited coating
Resistance to Protection against Wear resistance at Ease of Ease of The relative costa
sudden loading corrosion ambient temperature machining deposition (A ¼ the minimum cost) Coating
2 1 6 1 3 D Cr
6 5 1 6 6 A Electrodeposited Ni
4 6 Thermally treated 5 5 F Electrodeposited Ni with 9% of phosphor
1 4 3 3 4 B Sn–Ni (65:35)
5 3 2 4 1 E Co composite–CrC
3 2 5 2 2 C Anodized hardened Al
a
The costs depend on various factors such as workpiece and production rate – particularly in chemically deposited Ni.
Note: 1 is the minimum or worst; 6 is the highest or best.
3. Machining with high speed

4. Injection molds as economic alternatives for stainless steel
5. Self-lubricant surfaces
7.06.10 Selection
Abrasion is a complicated process, and generally more than one form of it is effective in a process. For instance, a parts surface can be
subjected to a relative motion in a corrosive solution containing abrasive powder. In this state, the designer chooses a hard coating
material such as Cr for the wear strength for scratch, attrition, and corrosion resistance. The low friction coefficient to deal with
adhesion-induced abrasion is along with scratching or spalling. In this state, chemically deposited Cr or Ni is the natural choice;
however, the softer coatings such as electrodeposited Cu or Ni are preferred to deal with scratch corrosion. The development of
abrasion-resistant coatings in which the hard particles are simultaneously deposited with a matrix metal (usually Ni or Co)
enhances the designing capabilities of surface operation. Hard particles applied for abrasion resistance are typically CrC or SiC, but
the softer materials such as molybdenum disulfate can be used for lubrication. It is also possible to apply chemical deposition
approaches for the synthesis of composites with unified thickness. To select a coating, the designer should pay attention to factors
such as facility of the machining process and shock resistance. Table 3 indicates appropriate guidelines about most important
electrodeposited engineering coatings. The mentioned criteria are general and theoretical, and can be useful as approximate guides.
It must be noted that it is required to consult with an expert industrial coater before making any decision about selecting a suitable
coating (6,21,22,26,36,38,59,70,73,91,105,113,126,138,142,159–165).
7.06.10.1 Design
The electrochemical deposition must be considered as an integrated part of the synthesis process. Also, the designer has to consult
with the coater in the initial steps to obtain the optimum results. The main characteristics of electrodeposited coating are deter-
mined by the following factors:
1. The utilized electrolyte system
2. Lack of local homogeneity of current density on the working piece
3. Dependency of deposition rate on current density, deposition time, and deposition range
The other general properties are disability for filling the holes, smoothing of the rough surface of the materials, and appropriate
removal of the defects. Although it is possible to deposit some coatings on such defects, the deposit will develop a weak bond with
the substrate. Besides, the cracks or surface stresses entrap air and gas bubbles, prevent effective control of the solution, and result in
a poor coating process. Generally, the electrolyte system is not under the control of the designer, but he can perform various actions
to reduce problems and complications induced by the other factors and contribute to an effective coating process
(3,9,44,65,92,95,96,107,124,166–175).
7.06.10.2 Piece Design

The principle of this process is avoiding sharp edges, intense changes in the section, closed spaces, and lumps and traps for
entrapment of dissolved or gas bubbles. Once it is required to couple and coordinate developed coatings, it is required to consider
the allowable level for coating thickness and variations of this thickness. For instance, recesses improve the evenness of the
deposition process. Since the coated pieces are required to be electrically connected to a circuit, their maintenance has to be per-
formed in a proper manner. Sometimes, this state is provided by designing bundles spaced from the piece surface that can be easily
removed after coating. Besides, these bundles can facilitate maintenance in the surface treatment and polishing step.
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Desirable Undesirable Desirable Undesirable
Round or recessed holes The sharp edges in the holes result Decrease of entrapment risk by The folded edge on the plate and
lead to unified coating in strong coating in the edges opening the edge closed circle confine the solution
of the holes’ edge
Recesses result in heterogeneous Creation of temporary holes in the The hollow objects can confine the
current distribution hollow objects leads to rapid process solution
segregation of the solution and
effective submergence
Reinforcing bands must have a flat Slight bend yields higher final quality The sharp bend leads to stress
and rather wide section as well as improved structure development in the deposit
The minimum curvature This state results in solution The outer edges should be flat Like the above state
radius of the internal confinement and then poor
surfaces must be throw power
12.5 mm
Removal of the edges and sharp The blades have to be wider and This shape creates various under-
corners of the slots with round edges stress spots in coating
Less overlapping reduces Wide overlap in plates joining The corners and edges of the recesses The sharp angles and recesses result
the solution confinement must be rounded, and their radius in solution confinement and the
effect has to be a minimum of one-fourth creation of stress concentration
of its depth spots
Reduction of bond zone Like the above case (butt welding) The blocked holes must be shallow This state results in low thickness of
decreases the solution and have round corners. Creation the coating in the recess’ bottom
entrapment risk of a hole prevents solution or gas spots with stress concentration
confinement
Since insoluble particles in the solution might deposit on the upper surface of the piece and, in turn, make it rough and reduce
its corrosion resistance, the designer should come up with a solution to place ineffective surfaces of the piece in an upside down
position during the coating process. Although barrel coating does not have many limitations of cell coating, it involves some
specific requirements, such as design considerations. Regarding uneven distribution of the final surface in the barrel, which is
created through the coating effects between neighboring pieces, it is worth mentioning that the flat pieces such as the washers can
be corrugated to avoid their sticking together. The hollow pieces also cannot be easily coated; thus, it is required to install some
slots in them for solution discharge.
7.06.11 Process Design for Cell Coating
Deposit thickness depends on current density, and thus it is greater in the edges, corners, and lumps, while it is less in the center of
wide and extensive areas and surface-recessed areas. Thus, even in a flat sheet, there will not be an evenly distributed current, and
subsequently no unified deposit is developed. Once efficiently coating the surface, it is possible to cope with uneven distribution of
the deposit through even current distribution, for example:
1. Proper installation of the anodes and their sizes
2. Using anodes with a shape rather similar to that of the surface or coating target surface
3. Install the extra cathode, which is electrically attached to the cathode in the vicinity of the areas with high current density, and
then decrease the deposit amount in those areas
4. Application of nonconductive protective shields to reduce the current in sharp edges
7.06.11.1 Substrate Materials

In all metals and the majority of the plastics used in engineering applications, it is possible to utilize the synthesized coatings
through electrical deposition, but in some specific cases some consideration and surveillance are required. The pressure on plastic
substrates depends on process temperature and compatibility. However, some steels are sensitive to the released hydrogen –
which itself is a contradicted process in electrical deposition. The hydrogen ions in the electrolyte are converted into atomic
hydrogen, which can quickly diffuse into the workpiece. This brittleness risk imposed by the hydrogen occurs whenever tensional
strength of the steel is above 1000 N mm2 or when the steel is subjected to the process of cold work before coating. Thermal
treatment at 200–250 C after the coating process emits hydrogen. Here, it is preferred to stress relieve the pieces before their
electrical coating.
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7.06.11.2 Surface Preparation

Substrate surfaces should be clean and polished, without any effective holes or chips produced by machining or polishing, or defects
such as cracks. Through efficient design of the current, it is possible to avoid these chips. Here, mechanical delicate polishing can be
the most effective. Precleaning involves degreasing by the solvent or an alkaline electrolyte bath, and then the pieces have to be
compatible with these processes. It is worth mentioning that the precleaning process is the responsibility of the coater. To prevent
unplanned coating, the areas with no need for the operation can be filled or covered using the band, seal, or appropriate coater or
print sheet. Also here, the workpiece is required to fit with the selected technique. To avoid problems, likewise all other coating
steps, it is very essential to conduct a consult between the customer and the coater.
7.06.11.3 Polishing
To prevent coating destruction, it is necessary to avoid reshaping the coated pieces, but some treating operations such as polishing
can be carried out just in case. It is ideal that the final surface of the coating be very similar to that of the main piece, although for the
pieces with closed tolerance, a machining process is necessary. If electrodeposition is performed in a way that the deposit is sub-
jected to tension, the fatigue strength drops. For pieces undergoing stress, such as plane parts, to deal with polish tensions, it is
required to perform balling operations before the coating to apply compressive stresses in substrates. The other stresses can be
decreased through thermal treating, where in this state the mechanical properties of the coating and substrate are not affected
unnecessarily. The coatings on plastic substrate cannot be stress relieved through the techniques mentioned here; in such cases, it is
required to select the electrodeposition process to minimize residual stresses.
7.06.11.4 Technical and Inspection Characteristics and Quality Guarantee

The designer is needed to determine these points: important surfaces on the piece, the coating targets, the coating cases, thickness
and tolerance distribution, coating hardness and other mechanical properties, coating appearance, and the other considered
requirements. The coater gives some advices about product and final surface shape and some suggestions about the cleaning
process, restrictions, coating, and so on. An approach for sampling and inspection processes that responds to these requirements
and an approach to move pieces rejected in the laboratory must be applied through consulting with the coater. Many of the
standards offer details of technical and inspection characteristics, but it must be emphasized that nondestructive tests for thin
coatings (with any nature) are limited and therefore play a key role in the quality of the piece used as the critical piece.
7.06.12 Application of Electrochemical Deposition for Micro- and Nanocoatings

7.06.12.1 Metallic-Based Coatings
Arrebola et al. (88) synthesized very uniform films of pure LiNi0.5Mn1.5O4 spinel on an Au substrate. To do so, they used the spin-
coating stoichiometric amounts of Mn(CH3COO)2 and Ni(CH3COO)2 dissolved in deionized water, and Li(i-OC3H7) dissolved in
a 1:2 CH3–COOH–i-C3H7OH mixture. Then, the obtained gel was transformed into a spinel through its calcining at a temperature
range of 400–800 C. In the next step, galvanostatic and potentiostatic measurements were applied to determine their electro-
chemical properties. The spinel was developed at 400 C with an earthworm-like shape, whose origin is ascribed to the formation of
a layer of undecomposed organic components. At 800 C, the film indicated noticeably improved crystallinity. Moreover, at this
temperature, the spinel particles adopted a polyhedral shape of submicron size with well-defined edges and faces, which in turn lead
to the interparticle connectivity. It was found that nickel atoms exist in two chemical environments, including Ni2þ and Ni3þ, where
the former is the major component. The obtained potentiostatic curves corresponded to the spinel formula since they present two
well-defined peaks in the 4.6–4.8 V region associated with the Ni2þ / Ni3þ / Ni4þ processes. Furthermore, both potentiostatic
and galvanostatic curves were consistent with a reversible Li insertion–extraction reaction. Nevertheless, the cells indicated
considerable overcharge probably because of the electrolyte decomposition catalyzed by gold. According to the findings of this
work, the obtained thin films deliver capacities around 148 mAh g1 and retain them effectively on the extended cycling. However,
rather low coulombic efficiency (around 50% at the 50th cycle) was shown for the deposits. By an increase in the film thickness,
coulombic efficiency increased to 85%, but the delivered capacity decreased. This can be attributed to increased resistance of the
electrode, although the capacity retention on cycling was maintained.
Atyaoui et al. (176) presented their findings for cerium doping effects on the photoluminescence properties of porous silicon.
Here, cerium was deposited through electrochemical deposition on porous silicon prepared by electrochemical anodization of
P-type (100) Si. Figure 10 shows 3D AFM images of an untreated porous silicon layer and porous silicon layer treated with Ce at
different times. Based on photoluminescence spectroscopy, it was indicated that the cerium-treated porous silicon can result in an
increase in photoluminescence when it is irradiated by light in comparison to the porous silicon layer without cerium. The results
indicated that the enhanced photoluminescence may be attributed to the change of Si–H bonds into Si–O–Ce bonds and to a newly
developed PS layer during electrochemical Ce coating.
Bajat et al. (177) obtained an electrochemically deposited Zn–Co alloy with optimum corrosion properties using a chloride bath
with higher Co2þ content (16 g dm3) at 5 A dm2. Besides, they indicated how the steel surface modification with this Zn–Co alloy
promotes the corrosion stability of a protective system based on an epoxy coating, compared with an epoxy coating on steel. During
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Figure 10 3D AFM images of (a) an untreated porous silicon layer and a porous silicon layer treated with Ce for (b) 3 min, (c) 5 min, and (d) 7 min.
Reproduced from Atyaoui, M.; Dimassi, W.; Monther, G.; Chtourou, R.; Ezzaouia, H. Electrochemical Deposition of Cerium on Porous Silicon to
Improve Photoluminescence Properties. J. Lumin. 2012, 132, 277–281.
the initial time of exposure to 3% NaCl, the electrochemical properties of the epoxy coating are not affected by the substrate
type; rather, they affect the sorption characteristics and the thermal stability. For both the surfaces, the kinetics of hydrogen
evolution during electrodeposition of the epoxy coating is almost the same. However, the lower wettability of the steel surface
results in accumulation of hydrogen on the cathode that, during subsequent curing leaves, generates more vacancies in the polymer
net and leads to the development of a more porous epoxy structure on a steel surface. As a result, the D(H2O) value for epoxy
coating on steel is higher compared to that of Zn–Co-coated steel. Besides, the amount of water absorbed inside this epoxy coating is
greater, which in turn results in lower overall corrosion stability. The corrosion stability of the protective system is significantly
improved by the Zn–Co alloy during a prolonged exposure time. Moreover, the Rp values remain constant over the entire studied
time because of the development of a passive layer of corrosion products, which serve as a good barrier to the transport of water,
oxygen, and electrolyte ions. Also, epoxy coating indicated appropriate adhesion on steel modified by Zn–Co, whereas the pro-
longed exposure time leads to epoxy coating detachment from the steel surface. This behavior is rather similar to the protective
system with Zn–Ni alloy coating. Owing to a more efficient crosslinking induced by the smaller porosity of this epoxy coating, the
thermal stability of epoxy coating on steel modified by a Zn–Co alloy is enhanced.
Boiadjieva et al. (178) investigated the electrochemical deposition and dissolution of Zn on Pt electrodes in sulfate electrolyte
through electrochemical methods. The main objective of this study was to contribute to a better understanding of the more complex
Zn–Cr alloy electrodeposition process. The current efficiency for the Zn reaction reduces by a decrease of the Zn electrolyte pH (from
5.4 to 1.0) so as to minimize or avoid the creation of hydroxo-products of Cr in the electrolyte for deposition of alloy coatings.
However, the cathode reaction rate considerably enhances because of the intense hydrogen evolution. According to the investi-
gations performed in Zn electrolytes with pH 1.0–1.6, it was observed that Zn bulk deposition is preceded by hydrogen evolution,
stepwise Zn underpotential deposition (UPD), and the development of a Zn–Pt alloy. Hydrogen evolution from H2O initiates in
the potential range of Zn bulk deposition. The assumption that electrochemical deposition of Zn proceeds at potentials more
positive than the reversible potential of Zn is further supported by the data obtained from electrochemical quartz crystal micro-
balance (EQCM) measurements. Using the anodic potentiodynamic curves for galvanostatically and potentiostatically deposited Zn
layers, it is possible to obtain some indirect evidence about the dissolution of Zn from an alloy with the Pt substrate. The expected
codeposition potential of Cr (1.9 V vs. Hg–Hg2SO4) is reached at a current density of about 300 mA cm2.
Hu et al. (179) explored the electrochemical deposition behavior of calcium phosphate coating using an aqueous electrolyte
with very dilute calcium and phosphorus species (Ca–P). The influences of temperature, current density, and duration were
studied in a systematic way, and the basic mechanism was comprehensively analyzed. Based on the observations of this work, in
a wide range of temperature and current densities, coating is mainly composed of hydroxyapatite. The temperature significantly
influenced the deposition velocity. Next, the apparent activation energy of 174.9 kJ mol1 was subsequently obtained, which
indicates the mass transfer control mechanism for the coating growth. It was also found that current density is a key factor for
structure controllability. Data of DRFTIR or Raman spectroscopic tests for the initial deposition phase highlighted the instan-
taneous and direct deposition of hydroxyapatite coating on the substrate; neither induction period nor precursor was detected in
this dilute Ca–P electrolyte system. A phase diagram of the Ca–P electrolyte system was developed. The diagram gave
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a thermodynamic explanation for the direct single-phase hydroxyapatite precipitation observed only in this system, but not in
traditional concentrated systems.
Lin et al. (7) report the formation and characterization of the I–III–VI2 semiconductor compound CuInS2 (CIS) on gold
substrate at room temperature through the electrochemical atomic layer deposition (EC-ALD) method. They applied the cyclic
voltammetry technique and amperometric I–t method to determine the optimum deposition potentials for each element in order to
prepare the semiconductor compound. It was found that the CIS thin films have a (112) preferred orientation. Moreover, the XPS
analyses of the films reveal that Cu, In, and S are present in an atomic ratio of about 1:1:2. In addition, their semiconductor band
gaps were determined as 1.50 eV by FTIR.
Muralidhara et al. (64) deposited nanocrystalline zinc coatings from an acid zincate bath containing freshly synthesized
condensation product. Here, Hull cell experiments were carried out to investigate the effects of bath constituents, pH, temperature, and
current density on the deposit nature. In addition, parameters such as current efficiency, throwing power, cathodic polarization,
and corrosion behavior were studied in 3.5 wt.% NaCl under an optimum concentration of additives. Based on salt spray testing and
electrochemical measurements, it was found that the nanocrystalline zinc coatings have higher corrosion resistance compared to the
zinc coatings deposited from a simple acid zincate bath without additive. Addition of condensation product of thiamine hydrochloride
(THC) and furfural (FFL) resulted in a more uniform nanocrystalline deposition, with the grain sizes varying from 20 to 22 nm.
Peng et al. (85) reported the electrochemical deposition of adherent and optically semitransparent thin calcium phosphate
(CaP) films on titanium substrates in a modified simulated body fluid (SBF) at 37 C. Coatings deposited by applying the periodic
pulsed potentials demonstrated favored adhesion and mechanical properties compared to those deposited via applying a constant
potential. The coatings indicated a polydisperse porous structure with pores in the range from a few nanometers to 1 mm. In
addition, X-ray diffractometry and the O(1s) satellite peaks in X-ray photoelectron spectroscopy imply that the coatings have
a surface chemistry similar to that of natural bone minerals. These findings were confirmed via inductively coupled plasma optical
emission spectrometry, which yielded a Ca:P ratio of 1.65, close to that of hydroxyapatite. Based on contact mode AFM, it was found
that the average thickness of the coatings was on the order of 200 nm. Moreover, the root mean square (RMS) roughness values,
derived by AFM, were found to be much higher on the titanium–CaP surfaces compared to the untreated titanium substrates; the
RMS values were about 300 and 110 nm, respectively. According to the cell culture experiments, it was found that the CaP surfaces
are nontoxic to MG63 osteoblastic cells in vitro and are able to support cell growth for up to 4 days. This is higher than the
performance of the untreated titanium surface in a direct comparison. These easily prepared coatings show a promising ground for
hard-tissue biomaterials.
Plieth (99) introduced the concept of the residence time of an atom in a kink position to predict the structure of electro-
chemically deposited surface coatings. To obtain the residence time, the reciprocal value of the rate constant for separation from the
kink position was applied. Here, residence times and deposition rates indicate the density of kink positions [ksp] on the growing
metal film. For equilibrium conditions (Nernst potential), the density of kink positions [ksp]0 is controlled by the exchange current
density i0 and the residence time s by the equation:
i0 sNL
½ksp0 ¼ ;
zF
where NL is Loschmidt’s or Avogadro’s number, F is Faraday’s constant, and z is the charge of the metal ions in the electrolyte.
Calculated values of residence times are indicated for pure metals and for silver–lead and nickel–aluminum alloys.
Rakngarm et al. (53) applied the cathodic polarization to perform the electrochemical depositions of CaP film on commercially
pure titanium (CP–Ti) and Ti–6Al–4V in two kinds of electrolytes, including mono-calcium phosphate monohydrate (MCPM)-
based aqueous solution and supersaturated calcium phosphate solution (SCPS). The CaP coating layer was successfully deposited
on CP-Ti and Ti–6Al–4V under 3 mA cm2 current density for 45 min. The main phases observed in the film included DCPD
(brushite) coexisted with octacalcium phosphate (OCP). After being soaked in the revised simulated-body-fluid (r-SBF), the
amorphous bonelike apatite became a single phase within a day for the sample obtained from MCPM electrolyte. The specimens
obtained from SCPS electrolyte took a week to complete apatite precipitation in r-SBF. Based on this preliminary research, the
highest critical load of 87.2 N was obtained from the as-deposited rodlike DCPD on CP-Ti substrate. For all specimens, the critical
load was decreasing almost 50% after apatite precipitation in r-SBF. The decrease of critical load can probably be attributed to the
loosening of the film structure during a soak of the samples in r-SBF. The films had an average thickness of 44–55 mm, which
satisfied the qualification for using as an implant material.
Supicova et al. (75) studied the electrolytic deposition of Ni on a paraffin-impregnated graphite electrode. To do so, they used
supporting chloride electrolyte (0.5 mol dm3 NaCl) adjusted to the required pH using dilute HCl. The influence of electrolyte
composition on the Ni electrodeposition is investigated through the linear sweep voltammetry in the cathodic region. In addition,
an elimination voltammetry process was conducted to investigate the polarization curves. The main objective of this project was to
deduce the mechanism of Ni reduction in the chloride bath, plus the influence of boric acid on it. It was found that the positively
charged NiClþ ions are the electroactive particles in the Ni reduction mechanism. The strong competition between the NiClþ, Cl,
and Hþ ions for active sites at the electrode was elaborated. Moreover, the kinetically controlled adsorption or desorption processes
of various species were confirmed through elimination voltammetry with a linear scan. Study of gaseous hydrogen, catalyzed by the
freshly deposited Ni, took place along the electrodeposition process. The presence of boric acid at a considerably high concentration
level prevents deposition of Ni and, simultaneously, improves the morphology, brightness, and the adhesion of the deposited Ni.
Elimination voltammetry with a linear scan was found to be an adequate way to evaluate current–potential curves that reflect the
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electrodeposition of one-component Ni coatings. Through eliminating selected currents, some other piece of interesting and helpful
information can be obtained from voltammetric data.
The superhydrophobicity of plant leaves is an advantage induced by the hierarchical structures of their surfaces. Recently, these
structures have been imitated to produce synthetic surfaces. A novel approach was applied for the fabrication of biomimetic
hierarchical structures through applying electrochemical deposition of a metal on porous alumina. Here, an aluminum specimen
was anodically oxidized to obtain a porous alumina template. Such a template was used as an electrode to create a surface with
microstructures via electrochemical deposition of a metal such as nickel and copper after the pores enlargement. Surprisingly,
a hierarchical structure with nanometer pillars and micrometer clusters was created in the pores of the template. The nanometer
pillars were detected by the nanometer pores. Development of micrometer clusters can be attributed to the thin walls of the pores
and the crystallization of the metal on a flat surface. Using the as-prepared biomimetic surfaces, it was allowed to obtain lotus-leaf-
like superhydrophobic surfaces with nickel and copper deposition (180).
7.06.12.2 Ceramic-Based Coatings

Ban and Maruno (172) applied an electrochemical method in simulated body fluid at 5–62 C to deposit CaP coatings on titanium
plate. Based on performed X-ray diffraction (XRD) and Fourier transform infrared (FTIR) studies, it was found that the deposits are
amorphous at 5, 22, and 37 C, where as those at 52 and 62 C have Mg(OH)P, CaCO3, and carbonate apatite of poor crystallinity.
The calcium, magnesium, and phosphorus contents of the deposit increased in direct proportion to the square root of the loading
time of the cathodic potential. Here, all regression lines indicated induction periods, which is assumed as the time needed to reduce
the pH of the electrolyte around the cathode through the creation of H2 gas and to start deposition of CaP. In this temperature range,
the diffusion process is a rate-determining step in the electrochemical synthesis of CaP.
Chu et al. (181) examined the electrochemical behavior and corresponding mass variation of amorphous manganese oxide
(denoted as a-MnOx) in a simultaneous manner in a neutral electrolyte (see Figure 11). Here, the used electrolyte contained 10 mM
Na2SO4. To do so, cyclic voltammetry with a quartz crystal microbalance (QCM) was applied in the absence or presence of NaHCO3
or Na2HPO4. Then, a-MnOx was anodically deposited on the gold-sputtered quartz electrode using a potentiostatic method at 1.0 V
Figure 11 Surface morphologies of (a) a bare EQCM electrode, and (b) surface and (c) cross section images of an a-MnOx-coated EQCM electrode.
Reproduced from Chu, Y. H.; Hu, C. C.; Chang, K. H. Electrochemical Quartz Crystal Microbalance Study of Amorphous MnO2 Prepared by Anodic
Deposition. Electrochim. Acta 2011, 61, 124–131.
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for 60 s. SEM was applied to study the morphology and microstructure of a-MnOx with various potential windows of CV cycling in
the electrolyte (see Figure 12). Based on the findings of this EQCM study, it can be claimed that a-MnOx is unstable between 1.0 and
1.2 V in 10 mM Na2SO4 because of considerable dissolution of a-MnOx. The electrocatalytic activity of a-MnOx can be enhanced for
oxygen evolution through the repeated potential cycling – which also accelerates a-MnOx dissolution. Through the creation of
insoluble manganese carbonate or adsorption of phosphate by adding NaHCO3 or Na2HPO4 in the Na2SO4 electrolyte, it is
possible to successfully suppress the dissolution phenomenon and oxygen evolution. This, in turn, enlarges the potential window
for the charge and discharge of a-MnOx.
Ho and Yen (87) studied a novel method of electrolytic indium oxide coating in In2(SO4)3$9H2O aqueous solution. Here, three
major reactions were verified by cathodic polarization tests: (1) O2 þ 4Hþ þ 4e / 2H2O (w0.6 to 0.25 V); (2) 2Hþ þ 2e / H2
(0.25 to 0.6V); and (3) 2H2O þ 2e / H2 þ 2OH (0.6 to 1.5 V). There were four recognized steps for the TGA curve of the
as-coated films. The first and second were the evaporation of physical water from 2In(OH)3 surface between 20 and 200 C,
transformed into 2InOOH by the removal of 2H2O from the gel bulk (corresponding to 10% weight loss, between 200 and 300 C),
and finally condensed into In2O3 and H2O. The In2O3-coated film with thickness of about 100 nm indicated great adhesion with
substrate. Besides, the particles indicated a uniform distribution in terms of the particle shape, size, and texture. Figure 13 shows
SEM micrographs of the In2O3-coated and -annealed film.
Hsieh et al. (182) applied cathodic electrochemical deposition to deposit vertically aligned ZnO nanorod arrays with various
heights on the ZnO-seeded ITO substrate from zinc nitrate at 60 and 80 C. As-grown ZnO nanorods indicated the presence of Wurtzite
crystal structure, and their heights can be well controlled by different deposition times. The fluorination coating tends to induce
a superhydrophobicity of ZnO nanorods (i.e., the maximal value of contact angle: 166.9 ). An explanation for the observed extreme
water repellency can be the confined air layer in the nanorod arrays, which in turn results in water droplets sitting on the ZnO surfaces.
This phenomenon is known as the Cassie state. Interestingly, it was found that their water contact angles vary with the heights of ZnO
nanorods, ranging from 99.8 to 746 nm (see Figure 14). It is possible to appropriately predict the superhydrophobicity of ZnO surfaces
Figure 12 (a) Cyclic voltammograms and (b) m–E curves of a-MnOx measured between 0.2 and 1.2 V at 25 mV s1 for five cycles in 10 mM Na2SO4.
The solid lines stand for the positive scans, and the dashed lines represent the negative scans. Reproduced from Chu, Y. H.; Hu, C. C.; Chang, K. H.
Electrochemical Quartz Crystal Microbalance Study of Amorphous MnO2 Prepared by Anodic Deposition. Electrochim. Acta 2011, 61, 124–131.
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Figure 13 SEM micrographs of the In2O3-coated film annealed at 500 C for (a) surface morphology and (b) a cross-sectional view. Reproduced from
Ho, W. H.; Yen, S. K. Preparation and Characterization of Indium Oxide Film by Electrochemical Deposition. Thin Solid Films 2006, 498, 80–84.
through a proposed model that is capable of determining the wetted fraction of ZnO pillars. This satisfactory result would enable one
to understand how the variation of rod height induces the superhydrophobic behavior of ZnO nanorod arrays.
Huang et al. (183) produced hydroxyapatite coatings through electrochemical deposition and posthydrothermal synthesis.
Particularly, the mechanism and kinetics of hydrothermal synthesis were studied. Moreover, the influence of temperature and time
on the hydroxyapatite formation rate was investigated. The electrochemical deposition coatings are composed of CaHPO4$2H2O
crystals, which are converted into needle-like hydroxyapatite crystals after posthydrothermal treatment. The hydroxyapatite content
of the coatings rises with the treatment temperature and time. The synthesis rate also rises with the pH value of the water.
Development of hydroxyapatite coatings is attributed to a combination of several reactions. It was found that there is an Arrhenius
relationship between the hydroxyapatite formation rate and the temperature. Finally, the apparent activation energy of
94.4 kJ mol1 was obtained through the calculation process.
Hu et al. (184) applied an innovative technique for electrochemical processing of hydroxyapatite coating. To enhance the
adhesion level between HA coating and titanium substrate, they added vinyl acetate in the electrolytes of calcium and phosphorous.
According to X-ray powder diffractometer spectra data, the vinyl acetate did not interfere with the deposition of hydroxyapatite on
the surface of titanium cathodes. It was found that both vinyl acetate and hydroxyapatite were deposited on the titanium cathodes.
Moreover, hydroxyapatite crystalline morphology in the deposition layer was changed by vinyl acetate. There was a significant
difference between the shape and growth direction of the hydroxyapatite crystals in the coating with vinyl acetate and those of
hydroxyapatite deposition. The addition of vinyl acetate enhanced the coating strength noticeably; however, further improvement is
required for clinical applications. Furthermore, a preliminary study of the bioactivity indicated that osteoblastic cells had higher cell
proliferation potential on the hydroxyapatite–vinyl acetate coating compared to pure hydroxyapatite.
Li et al. (4) synthesized silicon-substituted hydroxyapatite (Si–HA) coatings on titanium substrates. To do so, they applied the
electrolytic deposition technique in electrolytes containing Ca2þ, PO3 4 , and SiO3 ions with various SiO3 –(PO4 þ SiO3 ) molar
2 2 3 2
ratios (hsi). The deposition was performed at a constant voltage of 3.0 V, with titanium and platinum substrates as cathodes and as
anodes, respectively, for 1 h at 85 C. The silicon content in the coatings rises linearly to about 0.48 wt.% at first with increasing hsi
between 0 and 0.03, then increases gradually to about 0.55 wt.% between 0.03 and 0.10, and finally maintains at a level around
0.55 wt.% between 0.10 and 0.30. The dendrite-form Si–HA crystals were observed in the coatings prepared in the electrolyte of
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Figure 14 Top and cross-sectional views of field emission SEM (FE-SEM) images of ZnO nanorods grown onto the ZnO seed layers by cathodic
electrodeposition from Zn(NO3)2 at 80 C for different periods. Top view: (a) 5 min and (b) 10 min. Cross-sectional view: (c) 5 min and (d) 10 min.
Reproduced from Hsieh, C. T.; Yang, S. Y.; Lin, J. Y. Electrochemical Deposition and Superhydrophobic Behavior of ZnO Nanorod Arrays. Thin Solid Films
2010, 518, 4884–4889.
hsi ¼ 0.20. Moreover, the presence of silicon in electrolytes reduces the thickness of the coatings; this effect is more noticed with further
increase of hsi. Furthermore, the substitution of Si causes some OH loss and modifies the lattice parameters of hydroxyapatite.
Lin et al. (111) developed an electrochemical method of depositing adherent octacalcium phosphate (OCP) and other CaP
coatings on titanium alloy (Ti6Al4V) substrates with different shapes and surface preparations. Besides, it was tried to characterize
the developed coating in terms of its composition, morphology, thickness, and dissolution. Another objective of this work was to
observe transformation of OCP to carbonatehydroxyapatite (CHA) in simulated body fluid (SBF). Applying the modulated pulse
time, electric fields programmed with a custom-made dual microprocessor, titanium (Ti)-alloy plates, tensile bars with four types
of surfaces (grit blasted with apatitic abrasive, chemically textured, arc deposited, and CoOCr beaded), and dissolution cylinders
were electrochemically coated. Modulated electrochemical deposition (MECD) was conducted with pH and temperature
conditions favorable for OCP formation. According to XRD and FTIR analyses, it was found that the pure, uniform OCP coatings
are produced on Ti6Al4V surfaces with coating-to-substrate tensile strengths above 7000 psi. Coatings on Ti arc-deposited surfaces,
chemically textured surfaces, and CoOCr-beaded surfaces all yield tensile strengths of 5000–7000 psi, with no coating shadows in
the crevices. The findings indicated that OCP crystal size can be controlled by the current density and relative pulse time
modulation. Their work showed that a highly adherent CaP (e.g., OCP) coating of uniform compositions (e.g., OCP) on Ti-alloy
substrates can be obtained at low temperatures by MECD through optimization of the pulse time modulation of the electric field,
reaction pH, temperature, and electrolyte composition. Additionally, it was found that OCP readily transforms to CHA once
exposed to SBF.
Popa et al. (24) synthesized passivating coatings of brushite (CaHPO4$2H2O) on Ti and Ti–6Al–4V ELI alloy substrates by
cathodic polarization. After being soaked in Ringer’s solution for 48 h, brushite was transformed to hydroxyapatite
(Ca10(PO4)6(OH)2). Based on the electrochemical cyclic polarization curves of the coated biomaterials synthesized in Ringer’s
solution at pH values of 7.1 and 8.91 as well as in Hank’s Balanced Salt Solution (HBSS) at pH value of 7.4, they were found to
have a nobler behavior compared to the uncoated biomaterials. Moreover, the coated biomaterials had lower corrosion rates
than the uncoated biomaterials. This, in turn, implies a protective feature of the hydroxyapatite coating. Because of the
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protective, very resistant layer (the thickness of which increased with soaking time), the EIS demonstrated capacitive behavior.
Because of the protective effect of the coating, the coated biomaterials indicated higher electropositive open circuit potentials
compared to the uncoated biomaterials. As the coatings became denser, smoother, and more adherent, the morphology of the
coatings varied with soaking time. Accordingly, such coatings may provide a favorable structure for cell adhesion and
proliferation.
Qiu et al. (28) synthesized branched hierarchical ZnO nanowire arrays on fluorine-doped tin oxide (FTO) substrate through
a two-step electrochemical deposition process. This process involves the electrodeposition of ZnO nanowire arrays on conductive
glass substrate, followed by the electrochemical formation of ZnO nanorod branches on the backbones of the initial ZnO nano-
wires. A development mechanism of the branched hierarchical nanostructure was discussed. The findings indicated that coating of
the initial nanowire arrays with a ZnO nanoparticles seed layer significantly affects the synthesis of the branched hierarchical ZnO
nanostructure. It is possible to adjust both the density and length of the secondary nanorod branches in the hierarchical nano-
structures, through controlling the concentration of Zn(CH3COO)2 colloid in the coating process and the reaction time of the
second-step deposition. In addition, the photoelectrochemical characteristics of the dye-sensitized solar cell (DSSC) are investigated
based on branched hierarchical ZnO nanowire arrays. Because of the enlargement of the internal surface area within the branched
nanostructure photoelectrode, the DSSC made of branched hierarchical ZnO nanowire arrays produces a power conversion effi-
ciency of 0.88%. It must be noticed that this value is almost twice higher than that of the DSSC fabricated through the bare ZnO
nanowire arrays. Figure 15 shows SEM images of branched hierarchical ZnO nanowire arrays synthesized by a two-step electro-
deposition process with different reaction times of the second-step deposition.
Suzuki et al. (48) electrochemically deposited crystalline TiO2 (c-TiO2) film on a 10 cm 20 cm hot-dip-galvanized (HDG) steel
plate at 60 C. They used an alkaline aqueous solution containing 0.1 M titanium potassium oxalate dehydrate and 1 M
hydroxylamine. The electrochemical deposition was conducted through a galvanostatic method. To do so, first, a current density of
10 mA cm2 was applied for 5 min. This resulted in the formation of a uniform coating of TiO2 on a 1 cm 1 cm small HDG plate.
However, a crystalline layer was observed only in the central area, whereas the upper and the edge areas were amorphous. Both
calculations and measurements attributed this to the difference of the local current densities in the vicinities of different areas. Next,
three different currents (5 mA cm2 (2 min), 10 mA cm2 (2 min), and 20 mA cm2 (1 min)) were continuously applied so that the
local current density for each part of the substrate reached the satisfactory deposition conditions. Hence, the obtained films were
crystalline in all areas and had uniform thickness.
Wang et al. (60) produced hydroxyapatite coating on titanium substrate using an electrochemical deposition technique. Here,
a well-oriented and uniform titanium oxide nanotube array on the surface of titanium substrate was applied using an anodic
oxidation pretreatment in order to promote the bonding strength between hydroxyapatite coating and Ti substrate. In the next step,
the calcium hydrogen phosphate (CaHPO4$2H2O, DCPD) coating, as the precursor of hydroxyapatite coating, was electrodeposited
Figure 15 SEM images of branched hierarchical ZnO nanowire arrays synthesized by a two-step electrodeposition process with different reaction
times of the second-step deposition: (a and b) 0.25 h and (c and d) 1 h. Preparing conditions for first-step deposition: T ¼ 80 C, t ¼ 2 h,
CZn2þ ¼ 0.5 mM, E ¼ 1.0 V vs. SCE; and for second-step deposition: T ¼ 80 C, CZn2þ ¼ 1 mM, E ¼ 1.0 V vs. SCE. Reproduced from
Qiu, J.; Guo, M.; Feng, Y.; Wang, X. Electrochemical Deposition of Branched Hierarchical ZnO Nanowire Arrays and Its Photoelectrochemical
Properties. Electrochim. Acta 2011, 56, 5776–5782.
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on the anodized Ti. At the early stage of electrodeposition, the DCPD crystals, in nanometer precipitates, are anchored in and
between the tubes. As the deposition time rises, the nanometer DCPD crystals are connected together to develop a continuous
coating on a titanium oxide nanotube array. Finally, the DCPD coating was transformed into hydroxyapatite coating through its
soaking in alkaline solution.
Wu et al. (185) produced nanostructured nickel hydroxide electrode directly using the electrophoretic deposition (EPD)
technique. A nickel hydroxide nanoplatelet converts into nickel oxide once it is annealed at 300 C for 3 h. Electrophoretic
deposition is an efficient approach in depositing nickel hydroxide nanoplatelets from isopropyl alcohol suspension containing
iodine and water additives. Hydrogen ions are created through the reaction between iodine and water and then adsorbed on
the nickel hydroxide, which in turn resulted in positively charged nickel hydroxide. This positively charged nanoplatelet with
high zeta potential contributes to EPD and electrophoretic dispersion. An EPD-deposited electrode involves higher uniformity
than the one deposited by dip coating. The electrochemical performance of the electrodes is examined via cyclic voltammetry in
0.5 M KOH. The results of this work indicated that the specific capacitance of the nickel oxide electrode prepared by EPD is
higher than that of the one prepared by dip coating even at a very high rate of 500 mV s1. Moreover, an electrode prepared by
EPD also indicates excellent cycle life stability since its specific capacitance drops slightly after 5000 charging and discharging
cycles.
Wu et al. (80) presented an EPD strategy for the synthesis of network-like carbon nanotube (CNT) films free of polymer
binder for electrochemical hydrogen storage. Surface treatment plays a key role in enhancing the hydrogen storage capacity of
CNT films. The CNT film with dual surface modifications of nitric acid and Ni2B coating treatment indicated the highest
electrochemical hydrogen storage capacity. Nitric acid treatment led to the opening of CNTs, development of micropores on
CNT surfaces, and improvement of surface wettability. These factors result in an increase of the hydrogen storage capacity of
CNT films with increasing nitric acid treatment time. Nevertheless, excessive nitric acid treatment resulted in reduction of the
available surface area of CNTs for hydrogen storage. The optimal treatment time for obtaining the highest discharge capacity
was determined as around 5 h. Deposition of Ni2B nanoparticles on CNTs strongly increases the electrochemical activity of
these CNT films and, as a result, promotes the hydrogen storage capacity. Based on CV results, it was found that the storage
capacity of a bare CNT film mainly originates from the charge stored in the electric double layer instead of the faradaic reaction.
The capacity of Ni2B-coated CNT films is attributed to the faradaic reaction, which can store much more hydrogen in CNTs.
However, there is a balance between the storage capacity and Ni2B coating. Based on findings of this work, the optimal amount
of Ni2B coating was about 45 wt.% in terms of the highest discharge capacity. Insufficient Ni2B cannot provide adequate
electrochemical activity, whereas excessive Ni2B results in reduction of the availability of CNT active sites for hydrogen storage.
Moreover, the Ni2B coated on the CNT film can prohibit CNT detachment from the film surface, which increases the stability of
the film during charge–discharge cycling. The CNT film treated with nitric acid for 5 h (before the EPD of film) and coated with
45 wt.% Ni2B indicated an excellent high-rate capability and a stable life cycle. Hence, it is an efficient candidate for elec-
trochemical hydrogen storage applications.
7.06.12.3 Polymeric-Based Coatings

Akundy et al. (186) successfully applied the electrodeposition of polyaniline–polypyrrole composite coatings on aluminum
through cyclic voltammetry (see Figure 16). They used oxalic acid as the electrolyte. Then, electrodeposition was performed by
varying the number of cycles. It was observed that there is an anodic peak current in the cyclic voltammograms at around 0.1 V vs.
SCE. Such a peak is created because of the hydrogen oxidation and adsorption. Besides, the cyclic voltammograms indicated another
anodic peak current at around 1.0 V vs. SCE, which is the specific peak of the polyaniline–polypyrrole composite. The behavior of
this peak is elaborately discussed in terms of the number of cycles. Moreover, a corresponding cathodic peak current was seen at
around 0.7 V vs. SCE in the cyclic voltammograms. Using the infrared spectra of the composite coatings, the infrared peaks of both
polypyrrole and polyaniline were observed. Finally, the scanning electron micrographs of the coatings presented completely
different morphology from its homopolymers.
Jelle et al. (187) synthesized solid-state electrochromic windows (ECWs) through incorporating polyaniline–Prussian blue
(PANI–PB) multilayers. In the early stages, ECWs with a transmission modulation of 49% of the total solar energy were produced,
which can be compared with the results reported in the earlier studies (49–50%) for ECWs with PB deposited on PANI. Here,
a noticeably higher modulation (>39%) was reported for ECWs based on PANI (and WO3) without PB. It is worth mentioning that
the PANI-PB multilayer ECWs are quite dark in the colored state, and they are able to regain a significantly high transparency.
Nevertheless, the promising results obtained in these preliminary experiments show it is probable to achieve further improvements
in electrochromic performance of ECWs via optimization of the multilayer deposition technique. Deposition of PANI-PB multilayer
films in electrolytes made of both PANI- and PB-developing chemicals produces some beautiful blue films; however, no color
change in solid-state ECWs has been achieved yet. Furthermore, through depositions of PANI-PB multilayer films through elec-
trolyte modification for each PANI or PB deposition, it was possible to successfully produce the films that change color in solid-state
ECWs with a high solar modulation. The film-drying time (at least 1 h) in air seems to be a critical issue for the following PANI-PB
depositions.
Yang et al. (188) deposited microporous films of the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) and
polypyrrole (PPy) through the electrochemical approach on the microelectrodes of neural probes from aqueous solution of lithium
perchlorate (LiClO4). Polystyrene latex spheres with various sizes were applied as templates. Using SEM for these samples, a three-
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Figure 16 Comparison of SEM micrographs of the coatings formed on aluminum: (a) polyaniline coatings; (b) polypyrrole coatings; and
(c) polyaniline–polypyrrole composite coatings. Reproduced from Akundy, G. S.; Rajagopalan, R.; Iroh, J. O. Electrochemical Deposition of Polyaniline-
Polypyrrole Composite Coatings on Aluminum. J. Appl. Polym. Sci. 2002, 83, 1970–1977.
dimensionally microporous structure consisting of voids with interconnected channels was observed. The effect of the amount of
deposited conducting polymer on the morphology of the microporous coatings was elaborately studied. It was found that the
surface morphology of the films changes with the particle size of polystyrene latex spheres and coating thickness. In addition,
a highly uniformed pore size was observed for the microporous conducting polymer films with different pore sizes electrodeposited
on the electrode sites.
Joseph et al. (189) deposited Cu2O coatings with (111) orientation, including crystallites with a triangular pyramidal
morphology at pH ¼ 12 from baths stabilized with a variety of ligating agents. This indicates that the oriented crystallization is
independent of the ligand structure. Once performing deposition at very high [OH] concentrations (pH > 14), the coatings are
unoriented and consist of crystallites with octahedral morphology. In some coatings, the loss of orientation can be attributed to
the random tilt of the long axes of the crystallites with respect to the normal of the substrate. In other cases, the loss of orientation
is mainly because of the redissolution of pregrown faceted crystallites. Regarding the fact that the dominant morphology of the
crystallites obtained under these conditions is octahedral, crystal formation occurs under thermodynamically controlled
conditions.
Electrodeposition is a common process in the synthesis of metallic coatings improving surface properties in engineering operations.
Although its principles are rather similar to the processes performed in relatively thin coating applications for aesthetic and
corrosion protection purposes, the surface-engineering type of electrodeposition is considered a specialized process and is different
from the other ones in some aspects. In this chapter, the application of specific metallic coatings is elaborately discussed through
chemical reduction and anodic oxidization processes. Economic aspects of the process are also important. In electrical deposition or
electroplating, the coating target is designed as a cathode (negative electrode) and placed in a liquid-containing cell. Typically,
electrolyte is a solution with salty metal (containing a target deposit). The electrical circuit is completed by an anode or positive
electrode, which typically is made of a metal that performs deposition and should be placed within a small distance of the cathode.
In the case of applying DC current at low voltages, metallic ions are positively charged and move toward the cathode in the
electrolyte. Indeed, this place is part surface and is considered a spot where the ions are subjected to the metallic atoms and are
deposited on the cathode. The structure and properties of the deposited metal depend on the chemical composition of the elec-
trolyte, its temperature, as well as its acidity or alkalinity level (pH). These factors, especially the electrical current density in the unit
surface of the cathode, determine the deposition rate.
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7.07 Thin Film Coating for Polymeric Micro Parts
L Xie, Xi’an Jiaotong University, Xi’an, China and ABB Corporate Research Switzerland, Dättwil, Switzerland
D Abliz, Xi’an Jiaotong University, Xi’an, China and Clausthal University of Technology, Clausthal-Zellerfed, Germany
D Li, Xi’an Jiaotong University, Xi’an, China

7.07.1.1 Polymeric Micro Parts 157
7.07.2 Surface Coating Technology for Polymer Products 157
7.07.2.1 Electrodeposition 158
7.07.2.2 Physical Vapor Deposition 159
7.07.2.3 Chemical Vapor Deposition 162
7.07.2.4 Painting 162
7.07.3 Thin Film Coating Technology for Micro Polymer Parts 165
7.07.3.1 Specific Requirements for Surface Functions of Micro Polymer Parts 165
7.07.3.2 Typical Coating Processes for Micro Polymer Parts 166
7.07.3.2.1 Atomic Layer Deposition 166
7.07.3.2.2 Magnetron Sputtering 166
7.07.3.2.3 Polymer Coating 166
7.07.3.3 Properties and Testing Methods of the Coatings in Micro Polymeric Parts 166
7.07.3.3.1 Thin Film Thickness Testing 167
7.07.3.3.2 Surface Quality 167
7.07.3.3.3 Mechanical Properties 168
7.07.3.3.4 Interfacial Properties 168
7.07.3.3.5 Optical Properties 169
7.07.3.4 Application Cases 169
7.07.4 Future Trends and Perspectives 169
Acknowledgement 170
References 170
7.07.1 Introduction
7.07.1.1 Polymeric Micro Parts
Due to the macro-molecular nature and consequently an infinite number of possible molecular assemblies, polymeric materials hold
a large variety of freedom in structural formation. The resulting material properties are extremely versatile, and different mechanical,
optical, and electrical functions can be achieved with these materials. Competing or even contradictory functionalities (e.g., insulative
versus conductive, hydrophilic versus hydrophobic, and transparent versus opaque) needed by a product may easily be realized with
appropriate formulation and selection of polymers. The recent developments in semiconductive polymers, piezoelectric polymers,
polymeric electrolytes, and other functional polymers, not only allow polymers to be used as a substitute for silicon, metals, and
ceramics in many miniature devices and systems, but also make applications possible that could not be realized before.
Because of the versatile properties and mass-production capabilities of polymers, popularity of using polymers as a replacement
for conventional materials is increasing. Especially in micro-devices and microsystems, the polymeric materials applied in a broad
range, including micro-optics (waveguides, micro lenses, and fiber connectors), micro-mechanics (micro-gears, micro-actuators,
micro-pumps, and micro-switches), information storage and data carrier devices (CDs, DVDs, and sensor discs), microfluidic
systems (blood analysis and DNA analysis), and medical technology (hearing aid and components for minimal invasive surgery).
In polymeric parts, in order to get specific functionality, improve mechanical properties, or decorate the surface of polymer parts,
they are coated with various metallic or polymeric layers after polymer processing. In regards to micro polymeric parts, in order to
achieve special electrical, magnetic, and mechanical properties to satisfy with the MEMS’s multifunctional demands, surface coating
is facing new and exciting challenges. In this chapter, the current scenario in relation to surface coating for micro polymeric parts is
presented. Preparation, processing, and application issues are addressed corresponding to the special requirements and challenges
of micro polymeric parts in particular.
7.07.2 Surface Coating Technology for Polymer Products
Coatings are used because they efficiently impart a host of desirable features to substrates, such as enhanced aesthetics, greater
barrier to moisture and chemicals, improved resistance to weathering and surface damage through physical impact, and certain

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158 Thin Film Coating for Polymeric Micro Parts
special characteristics and functionalities. Both durable and nondurable applications often require the plastics to be either painted
or coated with specific materials. Table 1 shows some common materials and their physical properties in this-film coatings. There
are different methods for the coating of plastics, among which the most popular applied ways are: electrodeposition, Physical Vapor
Deposition (PVD), Chemical Vapor Deposition (CVD), and painting (1–3). There are plenty of publications related to the surface
coating technology for polymeric materials. In this section, only a brief summary of the technology relevant to the subject of the
polymeric micro parts coating will be discussed to establish a proper perspective for the processes.
Table 1 Common materials in thin-film coatings
Materials Hardness (HV) Color
Titanium carbonitride 4000 Silver

Titanium aluminum nitride 2600 Brown
Titanium nitride 2900 Gold
Chromium nitride 2500 Silver
Zirconium nitride 2800 Gold
Amorphous DLC 1000–5000 Black
Reproduced from http://www.efunda.com/processes/surface/thinfilm_coatings.cfm
7.07.2.1 Electrodeposition
Electrodeposition is the process of producing a coating, usually metallic, on a surface by the action of electrochemical interaction.
Based on the electric-conductivity of the target object to be coated, there are two types of electrodeposition: electroplating and
electroless plating. In the electroplating process for electric-conductive material, the deposition of a metallic coating onto an object
is achieved by putting a negative charge on the object to be coated and immersing it into a solution which contains a salt of the
metal to be deposited (in other words, the object to be plated is made the cathode of an electrolytic cell). The metallic ions of the salt
carry a positive charge and are thus attracted to the object. When they reach the negatively charged object that is to be electroplated,
it provides electrons to reduce the positively charged ions to metallic form. Figure 1 shows the work principle of electroplating
process for metallic parts.
Because polymeric substrates are electrically nonconductive, they cannot be immersed in a plating solution and coated in the
way that metal objects can in the electroplating process. Therefore, an electroless plating process with the aid of a chemical reducing
agent in solution, and without the application of external electrical power, is used for the electrodeposition of plastics substrates.
Normally, the electroless plating of a plastic surface includes the following three steps:
1. Surface preparation: in order to improve the adhesion and surface seeding of the electroless catalysts, the surface preparation
process normally needs an etching process to modify the nonconductive surface, mostly using chromic acid etchants (4). The
etchant partially dissolves the polymer segment and changes its wettability, so as to increase the surface roughness to achieve
improved mechanical adhesion.
2. Surface activation: an activator (or catalyst) is applied by submersing the part in a palladium tin colloid bath. Metallic palladium
which is deposited by the following reaction is present on the surface of the part surrounded by hydrolyzed hydroxide and serves
as a catalyst for the deposition of the metal coatings.
Sn2þ þ Pd2þ /Sn4þ þ Pd [1]
Figure 1 Schematic illustration of electroplating.
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Thin Film Coating for Polymeric Micro Parts 159
3. Electroless plating based on the reduction reaction of metallic ions with a reducer: this is accomplished by using a semistable
solution containing a metal salt, a reducer, a metal complexer, a stabilizer, and a buffer system. When a palladium-bearing
surface is introduced into the solution, a chemical reduction of the metal occurs on the palladium sites, and through autoca-
talysis, continues until the part is removed. The metals nickel and copper are the most widely used materials for coating, and the
basic reactions for copper and nickel are:
Pd
Cu2þ þ 2HCHO þ 4OH ! 2HCOO þ Cu0 þ H2 [2]
Pd
Ni2þ þ H2 PO2 þ 3OH ! HPO3 2 þ Ni0 þ 2H2 O [3]
Electroless plating based on chromic acid etching is considered an environmentally unfriendly process due to the cancerogenic
nature of hexavalent chromium, and therefore banned in Europe [2007 Restriction of Hazardous Substances Directive (RoHS)] and
heavily regulated in the United States by the Environmental Protection Agency (EPA). Recently, for this reason, different chromium-
free etching processes using different solutions (5), or ion-assisted laser treatment (6), plasma modification (7), excimer UV lasers
(8), and intermediate graphene layers (8) are being investigated to replace the chromium-based processes. Once the plastic
component has been coated with this electrically conductive and adherent surface layer, it subsequently can be electroplated using
conventional technology (9).
Moreover, direct plating processes for plastics are investigated which do not use precious metals to activate or electroless
chemistries to produce the first conductive metallic layer (4,10,11). For example, Königshofen et al. (11) investigated a palladium-
free direct-plate process for plating on plastics, which employs a mild etching process that allows electrolytic nickel to plate directly
onto the plastic substrate and ensures a high degree of adhesion. Figure 2(a) shows an ABS (acrylonitrile-butadiene-styrene) plastic
surface that has been etched in a conventional colloidal ABS process chromic-sulfuric acid etch. The rough, heavily attacked surface
required by the classic type of colloidal activation process is depicted here. This aggressive etch is necessary for proper adhesion in
a colloidal process. As a result of such strong roughening, the surface of the molded part may be destroyed. The result could impact
adhesion and degrade the surface quality. Figure 2 shows a surface that has been etched under mild conditions in the direct-plate
process. This slightly roughened plastic surface with individual cavities is well suited for the “buttonhole” adhesion mechanism
between the surface of the substrate and the metal deposit. This is very important as it provides a high degree of adhesion while
maintaining the “Class A” as-molded parts’ surfaces. Moreover, it was found that the mild etch enhances the formation of polar
functional groups (–OH, –C]O, –COOH) on the plastic surface, where the percentage of hydroxyl groups (–OH) are found to be
particularly high. These make a chemical link with the positively charged activator molecules possible. In the following conducting
solution, the active metal is “wetted” to the plastic substrate via a bridge of sulfur as a result of a kind of vulcanization. These two
reactions achieve an additional chemical adhesion.
Figure 2 Comparison of plastic surface by different etching processes. (a) Colloidal etching and (b) mild etching. Reproduced from
Königshofen, A.; Griffith, B. Palladium-free Direct-plate Technology for Plating on Plastics. Prod. Finish. 2005, 69 (12), 46.
7.07.2.2 Physical Vapor Deposition

Physical vapor deposition (PVD) is a high vacuum coating technique used for surface protection as well as for optics, photovoltaic
conversion, and decorative applications. PVD deposition is the result of producing a vapor stream in-vacuum from a solid material
(usually named the target) by physical means (arc discharge, sputtering, heat transfer by laser or electron beams, etc.). A great variety
of PVD techniques exists, including thermal evaporation (Figure 3), electron beam evaporation, sputter deposition in plasma,
reactive sputter deposition, and cathodic arc deposition, which are described in detail elsewhere (12).
Unlike electroless plating, PVD coating is more environmentally friendly and can generate a smoother substrate surface,
compared to the rough substrate surface generated by the etching process in electroless plating. Therefore, PVD is attractive in certain
applications, including 3D circuit boards or homogenous, thin conductive coatings, and therefore is a widely used method for the
coating of polymers (13–16).
Fruth et al. (17) have studied the PVD-coating of PA plastic materials and the friction behavior against metal counterparts, as
shown in Figures 4–8. Their results showed that maximum adhesion of strengths (about 14 N mm2) was obtained using a tita-
nium adhesive layer. Moreover, PVD-coatings remarkably reduced the coefficient of friction, in which Ti and a-C coatings showed
the best results. Besides, there are several investigations on the PVD coating of plastics for readers’ reference (16,18–21).
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Figure 3 Schematic illustration of PVD process by thermal evaporation.
Figure 4 Micro-hardness and Young’s module of PVD-coated PA polymers. Reproduced from Fruth, W.; Meerkamm, H.; Krumpiegl, T.; et al.
Tribological Behaviour of PVD-coated PA Plastic Material Sliding against Metal Counterparts. Surf. Coat. Technol. 1999, 120, 470–475.
Figure 5 Dependence of the adhesive strength on etching time on PVD process. Reproduced from Fruth, W.; Meerkamm, H.; Krumpiegl, T.; et al.
Tribological Behaviour of PVD-coated PA Plastic Material Sliding against Metal Counterparts. Surf. Coat. Technol. 1999, 120, 470–475.
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Figure 6 Friction behavior of the PVD-coated polyamide samples against refined steel. Reproduced from Fruth, W.; Meerkamm, H.; Krumpiegl, T.;
et al. Tribological Behaviour of PVD-coated PA Plastic Material Sliding against Metal Counterparts. Surf. Coat. Technol. 1999, 120, 470–475.
Figure 7 Adhesion strength of Cu/Cr PVD layers on LCP substrates after oxygen pretreatment with different pressure. Reproduced from Fruth, W.;
Meerkamm, H.; Krumpiegl, T.; et al. Tribological Behaviour of PVD-coated PA Plastic Material Sliding against Metal Counterparts. Surf. Coat. Technol.
1999, 120, 470–475.
Figure 8 Adhesion strength of Cu/Cr PVD layers on LCP substrates before and after thermal shock. Reproduced from Wang, B.; Eberhardt, W.;
Kuck, H. Plasma Pre-treatment of Liquid Crystal Polymer and Subsequent Metallization by PVD. Vacuum 2006, 81 (3), 325–328.
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Figure 9 Schematic illustration of the difference in PVD and CVD principle.
Figure 10 Experimental apparatus of plasma CVD process. Reproduced from Anma, H.; Yoshimoto, Y.; Warashina, M., et al. Low Temperature
Deposition of SiC Thin Films on Polymer Surface by Plasma CVD. Appl. Surf. Sci. 2001, 175, 484–489.
7.07.2.3 Chemical Vapor Deposition

Chemical vapor deposition (CVD) is a process that involves depositing a solid material from a gaseous phase (often diluted
in carrier gases), which differs from the PVD process that the precursors are solid, with the material to be deposited being
vaporized from a solid target and deposited onto the substrate. CVD covers processes such as: atmospheric pressure CVD,
low pressure CVD, metal-organic CVD, plasma-assisted CVD, laser CVD (LCVD), photochemical vapor deposition, chemical
vapor infiltration, and chemical beam epitaxy. Among them, the three main CVD techniques are thermal CVD, plasma-
enhanced CVD (PECVD), and laser CVD (LCVD). While all of them need volatile precursors, the chemical composition of
which is changed during the deposition process. In thermal CVD, the precursor forms a deposit when it comes into contact
with a hot surface. In PECVD, the vapor of the precursor is decomposed by contact with the plasma. This might have
already happened in the gas phase, or the precursor is adsorbed at the substrate and subsequently decomposed by the
bombardment of charged particles or photons. In LCVD, the precursor is decomposed in a photochemical process or by
pyrolysis when it comes into contact with a surface that has been heated by a laser. Compared to the PVD process, CVD is
more conformal and allows for batch processing of 3D substrate geometries. For more detailed information, the reader is
redirected to Ref. (22).
One of the most important considerations for the CVD coating of the polymeric substrate is the temperature, due to the
low deformation or degradation temperature of plastic materials. Therefore, only low-temperature processing could be applied
for the CVD coating of plastics. Studies were carried out on modified plasma-assisted CVD coating of thin films on polymer
surface (23–25). Examples relating the plasma-assisted CVD process for polycarbonate (PC) are provided below. Figure 10
shows the experimental apparatus of plasma CVD for PC, Figure 11 shows the solar UV resistance of SiC coated PC substrate
by CVD.
7.07.2.4 Painting
The painting process of plastics is an aspect of the application for the coating of plastics, which includes first applying wet or dry
organic coating material to the substrate material and drying or curing to convert the applied paints into the final coating (2,12,26).
Unlike conventional materials, the main problem in the painting of plastics is their poor adhesion due to the low surface tension of
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Figure 11 Comparison of solar UV resistance of original (a) and Sic coated PC substrate (b) by CVD. Reproduced from Anma, H.; Yoshi-
moto, Y.; Warashina, M., et al. Low Temperature Deposition of SiC Thin Films on Polymer Surface by Plasma CVD. Appl. Surf. Sci. 2001, 175,
484–489.
plastics. For successful coating design, the physical and chemical characteristics of the polymer substrate or plastic surface to be
coated, including surface tension, modulus, coefficient of thermal expansion, response to coating drying and cure, as well as the
chemical structure and conformation of the polymer, needs to be considered to select the proper type of coating required for
a particular application (26).
One of the basic criteria to achieve good coating adhesion is surface wetting. Regardless of the coating and the surface it is
applied to, the coating must adequately wet out, and usually adhere well to that surface. Normally, there are three principle
wetting phenomenon that apply to coatings. These are spreading, adhesional, and penetrational or immersional wetting.
Spreading and adhesional wetting will directly impact the application of a coating to a particular surface. Penetrational or
immersional wetting will impact the application of a coating to a porous surface structure or the dispersion of particulate matter
(including the possibility of a plastic or polymer media, pigment, or filler) into a coating composition. The below provides
a brief introduction about the spreading wetting from the above different wetting processes, which is mostly used for the
painting process (28).
The spreading of a liquid over a solid is defined by eqn [4].
SL=S ¼ gSA ðgLA þ gSL Þ [4]
where gSA denotes the surface tension of the substrate under air, gLA denotes the surface tension of the liquid coating under air, and
gSL denotes the interfacial tension or free energy of the substrate/liquid coating interface.
When SL/S is:
1. positive, coating fluid spreading is spontaneous,
2. zero, coating fluid spreading is spontaneous,
3. negative, coating fluid spreading is not complete.
The surface tension of the plastic is given by the nature of the polymer used to construct it. Table 2 lists several types of
plastics and their respective surface tensions (29). When evaluating coating compositions, it will be quite evident whether the
coating fluid has a comparable surface tension. If the coating does not flow out well, pinholes or fisheyes occur, or if thick edges
or picture framing occurs, the coating surface tension is probably too high relative to that of the plastic surface. In terms of eqn
[4], the formulator only has control of the surface tension of the coating fluid. Typically, interfacial tension is not accurately
determined with ease, but is assumed to be made minimal when the surface tension of the substrate and the coating fluid are
the same or near the same. Therefore, for best coating uniformity, the formulator should keep gLA and gSL as low as possible
relative to gSA.
Another method of determining spreading wetting is through contact angle measurement. The contact angle is simply the angle
tangent to the edge of a droplet of fluid in contact with a surface. Equation [5] describes spreading wetting in terms of the contact
angle that the fluid makes with the substrate.
SL=S ¼ gLA ðcos q 1Þ [5]
The contact angle must be zero for spontaneous spreading wetting, unless the surface is rough. Equations exist which account for
substrate roughness or rugosity, and we find that spontaneous spreading can occur, provided that the contact angle is less than 90 .
Contact angle measurements are very useful in situations where (as is usually the case) gSA < gLA, and when gSA > gLA, the contact
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Table 2 Surface tension of polymeric materials
Polymer Surface tension (dyne cm1)@ 20 C
Cellophane 45
Cellulose 36–42
Cellulose acetate 46
Cellulose acetate butyrate 34
Epoxy resins 45–52
Ethylcellulose 32
Nitrocellulose 38
Nylon 12 36
Nylon 6 38
Nylon 6,6 47
Phenoxy resins 43
Poly(2-ethylhexylacrylate) 30
Poly(acrylamide) 52
Poly(acrylonitrile) 50
Poly(butadiene) 43–49
Poly(butadiene-acrylonitrile) 51–53
Poly(chloroprene) 44
Poly(ethylacrylate) 37
Poly(ethylene) 33–37
Poly(ethylene-acrylic acid) 41–60
Poly(ethylene-propylene) 30–34
Poly(ethylene-propylene-hexadiene) 35
Poly(ethylene-vinyl acetate) 30–36
Poly(ethyleneterephthalic acid) 45
Poly(ethylmethacrylate) 36
Poly(hydroxyethylmethacrylate) 37
Poly(isoprene) 31–34
Poly(methacrylonitrile) 39
Poly(methylmethacrylate) 41
Poly(oxyethylene) 43
Poly(propylene) 29–30
Poly(styrene) 39–41
Poly(styrene-acrylonitrile) 37–43
Poly(tetrafluoroethylene) 24
Poly(vinyl acetate) 37
Poly(vinyl alcohol) 37
Poly(vinyl butyral) 38
Poly(vinyl butyrate) 31
Poly(vinyl chloride) 42
Poly(vinylidene chloride) 45
Poly(vinylidene fluoride) 33
Polycarbonate of bisphenol A 43–45
Polyimides 38–41
Polyimines 22–26
Polysiloxanes 19–26
Polysulfone 47
Polyurethanes 36–39
Starch 39
Reproduced from Brandrup, J.; Immergut, E, H. Polymer Handbook, 3rd ed.; John Wiley & Sons,
Inc., 1989.
angle will always be zero. The contact angle that a liquid makes with the surface it is sitting on provides a means of determining
surface tension relationships. A contact angle of zero implies spontaneous spreading wetting, although spontaneous spreading
wetting can occur provided that the contact angle is less than 90 .
The following are the typical guidelines for good spreading wetting (26):
1. Adjust the fluid surface tension to match to that of the substrate.
2. Check the contact angle and maintain it below 90 .
3. When using surfactants to adjust fluid surface tension, select surfactants to perform to the highest potential at the lowest
concentration.
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Table 3 Typical coating and substrate interaction
Type Bonding type Energy (kcal mol1)
Primary Covalent 15–170

Primary Lonic 140–250
Primary Metallic 27–83
Secondary Hydrogen bond <12
Secondary Dispersion <10
Secondary Dipole <5
Secondary Induction <0.5
Reproduced from Paul, S. Painting of Plastics: New Challenges and Possibil-
ities. Surf. Coat. Int. Part B: Coat. Trans. 2002, 85 (2), 79–86.
After the initial wetting of the plastic surface has occurred, the next important requirement to obtain good adhesion is to have
good interfacial interaction between the substrate and the coating. In generation, the interaction can be divided into two main
groups: primary valency forces and secondary valency forces (30). The types and the magnitude of the forces are summarized in
Table 3.
Thus, it is evident that in order to obtain good adhesion, the primary interactions are preferred due to their strong bond energies
compared with the secondary interactions. In cases where it is difficult to obtain primary interactions between the coating and the
substrate, secondary interactions of the hydrogen bond and dispersion types will be applied in order to obtain good adhesion
because they also exhibit relatively high bond energies.
In order to design a coating or modify a surface, it is essential to consider the various mechanisms which are generally operative
in the improvement of adhesion. The various mechanisms which may influence adhesion between the coating and the substrate
were summarized to the following (30):
l Weak boundary layer theory
l Mechanical theory
l Diffusion theory
l Electrical theory
l Chemical bonding theory.
This suggests that in order to paint plastics, it is essential to prepare the surface without adversely affecting the bulk properties of
the materials. Main techniques used for the surface preparation of plastics and their characterizations have been reviewed by Chan
(31) and can be briefly summarized as below:
l Surface degreasing (32,33)
l Flame treatment (34)
l Corona treatment (35–37)
l Plasma treatment and plasma polymerization (37–39)
l Chemical treatment (40–42)
l Radiation grafting (43,44)
l Adhesion promoter coatings (45–47).
Of course, there are other numerous concepts and principles that interplay with the science of painting design for plastics. The
quality of coatings on plastics depends to a considerable degree on the correct selection of the paint system and the state-of-the-art
preparation of the surface. The adhesion which is necessary for lasting protection generally can only be achieved by considering
plenty of factors influencing the process.
7.07.3 Thin Film Coating Technology for Micro Polymer Parts
Surface coating technology is facing new and exciting challenges from the advent of micro- and nano-manufacturing technologies,
and surface modification processes will have a major role in enabling the industrialization of several technologies in the near future,
such as micro-forming, micro-machining, or micro/nano-texturing. The miniaturization of mechanical components and machines
enables innovative future products. At the same time, for the improvement of functionality, reliability, and lifetime of those micro
systems, coatings with thicknesses in the submicron range are needed. Therefore, new and emerging technologies need to find novel
functional surfaces which could introduce new products able to outperform those already existing from classical concepts.
7.07.3.1 Specific Requirements for Surface Functions of Micro Polymer Parts

As mentioned above, heading to get the functional layer, to improve mechanical properties, or to decorate the surface of polymer
parts, normal size polymeric parts are coated with various metallic or polymeric layers after polymer processing. In regards to
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polymeric parts with a size of down to microscale, to satisfy the MEMS’ multifunctional demands, metallic layers/thin films with
special electrical, magnetic, and mechanical properties are always coated on the micro polymer parts’ surface as well by various
coating technologies, such as CVD, PVD, electroforming, etc.
However, due to the size-reduction and special surface effect in micro-scale parts, there are more critical quality requirements
for coating in micro systems in aspects of surface quality, mechanical property, optical property, electrical property, etc. For
instance, in the case of the coating for micro optical parts such as micro-lens, the surface roughness of the polymeric lens is
required to be in the range of 20 nm, which demands their surface coating roughness maximum 20 nm roughness as well; in
addition, the coating of the lens should possess antiscratching (high hardness), high wearing ability, and low refection index.
However, for the conventional coating process used in normal polymeric parts, it is quite challenging to achieve such critical
properties for coatings of micro polymer parts. For example, the CVD process normally offers the best quality and homogeneity
of the surface coating for the normal polymer parts, but in micro polymer parts, due to the small massive amount of the parts, the
surface of the micro parts is more likely to be burned by the high temperature generated in the normal CVD process, additionally
the high aspect ratio areas, like sharp corners, where of the micro parts could not be coated homogenously by the conventional
CVD process.
Therefore, many modified coating processes based on the conventional coating technologies as well as completely new processes
are developed. In the following section, they are classified according to their mechanism and discussed in detail.
7.07.3.2 Typical Coating Processes for Micro Polymer Parts

7.07.3.2.1 Atomic Layer Deposition
Atomic Layer Deposition (ALD) techniques can produce continuous, Angstrom-level-controlled, and defect-free films.
ALD, a variation on CVD, is a gas-phase method based on two sequential, self-limiting surface reactions. Each surface
reaction allows only one monolayer of deposition. In addition, it can employ more reactive precursor gases than CVD and
generate lower deposition temperature, which provides the possibility to apply this technology for coating micro polymer
parts.
For instance, Al2O3 ALD is a particularly robust and well-defined ALD system and can be deposited on polymer substrates.
Excellent gas diffusion barrier properties are observed for Al2O3 ALD films on polyethylene naphthalate (PEN) and Kapton
polymer substrates. Therefore, Al2O3 ALD could provide an ideal model system for the systematic investigation of thin-film coatings
to protect a polymer from hyperthermal atomic oxygen, which compromise their application in spacecraft outer material and micro
systems exposure in space conditions of high collision energy of oxygen atoms.
7.07.3.2.2 Magnetron Sputtering

Sputtering is one kind of PVD technology, which transfers the source material to the target materials substrate by the sputtering
method. The normal PVD process is challenged by problems of homogenously coating the side walls of the microstructures and the
processing temperature for some source material such as metallic nitride or oxides are too high for polymer materials. However, the
variation of the magnetron sputtering process can solve this issue through complex magnetron controlling. Jian Zhou et al. (48)
used the DC reactive magnetron sputtering process to realize the AlN piezoelectrical thin film deposition on polymer substrate,
which can potentially be used for the development of flexible sensors, flexible microfluidic applications, micro systems, and lab-on-
chip systems.
7.07.3.2.3 Polymer Coating

For polymeric micro systems, there are some special needs for the polymer microstructure parts to have grading physical properties,
for example, the refractive index. The typical methods to satisfy with such requirements are building multilayer structures on the
polymer substrate by spin coating/casting or thin film binding. For instance, in order to solve the problem in the polymer waveguide
system about an inherent high propagation loss in the short visible wavelength range caused by absorption due to the added
photosensitizers, the researchers from Denmark Technology University dissolved polymethylmethacrylate (PMMA) in anisole and
doped them with styrene-arcylonitrile copolymer to vary the refractive index. The doped PMMA with a higher refractive index is then
spin coated onto a PMMA substrate with a lower refractive index to provide waveguide properties. Thereafter, the direct micro-
milling process was applied to fabricate a 100-mm wide optical waveguides structure. In this novel microfluidic system integrated
with optical waveguides structures, the propagation losses of less than 1 dB cm1 could be achieved throughout the entire visual
range down to a wavelength of 400 nm.
7.07.3.3 Properties and Testing Methods of the Coatings in Micro Polymeric Parts
In order to make sure that coatings which were formed by a certain defined process to satisfy the specified technological demands,
a wide range of the coating’s properties need to be characterized and tested. In general, the main physical properties of a thin film are
named as film thickness, surface quality, mechanical properties, interfacial properties, optical properties, and some special physical
properties such as electrical conductivity. It is mainly dependent on their application area and other concern to decide which key
properties of the thin film to be considered. In the following section, a general overview for the thin film properties characterization
with the specific focus on the thin films coated on polymeric parts will be discussed.
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7.07.3.3.1 Thin Film Thickness Testing

The film thickness is one most basic and important property for the coating, which is intensively related to other properties of the
thin film and determine their final qualities. Therefore, the thickness of the thin film is the first prior feature for film coatings. In thin
film coating for micro polymer parts, typically it is necessary to have a good understanding and control on the film thickness,
sometimes even real time during the deposition process. The case of optical coatings for micro-lens that mentioned above is a good
example for controlling the coating thickness very precise.
After decades of knowledge and experience accumulation, there are many different film thickness test methods, which are
summarized as shown in Figure 12. Regarding the thin film used for micro parts, one of the most reliable, accurate, and common
methods is quartz oscillator micro balance tests, which is commonly called quartz oscillator microbalance. It is generally used for
the in situ determination and control of the film thickness and deposition rate in the case of PVD methods. In commercially
available designs, film thicknesses in the range from 0.1 nm–100 mm and deposition rates in the range from 0.01–100 nm s1 are
permanently displayed.
Figure 12 The different thin film thickness determination methods. Reproduced from Goldschmidt, A.; Streitberger, H. BASF Handbook on Basics
of Coating Technology; Vincentz Network, 2007.
7.07.3.3.2 Surface Quality

The roughness is the representative parameter for surface quality of the thin film coating in micro parts. In principle, there are two
types of testing methods for thin film roughness measurement; the first is touch profile scanning, and the second is based on the
optical method. The most common touching test method for roughness determination of thin film in micro parts is the atomic force
microscope (AFM) and optical-based characterization.
7.07.3.3.2.1 Atomic Force Microscope

The AFM is the variation of the scanning tunneling microscope to insulation surfaces. A micro scale cantilever (mostly made
of Si or Si3N4) having a tip structured with an opening angle of 20–50 on its end and with approximately 20–50 nm tip
curvature is used to detect the surface. The basic principle of the measurement process is: the contact of the tip with the
surface will deflect the cantilever and meanwhile, the deflection is measured and kept constant by using the feedback
principle.
Today, the most common method to measure the cantilever deflection is to detect the displacement of a laser beam reflected
from the backside of the cantilever by a four quadrant photodiode, by which the deformation of vertical and lateral cantilever can be
detected. Another method is the application of a conductive tip onto the backside of the cantilever where the deflection of the tip
can be transformed as a tunneling current signal. This principle is common for AFMs used in ultra high vacuums with less noise and
disturbance.
As mentioned above, one advantage of the AFM is the non-necessity for the electrical conductivity of the sample. The testing
process can be also used for some mechanical test, such as the local friction coefficient, the local hardness, etc., of the sample by
direct contact between tip and sample surface.
Whereas, there are some disadvantages for this direct contact testing method: the atomic resolution cannot be achieved due to
the high tip curvature. The surface is mechanically loaded and there is a high probability of tip contamination.
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Recently, many pilot methods have been developed based on AFM, which allow the determination of a great variety of surface
properties on different materials, such as Magnetic Force Microscopy (MFM) and Scanning Near field Optical Microscopy (SNOM).
MFM is used for the investigation of magnetic surfaces and SNOM allows performing optical spectroscopy on a molecular level, thus
yielding chemical information on the nm scale.
7.07.3.3.3 Mechanical Properties

The mechanical properties of thin films including the hardness and elastic modules, etc., which are primarily characterized by the
nano indentation method.
During the nano indentation test, a force is applied by the transducer and the resulting displacement is detected and recorded to
produce a traditional force versus displacement curve. The nano indentation measures the force versus displacement of the nano
indentation probe with a unique patented three-plate capacitive transducer design. This transducer design provides an unsurpassed
noise floor and ultra-low working force. Figure 13 shows the a typical nano indentation testing curve and the in situ microscopic
image of the indentation.
Analysis of the measured force versus displacement curve (particularly the unloading segment) provides the user with infor-
mation regarding the mechanical properties of the sample. Values typically obtained from quasi-static nano indentation testing are
reduced modulus [Er] and hardness [H]. However, other information such as fracture toughness, stiffness, delamination force, and
film thickness can also be obtained.
Figure 13 (a) Force versus displacement curve on fused quartz showing typical response of elastic–plastic material. (b) Resulting in an in situ
SPM image of quartz surface after quasistatic nano indentation showing residual indent impression. From http://hysitron.com/.
7.07.3.3.4 Interfacial Properties

As for the micro system with single or multilayers of thin film coatings, there are numerous quality issues related to the
interfacial properties between the coating and the substrates or between the internal multithin films layers. One key interfacial
property is described as the adhesion force which is characterized by different adhesion testing methods as shown in
Figure 14.
Among them, the most common and effective method for characterizing the interfacial attachment between the thin film and
micro polymer parts is the scratch test based on a nano indentation instrument. For the scratch test instrument, a rounded cone
made of steel, tungsten carbide, or diamond is moved across the sample perpendicular to the surface and loaded with increasing
force L. At a critical load LC, the film can no longer follow the deformation of the substrate and cracks or delaminates from the
substrate. LC is dependent on the material of the coating and the substrate is a measure for the adhesive strength. The analysis of the
scratch deformation is often completed in a SEM or, for automatic devices, by an acoustic emission detector which records
the noises generated upon cracking of the film.
In principle, the scratch test is well suited for a quantitative assessment of adhesion strength and is therefore widely used.
Unfortunately, the scratching process is so complex that there is no valid theory which comprises all the aspects that influence an
absolute measurement until now. In the case of relative measurements, the present method is well reproducible and is even well
suited for coatings with excellent adhesion.
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Figure 14 Methods of measuring the adhesion of coatings. Reproduced from Goldschmidt, A.; Streitberger, H. BASF Handbook on Basics of Coating
Technology; Vincentz Network, 2007.
7.07.3.3.5 Optical Properties

Optical coatings for micro polymeric parts are one of the first technologically relevant applications of thin films. For instance, the
application of antireflex coatings in the first half of the twentieth century was indicated to be one of the few fundamental advances
in applied optics. The field of interference optics has also considerably widened by the development of new coating technologies, by
improvements in instrumentation, and by the development of new scientific and technological fields. Currently, the optical
constant testing is mostly done by the ellipsometer and the rotating analyzer ellipsometer set up is most popular in real application
cases.
7.07.3.4 Application Cases

As mentioned in Section 7.07.3.2, the thin films for micro polymer parts are headed to bring or improve the mechanical, optical,
and conductive properties for the polymer substrates. There are many industrial application cases. For example, the company
Nanofilm uses various PVD metal coatings on polymer parts to bring the super hardness colorful layer on the polymer surface so
that the wear ability of the polymer parts can be improved; The Sun Microsystem Inc. use NANOCUBIC coating technology from
Fujifilm media products to develop the media tape with ultra high storage capacities. The Fraunhofer institute EMFT developed the
coating technology of polytronic to manufacture active functional components where organic materials and polymers have a key
role to play, in which a wide range of components are now in development such as organic solar cells, integrated polymer circuits,
and polymer sensors. The coating system developing company, Roth & Rau builds the customized PVD system for large area roll of
flexible materials such as polymer, where the coating width is up to 300 mm. The system is used for OLED and the photovoltaic
industry.
In addition, researchers are currently investigating how the functional thin film coating influence the mechanical properties of
the polymer micro parts. For instance, the authors investigated the effect of the PVD Al and Ti thin film coatings on mechanical
properties of micro injection molded polymer parts.
7.07.4 Future Trends and Perspectives
With increasing applications of polymeric micro systems in genetic analysis, biomedical, micro optical systems, micro sensor,
actuator, etc., the thin film coatings for micro polymer parts are requested to possess more complex biological, acoustic,
mechanical, optical, and thermal properties. The following examples partially point out the trends of thin film coatings for micro
polymer parts.
l Organic or inorganic grafted coating layer in molecular or atomic scale for special DNA, virus, and drug analysis.
l In situ micro/nano coating technology with micro/nano fabrication technology, e.g., the micro over-molding technology.
l Low stress, highly homogenous multimaterial composites nano scale thin layers coating, e.g., the conductive, thermal barrier,
and electrical insulation multilayers for micro/nano polymer capacitor.
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Acknowledgement
The authors would like to thank the NSFC for the financial supports for the relevant works (51290294 and 51105299).
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43. Balart, J.; Fombuena, V.; Espana, J. M., et al. Improvement of Adhesion Properties of Polypropylene Substrates by Methyl Methacrylate UV Photografting Surface Treatment.
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44. Decker, C.; Zahouily, K. Surface Modification of Polyolefins by Photografting of Acrylic Monomers. Macromol. Symp. 1998, 129, 99–108.
45. Lawniczak, J. E.; Williams, K. A.; Germinario, L. T. Characterization of Adhesion Performance of Topcoats and Adhesion Promoters on TPO Substrates. JCT Res. 2005, 2 (5),
399–405.
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7.08 Electric Field–Assisted Chemical Vapor Deposition
for Nanostructured Thin Films
MEA Warwick, University College London, London, UK and UCL Energy Institute, London, UK
L-M Romero-Nunez, Queen Mary University of London, London, UK
AJT Naik, University College London, London, UK
R Binions, Queen Mary University of London, London, UK

7.08.2 Theoretical Basis 171
7.08.3 Experimental Concerns 173
7.08.3.1 Film Synthesis 173
7.08.3.2 Materials Characterization 174
7.08.3.3 Gas Sensor Characterization 174
7.08.4 Results and Discussion 174
7.08.4.1 Vanadium Dioxide 174
7.08.4.2 Titanium Dioxide 179
7.08.4.3 Tungsten Trioxide 184
7.08.5 Conclusions 189
Acknowledgments 189
References 189
7.08.1 Introduction
Metal oxide thin films have been subject to enormous research activities in recent years due to their wealth of interesting properties
and applications in a diverse range of areas from chromogenic materials (1,2), catalyst materials (3), energy materials (4,5), and
sensors (6,7). It is highly desirable to be able to produce materials with high surface areas and tailored nanostructures in order to
maximize the materials’ performance and efficiency in these increasingly important applications.
Chemical vapor deposition (CVD) is a useful method for depositing thin films of metal oxides and has been shown to be
capable of producing a range of material architectures (8). The effect of an electric field in CVD reactions of any kind is largely
unknown; Williams et al. noted that while trying to follow WO3 film growth from an aerosol-assisted chemical vapor depo-
sition (AACVD) using impedance measurements, the bias of the measuring circuit led to a change in film microstructure (9).
The authors of this chapter have conducted a number of studies on the effect of electric fields in CVD reactions to produce
various metal oxides (10–15). In this chapter, they review the use of electric field–assisted CVD to produce thin films of vanadium,
titanium, and tungsten oxides and their application as metal oxide gas sensors.
7.08.2 Theoretical Basis
Previous investigations (10–15) have shown that the application of an electric field during a CVD reaction influences the crystal-
lographic orientation, microstructure, and subsequent physical of the deposited materials. Indeed, it is well known that functional
properties depend strongly on such material. The authors have suggested previously that a variety of phenomena may be occurring
when an electric field is applied to CVD growth (10–15).
Applied electric fields can cause an increase in growth rate and nucleation rate, leading to pseudodendritic type morphologies
as a result of accelerating gas phase species toward the surface (11). The authors consider this to be the result of an interaction
between a permanent or induced dipole in the CVD precursor species and the applied electric field; greater kinetic energy
increases the probability of nucleation on the gas sensor substrate surface increasing film growth rate as well as leading to
a reduction in the scale length of the deposited particles. In the gas phase, the applied electric field may also cause the precursor
molecule to orientate in a particular way toward the surface (Figure 1(a)), and may also activate some of the precursor bonds, by
causing an extension in a bond along the axis of a dipole, essentially pulling the precursor apart, and thus lowering the energy of
nucleation and leading to a favored growth orientation (Figure 1(b)). Gas phase effects are undeniably important in electric field
CVD (EFCVD) processes; however, the authors anticipate that other, surface-related effects are also important (Figure 1(c)).
Crystallographic orientation is likely to be strongly influenced by strong, localized surface dipoles. This is particularly likely
where the precursor molecule has no permanent dipole present and therefore is unlikely to interact with the applied electric field
in the gas phase.

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172 Electric Field–Assisted Chemical Vapor Deposition for Nanostructured Thin Films
Figure 1 Schematics of possible effects in electric field–assisted chemical vapor deposition. (a) Gas phase alignment and acceleration to substrate
surface, (b) bond activation where the precursor molecule is effectively pulled apart, and (c) surface-induced dipoles leading to pseudodendritic/
preferred growth.
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Electric Field–Assisted Chemical Vapor Deposition for Nanostructured Thin Films 173
7.08.3 Experimental Concerns

7.08.3.1 Film Synthesis
The deposition of tungsten oxide was carried out on alumina gas sensor substrates. The substrates were 3 mm 3 mm chips with
interdigitated gold electrodes with a gap of 45 mm between the electrodes; 50.8 mm platinum wires (Alfa Aesar) were spot welded to
the platinum heater track on the bottom of the substrates and the electrodes on the top, using a MacGregor DC601 parallel gap
resistance welder. The chips were then further welded onto individual sensor housings. A dielectric glaze (4913G, ESL Europe) was
applied over the heater track to avoid short-circuiting the heater track during the deposition. A schematic of a gas sensor chip is
shown in Figure 2.
The experiment was carried out in a cold wall reactor, which has been previously reported (11–13) (Figure 3). The reactor
was a cylindrical stainless steel tube with dimensions of 3 cm diameter and 36 cm length. The dimensions of the reactor were
such that they allowed enough area around the sensor substrate for the combined aerosol–gas vapor to flow over and beyond
the substrate.
The precursors used for the depositions were tungsten hexaphenoxide (W(OPh)6) (synthesized as in previous reports) (16),
vanadyl acetylacetonate (VO(acac)2) (Aldrich 99.9%), and titanium tetraisopropoxide (Ti(iOC3H7)4) (Aldrich 99.99%). For each
deposition, standard solutions of 15 ml of 0.05 M in toluene for tungsten and titanium oxides and ethanol for vanadium oxides
were used, with the precursor dissolving readily upon contact with the solvent.
An aerosol was created using a Vicks ultrasonic humidifier, and the mist was observed before the reaction was initiated by the
addition of the carrier gas, which was N2 (BOC, 99.99%). In all cases, the carrier gas flow rate was 1 L min1 and a substrate
temperature of 450–600 C was used. The substrate temperature was controlled by incorporation of the platinum heater track (on
the base of the sensor substrate) into a Wheatstone bridge circuit and all depositions were carried out for 10 min each.
Metal oxide
Alumina substrate
Gold electrodes
Figure 2 Schematic of a sensor chip.
Figure 3 Schematic of electric fields in CVD (EFCVD) experimental setup.
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An electric field was created by applying a specific potential difference across the electrodes of the gas sensor substrate. Both DC
and AC biases (the latter associated to a frequency of 50 Hz) were used and the voltage varied between 0 and 30 V.
7.08.3.2 Materials Characterization

Scanning electron microscopy (SEM) was conducted using a JEOL-6301F field emission scanning microscope operated with an
accelerating voltage of 5 kV. Raman spectroscopy was carried out using a Renishaw inVia Raman (Renishaw Raman System 1000)
microscope using a green argon ion laser of wavelength 514.5 nm. X-ray diffraction (XRD) was carried out using a microfocus Bruker
Discover D8 diffractometer with a wide angle Gadds detector using CuKa1þ2 radiation (l ¼ 1.546 Å) in reflection mode using
a glancing incident angle of 5 .
7.08.3.3 Gas Sensor Characterization

Gas-sensing experiments on the sensors were performed on an in-house test rig (17) designed to maintain up to eight sensors at
a constant operating temperature via a heater driver circuit connected to each sensor’s heater track. The heater circuit was used to set
a range of operating temperatures between 250 and 500 C, and conductivity measurements were taken via the potential divider
circuits. The sensors were tested against various concentrations of NO2 (BOC, 0–800 ppb) and ethanol (BOC, 0–100 ppm) in dry
zero grade air (BOC). Gas response is defined as the ratio of the resistance of the sensor in a flow of synthetic air, R0, and the steady-
state resistance of the sensor in the analyte gas flow, Rg.
7.08.4 Results and Discussion

7.08.4.1 Vanadium Dioxide
The EFCVD and AACVD reaction of vanadyl acetylacetonate at 525 C in ethanol onto a gas sensor substrate afforded dark brown
films. The films were adherent to the substrate, they could not be wiped off with a piece of toweling, passed the Scotch tape test, and
resisted scratching with a brass stylus. They could, however, be abraded with a steel stylus. An electric field was created by passing
a specific voltage across the electrodes (Table 1), both DC and AC supplies were used, and the voltage was varied between 0.1 and 30 V.
Energy dispersive analysis of X-rays (EDAXs) spot analysis indicated that the films had a uniform composition across the
substrate close to VO2. SEM of films prepared from the AACVD route (Figure 4) indicated island growth morphology composed of
100 nm particles that have agglomerated into larger islands, a microstructure typical of AACVD reactions (18,19).
Table 1 Electric field strengths used in sample preparation
Field strength (V m1) Field strength (V m1)

Voltage (V) narrow gap substrate wide gap substrate
0.1 2.22 103 6.66 102

0.5 1.11 104 3.33 103
1 2.22 104 6.66 103
5 1.11 105 3.33 104
10 2.22 105 6.66 104
20 4.44 105 1.3 105
30 6.66 105 2.0 105
Figure 4 Scanning electron micrographs of vanadium dioxide thin films prepared by AACVD of (VO(acac)2) in ethanol at 525 C for 20 min as
described previously (Reproduced from Piccirillo, C.; Binions, R.; Parkin, I. Chem. Vap. Deposition 2007, 13, 145–151). Reproduced from Crane, J.;
Warwick, M.; Smith, R.; Furlan, N.; Binions, R. The Application of Electric Fields to Aerosol Assisted Chemical Vapor Deposition Reactions.
J. Electrochem. Soc. 2011, 158 (2), D62–D67.
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In contrast to the microstructures seen in Figures 4, 5, and 6 show electron micrograph images of films grown using the EFCVD
methodology and the resulting microstructures.
The use of AC and DC fields in the deposition was investigated by the use of variable time experiments. Depositions were
conducted for 1, 2, 5, 10, and 20 min and the resulting films examined by SEM (Figures 5 and 6).
The electron micrographs for the application of a 30 V AC field are shown in Figure 5. After 1 min, little film growth occurs and
a blank substrate is observed (Figure 5(a)). After 2 min, film growth is evident, w20 nm particles coalesce and form rodlike
structures 100 nm in length (Figure 5(b)). A 5 min deposition time leads to further nucleation of growth and the film micro-
structure is akin to a series of 300–400 nm porous spheres made of agglomerated nanorods (Figure 5(c)). After 10 min
(Figure 5(d)), the film microstructure has developed further and larger clusters of nanorods/particles forming spheres up to
a micron in diameter are apparent.
It is also clear at this stage that the nanorod structures are developing secondary nucleation sites and film growth is progressing in
a pseudodendritic manner. By 20 min of deposition (Figure 5(e)), the film morphology is one akin to a cauliflower, where large
porous islands between 1 and 2 mm across cover the substrate surface.
A similar situation is observed for the application of a 30 V DC field to these reactions (Figure 6). Figure 6(a) shows deposition
after 1 min, similar to the application of an AC field – little film growth can be detected and a blank substrate is observed. After
2 min, film growth is evident, once again 20 nm nanoparticles have formed rodlike structures growing in one dimension
(Figure 6(b)). As the deposition time increases to 5 min (Figure 6(c)), it is clear that film growth is occurring along the rod
structures in more than one dimension. After 10 min, the film growth has developed into porous spherical structures 200 nm in
Figure 5 Scanning electron micrographs of vanadium dioxide thin films prepared using the EACVD techniques from (VO(acac)2) in ethanol at
525 C with an applied AC field with different deposition times. Reproduced from Crane, J.; Warwick, M.; Smith, R.; Furlan, N.; Binions, R.
The Application of Electric Fields to Aerosol Assisted Chemical Vapor Deposition Reactions. J. Electrochem. Soc. 2011, 158 (2), D62–D67.
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Figure 6 Scanning electron micrographs of vanadium dioxide thin films prepared using the EACVD techniques from (VO(acac)2) in ethanol at
525 C with an applied DC field with different deposition times. Reproduced from Crane, J.; Warwick, M.; Smith, R.; Furlan, N.; Binions, R.
The Application of electric Fields to Aerosol Assisted Chemical Vapor Deposition Reactions. J. Electrochem. Soc. 2011, 158 (2), D62–D67.
diameter (Figure 6(d)). Finally, after 20 min, the film morphology (Figure 6(e)) is similar to the example in Figure 5(e), consisting
of large porous islands between 1 and 2 mm across that dominate the surface.
XRD of the electric field–assisted aerosol-assisted chemical vapor deposition (EACVD) samples (Figure 7) showed significant
peak broadening compared with films made from AACVD alone (20); the majority phase was monoclinic vanadium dioxide,
although the broadening of the peaks may obscure peaks from other phases such as V2O5. For this reason, the authors have not
sought to evaluate crystallite size from XRD data. The strength and type of the applied field made no discernable difference to the
observed XRD pattern, nor did the deposition time.
X-ray photoelectron spectroscopy of the film surface (Figure 8) indicated multiple vanadium and oxygen environments for all
samples examined. Modeled vanadium shifts (V2p3/2) of 515.4, 516.2, and 517.5 eV are consistent with those previously reported
for V2O3, VO2, and V2O5, respectively (20–22).
The O1s peak is centered at 530.1 eV, is quite broad, and is asymmetric, indicating more than one oxygen environment is
present. Modeling of the O1s peak (Figure 8) gives a good fit with three modeled curves, consistent with three vanadium oxide
environments. Previous work has reported the presence of fully oxidized vanadium at the surface (23), as such the multiple
environments are not surprising. However, a V3þ environment at the surface is unusual and normally found in the bulk of the
material and associated with doping by W6þ (24).
Raman spectroscopy (Figure 9) of the EACVD samples indicated that stretches corresponding to VO2 and V2O5 were both
present. Raman spectroscopy also confirmed the presence of graphitic carbon with two large, broad peaks centered on 1100 and
1400 cm1 (not shown).
Adjusting the strength of the applied field in EACVD reactions had a significant effect on the thickness of the film deposited
(Figure 10). In both cases, as field strength increases film thickness (and implied growth rate) also increases until an optimum level
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Figure 7 Typical X-ray diffraction pattern from a sample prepared using the EACVD methodology from (VO(acac)2) in ethanol at 525 C for 20 min.
Figure 8 X-ray photoelectron spectrum of the vanadium and oxygen regions of the surface of a typical thin film prepared using the EACVD
methodology (VO(acac)2) in ethanol at 525 C for 20 min. Reproduced from Crane, J.; Warwick, M.; Smith, R.; Furlan, N.; Binions, R. The Application
of Electric Fields to Aerosol Assisted Chemical Vapor Deposition Reactions. J. Electrochem. Soc. 2011, 158 (2), D62–D67.
is reached. Beyond this the film thickness decreases. It is anticipated that as field strength is increased the aerosol droplets experience
more acceleration and thus have a higher energy. As a result of this extra energy added to the system from the acceleration of the
aerosol particles due to the presence of an electric field, the likelihood of reaction with the substrate surface also increases. However,
at a particular point the incoming aerosol particles will have so much energy that instead of reacting with the substrate surface it may
collide and rebound; and the precursor contained within will not take part in any surface reaction. As the electric field strength
increases further, and the incoming aerosol droplets have a higher energy, it becomes more likely that this second phenomenon will
dominate and less surface reaction will take place, hence the deposited film thickness and associated growth rate at the highest field
strengths will be lowered.
Stronger electric fields lead to smaller average particle sizes (Figure 11). A smaller particle size can be rationalized in a similar
way to the changes in film thickness with field strength. Higher field strength leads to greater acceleration of the aerosol precursor
toward the substrate surface and hence the droplet has a greater energy. Rather than absorbing onto the surface substrate, this
increased energy allows the precursor to either nucleate and grow where it lands or travel a relatively short distance before
nucleating. As field strength increases, so will this tendency toward nucleation. The migration of absorbed species to nucleation sites
will become less favorable and resultantly smaller island sizes will be observed.
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25000
23000 + VO2
* V2O5
21000
+
19000
Number of counts
17000
*
15000 * +
+ +
+ *
13000 * *
+ +
11000
9000
7000
5000
0 100 200 300 400 500 600 700 800
Wavenumber (cm–1)
Figure 9 Raman spectrum of a typical thin film of vanadium oxide prepared by the EACVD methodology from (VO(acac)2) in ethanol at 525 C
for 20 min. Reproduced from Crane, J.; Warwick, M.; Smith, R.; Furlan, N.; Binions, R. The Application of Electric Fields to Aerosol Assisted
Chemical Vapor Deposition Reactions. J. Electrochem. Soc. 2011, 158 (2), D62–D67.
3500
DC field
3000 AC field
Film thickness/nm
2500
2000
1500
1000
1.00E+04 2.10E+05 4.10E+05 6.10E+05
Field strength (Vm−1)
Figure 10 Graph showing correlation between electric field strength and film thickness in EACVD experiments for both AC and DC fields. For
samples prepared from (VO(acac)2) in ethanol at 525 C for 20 min. Reproduced from Crane, J.; Warwick, M.; Smith, R.; Furlan, N.; Binions, R.
There appeared to be no obvious microstructural difference between films prepared using an AC or DC field, though at higher
voltages some organization along field lines can be discerned with an AC field (Figure 5(e)) that is not observed in the respective
sample prepared with a DC field. In all cases, no difference was observed in morphology between the electrode gap and on top of
the electrode. This is at first glance surprising because it is expected that differently charged species will be attracted to oppositely
charged electrodes, we anticipate that our precursor would become charged in a consistent manner as a result of aerosolization;
however, in an aerosol it is expected that both negatively and positively charged droplets are present as a result of charge transfer
during collisions between droplets. The amount of charge created in this way on the aerosol solvent is expected to far outweigh the
amount of charge created on the vanadyl acetylacetonate precursor as such precursor will be delivered both to electrodes and into
the electrode gap, where an aerosol droplet experiences less acceleration due to the electric field because of either a larger mass or
a smaller charge.
The use of an AC field gave some evidence for growth organization along the field lines at higher field strengths; this was,
however, minimal and may result from the frequency of the AC field used, which was kept at 50 Hz for all experiments. Considering
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70
60
50
Particle size/nm
40
30
20
10
0
1.00E+02 1.00E+03 1.00E+04 1.00E+05 1.00E+06
Field strength (Vm−1)
Figure 11 Graph showing correlation between electric field strength and particle size for samples prepared using the EACVD methodology from
(VO(acac)2) in ethanol at 525 C for 20 min with both AC and DC fields. Reproduced from Crane, J.; Warwick, M.; Smith, R.; Furlan, N.; Binions, R.
the flux of precursor to the reactor and the relatively small area the electric field propagates in, it may be that the precursor effectively
experiences a DC field and any organizational effects are essentially lost. The authors anticipate that by varying the frequency in
future investigations they will be able to add an element of organization into the film structures beyond that which has been
demonstrated here.
Growth appears to be occurring in a dendritic fashion. Normally, the authors would expect an AACVD reaction to occur via an
island growth mechanism (Figure 4), where precursor that comes into contact with the surface and is absorbed has a certain
mobility that allows it to move to a nucleation center and film growth is based around these sites. The addition of an electric field to
the reaction appears to greatly increase the number of nucleation sites. This is due to the addition energy given to the precursor
aerosol from acceleration by the electric field; the consequence is that nucleation can occur more freely and is less constrained by the
thermodynamics of the substrate surface.
A smaller particle size from reactions involving a stronger electric field can be rationalized in a similar manner; as the field
strength increases, acceleration of the precursor to the substrate surface increases, as does the energy of the precursor and the
tendency toward nucleation. As this tendency to nucleate increases, it becomes less probable that the absorbed precursor will
migrate to another nucleation site and contribute toward the growth of an island; hence with a larger number of nucleation sites the
average island size/particle size can be expected to decrease.
Thin films of metal oxides with high surface areas are of great interest generally in materials science and chemistry. They find
applications as chemical sensors, energy storage, and catalysis, to name but a few important applications. Authors anticipate that
this method will prove to be a generally applicable and facile route toward the synthesis of thin films with high surface areas.
7.08.4.2 Titanium Dioxide

The EACVD reaction of titanium isopropoxide at 450 C in toluene onto a gas sensor substrate afforded white thin films (Table 2).
The thin films were adherent to the substrate, they could not be wiped off with a piece of toweling, and they passed the Scotch tape
Table 2 Table of samples prepared from the EACVD reaction of 0.05 ml Ti(iOPr)4 solution in toluene at
450 C with a flow rate of 1.0 L min1 with an applied electric field

Sample Applied voltage (V) Electric field (V m1) Material phase (XRD/EDAX/WDAX)
A 0 0 Anatase TiO2
B 0.5 1.11 104 Anatase TiO2
C 1 2.22 104 Anatase TiO2
D 5 1.11 105 Anatase TiO2
E 10 2.22 105 Anatase TiO2
F 20 4.44 105 Anatase TiO2
G 30 6.67 105 Anatase TiO2
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test. EDAX and wavelength dispersive analysis of X-rays (WDAX) indicated that the composition of the films was uniform across the
substrate with a composition close to TiO2.
SEM of the films prepared from a normal AACVD reaction (Figure 12(a)) had a morphology comprising conjoined spherical
agglomerates some 10 mm in diameter spread across the surface of the sensor substrate. The agglomerate surfaces are heavily
textured, with some surfaces having an octahedral appearance.
Introducing and increasing the applied potential difference (and thus electric field) across the electrodes led to some differences
in the grown film microstructure (Figure 12(b)–12(g)). Increasing the field between 1.11 104 and 2.22 104 V m1 (Figure
12(b) and 12(c)) led to a decrease in the diameter of the spherical agglomerates to around 5 mm. The octahedral texture is also
proportionately decreased in size.
Higher field strengths (Figure 12(c)–12(g)) led to greater agglomeration, and individual agglomerates are hard to differentiate
in the dense film. The surface of the film is increasingly textured with octahedral-shaped features protruding from the surface.
XRD data were collected for the as-prepared films to investigate the materials phase. All of the titanium dioxide films grown were
found to be exclusively anatase matching the Joint Committee on Powder Diffraction Standards (JCPDS) database pattern closely.
Breakthrough to the underlying gas sensor substrate occurred in all cases, and peaks relating to the gold electrodes and silicate
material of the substrate can be easily discerned (Figure 13).
Analysis of the peak broadening shows that the crystallite sizes in all samples are approximately the same. The relative intensity
of the Bragg peaks associated with TiO2 appeared to change between the samples, indicative of preferred orientation. A Rietveld
refinement was carried out using the XRD data and accounting for the preferred orientation using the spherical harmonic model.
Figure 12 Scanning electron microscope images of samples prepared from the EACVD reaction of 0.05 ml Ti(iOPr)4 solution in toluene at 450 C with
a flow rate of 1.0 L min1 with an applied alternating electric field: (a) no field. (b) 1.11 104 V m1. (c) 2.22 104 V m1. (d) 1.11 105 V m1. (e)
2.22 105 V m1. (f) 4.44 105 V m1. (g) 6.67 105 V m1. Reproduced from Panjwani, N.; Naik, A.; Warwick, M. E. A.; Hyett, G.; Binions, R. The
Preparation of Titanium Dioxide Gas Sensors by the Electric Field Assisted Aerosol CVD Reaction of Titanium Isopropoxide in Toluene. Chem. Vap. Deposition
2012, 18, 102–106.
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Figure 13 X-ray diffraction data for samples prepared from the EACVD reaction of 0.05 ml Ti(iOPr)4 solution in toluene at 450 C with a flow rate of
1.0 L min1 with an applied electric field. Where peaks are marked A, S, and G indicates diffraction from the anatase titania film, substrate, and gold
electrodes, respectively. Reproduced from Panjwani, N.; Naik, A.; Warwick, M. E. A.; Hyett, G.; Binions, R. The Preparation of Titanium Dioxide Gas
Sensors by the Electric Field Assisted Aerosol CVD Reaction of Titanium Isopropoxide in Toluene. Chem. Vap. Deposition 2012, 18, 102–106.
This gives a quantitative measure of the preferred orientation, the J value, or texture index (25). This takes a value of 1 if there is no
preferred orientation, and greater than 1 if it is present. For sample A, the intensity of the anatase peaks was too low to reliably
model, but for samples D and F, values of J ¼ 1.2 were found for both patterns, indicating a small degree of preferred orientation.
For sample G, a value of J ¼ 5.1 was found, indicating significant preferred orientation in the crystallites. The relative intensity of the
gold and substrate peaks decreased from sample A through to sample G, indicating an increasingly thick film of TiO2, and reduced
scattering from the underlying layers.
Raman spectroscopy was used to analyze the samples and complement XRD data for phase identification. Figure 14 shows
a representative Raman spectra for all samples. All samples gave strong Raman bands centered at 147, 395, 513, and 642 cm1 and
a weaker band centered at 198 cm1, all of which are attributable to anatase titanium dioxide (26). No bands were identified as
Figure 14 Typical Raman spectra for a sample prepared from the EACVD reaction of 0.05 ml Ti(iOPr)4 solution in toluene at 450 C with a flow
rate of 1.0 L min1 with an applied electric field.
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belonging to rutile titanium dioxide. These would be expected at 143, 447, 612, and 826 cm1 (27). These are clearly absent in our
spectra.
Gas response was measured as the ratio between R0 (the point immediately prior to exposure to ethanol) and Rg (the resistance
when exposed to ethanol). The resistance was measured between the two electrodes of an interdigitated gold electrode structure on
an alumina tile.
All of the TiO2 gas sensors gave an n-type response to ethanol at different concentrations over time (Figures 15 and 16), though
only samples A and B gave significant gas response (Figure 16).
Figure 15 Plot of sensor gas response against ethanol concentration at the optimum sensor operating temperature of gas sensors prepared from the
EACVD reaction of 0.05 ml Ti(iOPr)4 solution in toluene at 450 C with a flow rate of 1.0 L min1 with an applied alternating electric field: (a) no field.
(b) 1.11 104 V m1. (c) 2.22 104 V m1. (d) 1.11 105 V m1. (e) 2.22 105 V m1. (f) 4.44 105 V m1. (g) 6.67 105 V m1. Reproduced from
Panjwani, N.; Naik, A.; Warwick, M. E. A.; Hyett, G.; Binions, R. The Preparation of Titanium Dioxide Gas Sensors by the Electric Field Assisted Aerosol
CVD Reaction of Titanium Isopropoxide in Toluene. Chem. Vap. Deposition 2012, 18, 102–106.
Figure 16 Gas response (R0/Rg) of TiO2 sensors (samples A and B) upon exposure to differing concentrations of ethanol in flowing air over time at the
sensors’ optimum operating temperature. Reproduced from Panjwani, N.; Naik, A.; Warwick, M. E. A.; Hyett, G.; Binions, R. The Preparation of Titanium Dioxide
Gas Sensors by the Electric Field Assisted Aerosol CVD Reaction of Titanium Isopropoxide in Toluene. Chem. Vap. Deposition 2012, 18, 102–106.
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The gas response was rapid, and a near plateau was reached within minutes of exposure to ethanol (Figure 16).
The sensors grown without an applied electric field (sample A) responded quickly to ethanol and rapidly saturated achieving
a steady state (28,29). When the ethanol flow was stopped, the response dropped to near baseline level and then tailed off more
slowly to the baseline. Sample B, grown with an applied field of 1.11 104 V m1, also displayed similar gas response charac-
teristics, although the magnitude of response was almost double that of the sensor grown without an electric field (sample A).
The response to ethanol was also tested at different temperatures. Figure 17 summarizes response behavior of the sensors to
100 ppm ethanol in dry air at operating temperatures between 250 and 500 C. It was found that for the majority of sensors (C–G),
there was no significant variation in gas response at different temperatures. For the sensor films grown without an applied electric
field (sample A), the optimum operating temperature was 350 C. For sample B, grown with an applied electric field of
1.11 104 V m1 the optimum operating temperature was found to be higher at 450 C.
The authors have suggested previously that a variety of phenomena in film growth from CVD reactions can occur when an
electric field is applied (11,14,15) and have previously observed an increase in growth rate in thin films of vanadium oxide produced
in the same experimental setup (11). This was attributed to an increase in the velocity of species as they approached the sensor
substrate surface and became affected by the electric field. This is thought to be either as a result of an interaction between the
permanent dipole of the CVD precursor species and the electric field or through an induced dipole in the CVD precursor species,
caused by the electric field. The incoming species is thought to have greater kinetic energy and therefore a higher probability of
nucleating on the substrate surface.
In this work, the authors anticipate that this is also an important effect; however, it is likely that other phenomena are also
occurring. The increase in preferential orientation with an increase in electric field strength seen from the XRD data indicates
that the electric field is aligning growth at the crystallographic level. They have previously suggested that some kind of
orientation may occur in the gas phase as the precursor approaches the substrate or once the precursor species has adsorbed
onto the substrate surface (33,34). However, in this instance, it is unlikely that the titanium tetraisopropoxide precursor is
orientating with the field as this precursor is for all intents and purposes electrically symmetrical. Therefore, the preferential
crystallographic orientation seen here with increasing field is most likely a result of the electric field influencing film growth
processes on the substrate surface.
SEM indicates a subtle change in microstructure as the electric field strength is increased in the deposition (Figure 12). This
suggests that reaction occurs at a faster rate; the smaller feature size seen in the samples grown with stronger electric fields (Figure
12(e)–12(g)) also supports this idea. As they have noted orientation effects, it is unlikely that this increase in reaction rate can be
attributed solely to an increase in precursor kinetic energy. The authors feel it is likely that the precursor species, once absorbed on
the substrate surface, may be activated by having the bonds along the axis of its permanent or induced dipole pulled, attracted by the
electric field.
This change in microstructure has significant implications for the gas-sensing capabilities of the sensors. The most widely
accepted theory of chemiresistive gas-sensing states that “when a metal oxide semiconductor gas sensor is exposed to air, oxygen
species are adsorbed on the surface of the sensor and go on to be ionized by electrons from the materials conduction band to form
Figure 17 The temperature dependency of the sensors to 100 ppm ethanol gas in dry synthetic air. Reproduced from Panjwani, N.; Naik, A.; Warwick,
M. E. A.; Hyett, G.; Binions, R. The Preparation of Titanium Dioxide Gas Sensors by the Electric Field Assisted Aerosol CVD Reaction of Titanium
Isopropoxide in Toluene. Chem. Vap. Deposition 2012, 18, 102–106.
www.iran-mavad.com
species such as O 2 ” (30). As such, in air, the measured resistance of TiO2 and other n-type semiconductors will increase due to the
lower concentration of free electrons in the materials’ conduction band (6). On exposure to a reducing gas such as ethanol, surface
reaction between the oxygen species and analyte gas can occur, leading to the release of electrons trapped in the ionized oxygen
species back into the materials conduction band, thereby lowering the measured resistance.
The ability of the sensor material to absorb and ionize oxygen species is fundamental to the sensor performance. The enhanced
performance observed here for sensor B is likely to be the result of two factors. The number of surface reactive sites increases and the
surfaces of the crystallites become significantly more reactive and are likely to absorb oxygen and form ionized oxygen species
(7,31,32).
The surface to volume ratio of sensor B is also increased (in comparison to sensor A). This is a result of increased surface texturing
and a higher density of surface protrusions (Figure 12(a) and 12(b)). This means that the amount of oxygen that can be absorbed
and ionized is increased. Increased texturing may also provide an increased number of lower energy step and kink sites that oxygen
will preferentially migrate to the surface. Indeed the performance of this sensor with a response of Rg/R0 of 6–100 ppm to ethanol
compares favorably with other TiO2 sensor films tested against ethanol (33–36) where responses are typically less than 2. The results
obtained here are comparable to sensors fabricated from TiO2 nanomaterials where the gas response is typically higher, between
5 and 10 (37,38).
Further gas response enhancement is not seen from the films grown with higher electric fields as the films become thicker
(implying a faster growth rate) there is a tendency for grains to coalesce and a continuous poorly porous film to be formed (Figure
12(c)–12(g)). This loss of porosity has a detrimental effect on the surface area of the film, preventing gas diffusion throughput the
material and leading to a reduction in gas adsorption and reaction sites and ultimately a lower response.
7.08.4.3 Tungsten Trioxide

The EACVD reaction of tungsten hexaphenoxide at 600 C in toluene onto the gas sensor substrates afforded blue or blue-black as-
deposited film, indicative of reduced tungsten oxide: WO3x. Upon annealing the sensors at a temperature in the range of 500–
600 C in air, a visible change in color of the films from blue-black to yellow was observed, indicative of fully oxidized tungsten
oxide, WO3. The pre- and postannealed colors of the films and the fibrous morphology obtained from the EACVD reactions were
retained (9,39).
An electric field was created by applying a specific potential difference across the electrodes of the gas sensor substrate. Both DC
and AC biases (the latter associated with a frequency of 50 Hz) were used and the voltage varied between 0 V and 30 V and these are
summarized in Table 3.
SEM images of the depositions are shown in Figure 16. Deposition carried out in the absence of an electric field, shown in
Figure 18(a), indicated that the film is comprised of 170 nm diameter and 1 mm long fibers, with a random anemone type
orientation in the electrode gap and short, simple, fibrous growth on the electrode surface.
Introducing and increasing the applied potential difference and thus the electric field across the electrodes of the gas sensor
substrates during the AACVD deposition led to a change in the morphology of the deposited films. As the electric field strength was
increased (Figure 18(b)–18(e) for a DC bias Figure 18(f)–18(h) for an AC bias), the deposited nanoneedles reduced in diameter
and grew longer. A diameter of w10 nm and needle length of several micrometers could be observed (Figure 18(h)). Increased field
strength was also found to cause a disruption to the anemone type growth observed for the sensor grown without an applied electric
field (Figure 18(a)). The predominant morphology at higher field strength was one of randomly oriented nanoneedles
(Figure 18(h)), although some evidence of central nucleation points remains (Figure 18(e)). The effect of an AC and DC applied
field was noted to be different. Where the same strength electric field of 1.8 105 V m1 was applied (Figure 18(d) and 18(h))
different morphologies prevailed. The DC field (Figure 18(d)) led to a morphology that still had an anemone type structure of
central nucleation points with extruded nanoneedles w100 nm in diameter and 1.5 mm in length, whereas the equivalent AC
sample (Figure 18(h)) had a morphology consisting of randomly orientated nanoneedles some 20 nm in diameter and up to 2 mm
in length with no apparent central nucleation point.
Glancing angle XRD studies of the postannealed WO3 films clearly indicated the formation of monoclinic g-WO3 (Figure 19).
All patterns corresponded to the JCPDS pattern ICDD 43-1035 (40). Some breakthrough to the gas sensor substrate could clearly
Table 3 Samples prepared from the EACVD reaction of tungsten hexaphenoxide in toluene at 600 C
Sample Voltage (V) Electric field strength (V m1)
A 0 0
B 1 DC 1.8 104
C 5 DC 9.1 104
D 10 DC 1.8 105
E 30 DC 5.5 105
F 1 AC 1.8 104
G 5 AC 9.1 104
H 10 AC 1.8 105
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Figure 18 SEM images of samples prepared from the EACVD reaction of 15 ml 0.05 M W(OPh)6 solution in toluene at 600 C with a flow rate of
1 L min1. Images above are: sample (a) no field sensor substrate, sample (b) 1.8 104 V m1 DC field, sample (c) 9.1 104 V m1 DC field, sample
(d) 1.8 105 V m1 DC field, sample (e) 5.5 105 V m1 DC field, sample (f) 1.8 104 V m1 AC field, sample (g) 9.1 104 V m1 AC field, sample (h)
1.8 105 V m1 AC field. Reproduced from Naik, A. J. T.; Warwick, M. E. A.; Moniz, S. J. A.; Blackman, C. S.; Parkin, I. P.; Binions, R. Nanostructured
Tungsten Oxide Gas Sensors Prepared by Electric Field Assisted Aerosol Assisted Chemical Vapour Deposition. J. Mater. Chem. A. 2013, 1, 1827–1833.
Figure 19 XRD data for samples prepared from the EACVD reaction of 15 ml 0.05 M W(OPh)6 solution in toluene at 600 C with a flow rate of
1 L min1. Where the peaks are marked with the strongest reflections from WO3 or with * indicating peaks due to breakthrough to the underlying
substrate or gold electrodes.
be observed. The samples prepared with no electric field applied and a field with a DC bias demonstrated a crystallographic
orientation in the (002) consistent with previous literature reports of films of WO3 prepared by CVD methodologies (16,41). In
contrast, the films prepared with an AC bias indicated no preferential orientation between the (002), (020), and (200)
orientation.
Raman spectroscopy (Figure 20) was used to analyze the postannealed samples and complement the XRD data in order to
identify the phase of WO3. In all cases, the Raman spectrum displays sharp, thin, and well-defined peaks, indicating the crystalline
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Figure 20 Typical Raman spectra of sample B, typical of all WO3 samples prepared from the EACVD reaction of 15 ml 0.05 M W(OPh)6 solution
in toluene at 600 C with a flow rate of 1 L min1. The peaks in the plot represent the following: 911 cm1 W6þ ¼ O stretch, 807 cm1 W–O–W
stretching mode, 720 cm1 W–O–W stretching mode, 335 cm1 W–O–W bending mode, 275 cm1 W–O–W bending mode.
nature of metal oxide. All samples gave strong bands at 911, 807, 720, 335, 275, 190, and 140 cm1, all of which have been
observed in previous studies and are attributable to monoclinic g-WO3 (9,42–44).
The gas-sensing response of the sample was defined as the ratio between R (the resistance of the sensor during exposure to
the target analyte) and R0 (the baseline resistance of the sensor prior to the first NO2 purge). The resistance was measured
between the two electrodes of the interdigitated gold electrode structure on the alumina tiles at a variety of operating
temperatures between 250 and 500 C. All of the WO3 sensors gave an n-type response to NO2 at different concentrations as
a function of time (Figure 21).
Figure 21 Plot of maximum sensor responses against NO2 concentration at the optimum sensor operating temperature of samples A, B, E, and F.
Reproduced from Naik, A. J. T.; Warwick, M. E. A.; Moniz, S. J. A.; Blackman, C. S.; Parkin, I. P.; Binions, R. Nanostructured Tungsten Oxide Gas
Sensors Prepared by Electric Field Assisted Aerosol Assisted Chemical Vapour Deposition. J. Mater. Chem. A 2013, 1, 1827–1833.
www.iran-mavad.com
Figure 22 shows the gas response of sample A to a variety of concentrations of NO2 at different operating temperatures. The
sensor responded quickly to NO2 although did not completely saturate at lower operating temperature, leading to a ‘shark fin’
response shape (28,29). When the analyte gas flow was stopped, the response dropped to near baseline level and then tailed off
more slowly to the baseline. A maximum response of 45 was observed at an operating temperature of 250 C to an NO2
concentration of 800 ppb.
Sample B, grown with an applied DC field of 1.8 104 V m1, also displayed similar gas response characteristics (Figure 23),
although the maximum response was two and a half times that of the sensor grown without an electric field (sample A, Figure 22)
under identical operating conditions.
Gas-sensing experiments on the sensors showed a universal pattern: an increasing response with decreasing operating
temperature (Figure 24), which was as low as 250, or 300 C for sensors that were prepared with a higher applied electric field. In
these cases, an operating temperature of 250 C led to a baseline resistance that was too high to obtain a reliable reading.
A large enhancement in response is observed at temperatures below 350 C. Above this temperature, sensor response was
generally low, with poor variation between different analyte gas concentrations.
Previous investigations (9,11,13) have shown that the application of an electric field during a CVD reaction influences the
microstructure, crystallographic orientation, and subsequent properties of the deposited materials. Indeed, it is well known that
sensor microstructure plays a significant role in the gas response of a gas-sensing material (28). The authors have suggested
previously that a variety of phenomena may be occurring when an electric field is applied to CVD growth (11,13–15). For example,
they have reported that electric fields can cause an increase in growth rate and pseudodendritic-type morphologies by accelerating
gas phase species toward the surface (11). This was considered to be the result of an interaction between a permanent or induced
dipole in the CVD precursor species and the applied electric field; greater kinetic energy would increase the probability of nucleation
on the gas sensor substrate surface, increasing film growth rate as well as causing a reduction in the scale length of the deposited
particles. In the gas phase, the applied electric field may cause the precursor molecule to orientate in a particular way toward the
surface; it may also activate some of the precursors bonds, by causing an extension in a bond along the axis of a dipole, thus
lowering the energy of nucleation. Gas phase effects are undeniably important in this work. The authors anticipate that other
surface-related effects may also be occurring as previously reported (13). The XRD data (Figure 19) are particularly compelling, in
that films grown with an AC field show no apparent overall orientation while films grown with a DC field show a bias along the
(002) plane. This suggests that the DC field is causing a consistent orientation or alignment of the precursor molecule to the initial
nucleation point that promotes growth in a specific crystallographic plane, most likely through a charge-mediated process, whereas
an AC field produces a random orientation. This is unlikely to occur as a result of a gas-phase effect given that the tungsten
Figure 22 Resistive response (R/R0) of WO3 sample A, upon exposure to increasing concentrations (50, 100, 200, 400, and 800 ppb) of NO2 gas
at varying operating temperatures. The inset zooms into the resistive response results of the lower concentrations for better clarity. Reproduced from
Naik, A. J. T.; Warwick, M. E. A.; Moniz, S. J. A.; Blackman, C. S.; Parkin, I. P.; Binions, R. Nanostructured Tungsten Oxide Gas Sensors Prepared
by Electric Field Assisted Aerosol Assisted Chemical Vapour Deposition. J. Mater. Chem. A 2013, 1, 1827–1833.
www.iran-mavad.com
Figure 23 Resistive response (R/R0) of WO3 sample B upon exposure to increasing concentrations (50, 100, 200, 400, and 800 ppb) of NO2 gas at
varying operating temperatures. The inset zooms into the resistive response results of the lower concentrations for better clarity. Reproduced from
Naik, A. J. T.; Warwick, M. E. A.; Moniz, S. J. A.; Blackman, C. S.; Parkin, I. P.; Binions, R. Nanostructured Tungsten Oxide Gas Sensors Prepared
by Electric Field Assisted Aerosol Assisted Chemical Vapour Deposition. J. Mater. Chem. A 2013, 1, 1827–1833.
Figure 24 Plot of maximum sensor resistive response of sample B as a function of temperature at various NO2 concentrations. The general
behavior is typical of all sensors tested. Reproduced from Naik, A. J. T.; Warwick, M. E. A.; Moniz, S. J. A.; Blackman, C. S.; Parkin, I. P.;
Binions, R. Nanostructured Tungsten Oxide Gas Sensors Prepared by Electric Field Assisted Aerosol Assisted Chemical Vapour Deposition.
J. Mater. Chem. A 2013, 1, 1827–1833.
www.iran-mavad.com
hexaphenoxide precursor is electrically symmetrical. Likewise the reduction in nanoneedle diameter and increase in length
(Figure 18) suggest a surface effect where growth is directed through a localized electric field rather than as a result of solely gas-
phase effects (11).
These changes in microstructure have significant effects on the gas-sensing behavior of the sensors. The most accepted theory of
chemiresistive gas sensor sensing states “when a metal oxide semiconductor gas sensor is exposed to air, oxygen species are adsorbed
on the surface of the sensor and go on to be ionized by electrons from the materials conduction band to form species such as O2”
(30). As such in flowing air, the measured resistance of WO3 and other n-type semiconductors will increase due to the lower
concentration of charge carriers in the materials’ conduction band (6). On exposure to an oxidizing gas such as NO2, surface
reaction between the oxygen species and analyte gas can occur, leading to the accumulation of electrons trapped in the ionized
oxygen species at the surface, thereby increasing the measured resistance. As such, the ability of the gas-sensitive material to absorb
and ionize oxygen species is of great importance when considering the sensor’s properties. The single biggest factor in the
improvement in the response of sensor B is most likely to be a reduction in scale length for the nanoneedles. Sensor A has a needle
diameter of some 170 nm, while sensor B has needles with a diameter of around 30 nm (Figure 18(a) and 18(b)). This will lead to
an increase in the relative surface area that causes an increase in sensor response, as more of the material’s surface is able to take place
in reactions that cause changes to the materials charge carrier concentration. It is also likely that the material’s surface becomes more
reactive and therefore likely to absorb and ionize oxygen (7,31,32).
Further gas response enhancement is not seen from the films grown with higher electric fields (above 9 104 V m1). This is
most likely an effect of microstructure. As electric field strength is increased, the nanoneedle morphology is altered, the needles
become thinner and longer (Figure 18); this has a detrimental effect on the gas sensor performance. Although the surface to volume
ratio is increased, the authors do not observe an enhanced response. This is due to the growing importance of the film grain
boundaries. The reduced needle diameter causes an increase in the resistance of the grain boundaries at the base of the sensor film.
Therefore, these sensors require an increased operating temperature and have a higher baseline resistance, as there are fewer
percolation pathways. Were the needles to be orientated between the electrodes, it might be reasonable to expect an increase in gas
sensor response, particularly if the needles were long enough to bridge the electrode gap.
The performance of sample B with a gas response of 110–800 ppb compares favorably to other WO3 gas sensors detecting ppb
levels of NO2 (45–48). Typically nanocrystalline WO3 sensors give a response (R/R0) to 550 ppb NO2 of 4 (48). WO3 sensors
prepared by sputtering (47) and CVD (45) methodologies give responses of 2.75–100 ppm NO2 and 7.4–200 ppb NO2, respec-
tively. Indeed, the response compared to other nanostructured WO3 gas sensors prepared by CVD is enhanced (9,46). With
a response of 28–200 ppb NO2 at an operating temperature of 250 C compared to 10 under the same conditions (46), or
a response of 110–800 ppb NO2 at 250 C compared to a response of 90 at 400 C (9), it can be summarized that the EACVD
method shows great promise for producing sensors with enhanced sensitivity.
7.08.5 Conclusions
The use of electric fields in the AACVD reactions of titanium isopropoxide, tungsten hexaphenoxide in toluene, or vanadyl ace-
tylacetonate in ethanol on gas sensor substrates led to the production of titanium, tungsten, or vanadium oxide thin films. Changing
the strength of the electric field could lead to dramatic changes in morphology, thickness, implied growth rate, and preferential
orientation of the deposited films. The gas sensor properties of the films were examined by exposure to parts per million amounts of
ethanol gas (titanium dioxide samples) or parts per billion amounts of nitrogen dioxide gas (tungsten oxide samples) in synthetic
air and measuring changes in the resistance of the film. The link between film microstructure and gas sensor performance is
confirmed. Applying an electric field during the deposition process led to films with enhanced microstructures for gas sensing,
leading to an increase in response between two and three times that of a sensor film grown without an applied electric field.
Acknowledgments
Russell Binions thanks the Royal Society for a Dorothy Hodgkin fellowship and the EPSRC for financial support (grant number EP/
H005803/1). Mr. Kevin Reeves is thanked for invaluable assistance with electron microscopy.
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www.iran-mavad.com
7.09 AFM Applications in Micro/Nanostructured Coatings

7.09.2 Basic Performance of AFM 195
7.09.3 Cantilever 196
7.09.3.1 Detection of Cantilever Orientation 196
7.09.3.2 Cantilever Geometry 196
7.09.4 Tips 200
7.09.4.1 Tip Interaction with Surface 201
7.09.5 Various Modes of AFM Devices 202
7.09.5.1 Contact Modes 202
7.09.5.2 Constant Force Mode 202
7.09.5.3 Constant Height Mode 202
7.09.5.4 Semicontact Modes 204
7.09.5.5 Constant Amplitude Mode 205
7.09.5.6 Phase Difference Imaging Mode 205
7.09.6 AFM Applications for Coatings 207
7.09.6.1 Investigation of Latex Particle Morphology and Surface Structure of the Coatings 207
7.09.6.2 Study on Crystallization 207
7.09.6.3 Study of DNA Molecules Stretched by Spin-Coating Technique 209
7.09.6.4 Morphology Formation in Thin Films Deposited by Different Methods 210
7.09.6.5 Study of Friction Process and Nanometric Changes in the Friction Bearing Pieces 210
7.09.6.6 Characterizing Coating Layer z-Directional Binder Distribution in Paper 210
7.09.6.7 Metallurgy and Wear 214
7.09.6.7.1 Characterization of Ultrathin DLC Coatings 214
7.09.6.7.2 Direct Visualization of Sliding-Induced Tribofilm on Nanocomposite Coatings 216
7.09.6.7.3 AFM of Ion-Etched Cross-Sections for Analyzing the Morphology of Dense Hard Coatings 216
7.09.6.7.4 Nanotribological Characterization of Coatings 217
7.09.6.8 Determination of Coating Young’s Modulus 217
7.09.6.9 Surface Topography, Membranes, and Filters 220
7.09.6.10 Testing the Surface Parameters of Coatings of Medical Implants 222
7.09.6.11 Control of Quality and Study of Surface Defects in Magnetic Memory Units 222
7.09.6.12 Parameterization of the Magnetite Coating Surfaces 222
7.09.6.13 Integration of AFM and Scanning Electrochemical Microscopy (SECM) Techniques 222
7.09.6.13.1 Pitting Mechanism on Stainless Steel Nanocrystalline Coating 223
7.09.6.13.2 Crystal Growth in Thin Films 225
7.09.6.13.3 Micronanotribology of Ultrathin Hard Amorphous Coatings 225
7.09.6.14 In Situ Thickness Measurements of Ultrathin Multilayer Films 225
7.09.6.15 Measurements of Elastic Properties of Ultrathin Coatings 227
7.09.6.16 Coupled Applications 227
References 238
7.09.1 Introduction
Atomic force microscope (AFM) is a powerful tool to investigate surface properties and structure of materials in nanometric scale.
Flexibility, large number of potential signals, and its performance in various modes have been a great assistance for researchers to
study different surfaces and different media, including vacuum, air, and liquid. Unlike many other techniques for the study of
surface properties, in this technique the type of surface and environment are not considered as important limitation. These devices
allow determination of conductive or insulate, soft or hard, bulk or powder, and organic or inorganic materials. It is also possible to
measure geometrical morphology, adhesion, friction, surface impurities, type of different spots of the surface, elasticity, magnetic,
different chemical bonds, distribution of surface electrical charges, and polarity of various electrical points (1–9). These capabilities
are technically utilized to evaluated cleanness, uniformity, roughness, friction, size, etc. Many researchers applied AFM in their work

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192 AFM Applications in Micro/Nanostructured Coatings
and nowadays this microscope becomes a handy tool for researches in nanoscale. Hosoi et al. studied fabrication of the AFM probe
on a GaAs wafer to develop a new structure microwave probe (10). Besides, they evaluated properties of the AFM probe using
various nanostructured metal coatings to understand performance of the probe for materials topography and microwave signals
propagation. Sputtering and the electron beam evaporation techniques were applied on the top and bottom surfaces of the GaAs
AFM probe with Au or Al film to introduce a waveguide. In addition, the open structure of the waveguide at the tip of the probe was
introduced through fabrication of the focused ion beam. According to the findings of their work, the produced probes coated with
Au or Al films involve nanometer order resolution. Furthermore, applying Au-coating probe developed by the electron beam
evaporation technique, the microwave emission was successfully detected at the tip of the probe once it approaches an Au film
sample.
Gu et al. applied AFM to investigate morphology and microstructure of an amine-cured epoxy before and after outdoor
exposure (11). They performed the necessary measurements using samples prepared in an essentially CO2-free, H2O-free glove
box, and samples prepared in ambient conditions. For the first group of samples, AFM imaging was carried out on (1) an
unexposed air/coating surface, (2) an unexposed coating bulk, (3) an unexposed coating/substrate interface, and (4) a field
exposed air/coating surface. In addition, for the latter groups, only unexposed air/coating surface was evaluated. The AFM
technique was applied to scan the same regions of the exposed samples over a periodic basis in order to monitor the variations
in the surface morphology of the coating during the progress of the UV exposure process. Also, small angle neutron scattering
and Fourier transform infrared spectroscopy were conducted in this work for microstructure verification and following the
chemical changes during outdoor exposure, respectively. The finding of this research indicated that amine blushing, which only
takes place under ambient conditions, significantly affects surface morphology and microstructure of the epoxy. Also, it was
found that the surface morphology of the samples prepared under CO2-free dry conditions was generally smooth and homo-
geneous. However, the interface and bulk samples revealed a clearly biphasic structure consisting of bright nodular domains and
dark interstitial regions, which indicate an inhomogeneous microstructure. This heterogeneous structure of the bulk was
consistent with findings obtained through small angle neutron scattering of unexposed samples and AFM phase imaging of the
degraded sample surface.
Garcia-Ayuso et al. applied AFM to study the relationship between the surface morphology and water vapor diffusivity of barrier
coatings on polymeric polyethylene terephthalate (PET) films (12). The aluminum oxide and/or silicon oxide coatings were grown
by various deposition techniques. Because of the inhomogeneous coating morphology, no correlation was found when the surface
roughness is measured over large scanned areas. Nevertheless, for scan sizes of 0.5 m in width in representative zones, which are
from bumps and pinholes, the films smoother than the PET substrate indicated a low permeability. This finding might support the
idea that some other mechanism, different from the existence of surface irregularities (including bumps, pinholes, etc.) and related
to the form of growth, should also play a role in the control of the barrier diffusivity.
Nowakowski et al. applied AFM to study thin Au films deposited under ultrahigh vacuum conditions on a glass support
maintained at 78 K (13). So, several thin gold film structures were determined and characterized ranging from (1) nanometric
isolated gold islands and (2) nanometric gold structures to (3) continuous gold films. All mentioned structures depended on the
amount of the deposited Au. Also, the effect of the amalgamation process was examined on thin Au films topography in this
work. An interesting finding of fundamental importance of this research was on the surface defects on amalgamation rate.
Moreover, the movement of small Au islands on glass obtained as the result of thermal decomposition of Au/Hg alloys was seen
in their work. According to the findings of their research: (1) Based on exposure time of the samples, deposition of gold on a glass
support maintained at 78 K leads to various unique gold structures including nanometric isolated gold islands, nanometric gold
structures, and continuous gold films. (2) In addition, the interaction of thin gold films with Hg vapor at 298 K results in a change
in the structure of the thin gold film. Nanostructures containing a large number of Au–Hg compounds can be developed based on
samples’ exposure time. (3) Here, the local defects on the thin gold film surface have a key role in the of amalgamation rate. (4)
Well-organized structures of Au/Hg alloys (which form regular tetrahedrons on the thin Au film surface) were observed. (5) Au/
Hg alloys’ structure is not stable; rather, it varies with time when stored under ambient conditions. (6) The thermal decompo-
sition of Au/Hg alloys allows Au islands displacement. In this study, a distinct movement of small Au islands on glass was
observed.
Grotenhuis et al. indicate that the application of the spin-coating technique is not limited to the preparation of microcrystals
of amphiphilic molecules, but it can also be utilized to deposit molecules with no hydrophilic headgroup (14). The hydrophilic
silicon wafers were spin-coated using anthracene solutions in chloroform. AFM images revealed the molecular packing of the
anthracene molecules on the surface of the microcrystals. Such structure is in agreement with the single crystal X-ray diffraction
data. They indicate that it is possible to deposit microcrystals of anthracene on oxidized silicon wafers using the spin-coating
technique. The molecular packing of the bulk crystals of anthracene was previously determined using the X-ray diffraction.
The created anthracene crystals can be cleaved along the ab-plane. This observation corresponds with previous results indicating
no microcrystals are formed in the case no plane of easy cleavage is present. This hypothesis is further supported by the
experiments with triphenylene, which could not be formed by spin-coating. According to the XRD analyses, the bulk structure
involves no cleavage plane. There is an agreement between the angles between the side-faces of the microcrystal with those
between different crystallographic orientations. They concluded that the directions of the a-axis and b-axis are along that of
x-direction and y-direction; which can be confirmed by the molecular resolution images. The axes’ lengths determined using the
AFM images of the ab-plane of anthracene correspond with the values obtained with XRD tests. To obtain the error values, several
AFM measurements were carried out. Via surface structure observation, it was concluded that no surface rearrangement occurred.
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AFM Applications in Micro/Nanostructured Coatings 193
They also indicated that the spin-coating method can also be applied for deposition of molecules with no hydrophilic headgroup.
Compared to the Lattice Boltzmann (LB) method, this can be considered as an advantage of the spin-coating technique since the
LB method cannot be utilized for deposition of this kind of molecules.
Barberi et al. applied AFM to examine the surface of a capillary after coating with ‘soft’ polymers, namely polyacrylamides (15).
The main objective of their work was the study of the efficiency of silica surface coating in order to decrease or eliminate the electro-
osmotic flow (EOF), which is considerably damaging in macromolecules separation. The quality of such coating is strongly
controlled by two variables including temperature and pH. In the first case, progressively higher temperatures lead to the creation of
open silica patches in which no polymer seems to be bound. At temperature of 50 C, a transition from coated to largely uncoated
surfaces takes place. Besides, the pH of the polymerizing solution has a strong effect on coating efficiency. The direct measurement of
EOF in coated and uncoated capillaries under an electric field completely confirmed the data obtained from AFM tests.
Rickerby et al. investigated the structure of RF sputtered multilayer Ti–BN coatings through applying low-voltage scanning
electron microscope, energy-dispersive X-ray spectrometry, transmission electron microscope, and atomic force microscope (16).
Suitable specimen preparation methods – fracture of the substrate, masking the growing film to produce a taper section, and ion-
beam milling of embedded cross sections – were explained for each technique. The presence of similar composition contrast in
scanning electron micrographs with AFM images facilitated the creation of correlation between them. Quantitative X-ray
microanalysis of the layers was conducted using the f(pz) approach. Selected-area electron diffraction and convergent-beam
microdiffraction as c-w-titanium and FCC titanium nitride were utilized to detect the crystalline structures of nanocrystalline
grains nucleated by interdiffusion reactions during thermal annealing. In their study, parameters such as layer thicknesses,
chemical composition, interdiffusion, and crystalline structure in Ti–BN multilayer films were measured using a combination of
techniques including low-voltage SEM, transmission electron microscopy, and AFM. Either low voltage SEM or AFM could easily
be applied to measure interlayer distances. The findings of this work allowed an understanding of phase transformations related
to interdiffusion reactions in Ti–BN multilayers. These projects contribute to the formation of hard multilayer coatings for
tribological applications.
Tocha et al. studied nanotribological properties of nanostructured thin films of tetragonal ZrO2 on oxidized Si(100) (17).
To evaluate these properties as a function of grain size and relative humidity (RH), they applied atomic force microscopy. They
indicated that nanostructured ZrO2 shows a 50% decrease in friction coefficient m in comparison to oxidized Si(100) in dry nitrogen
atmosphere and 40% RH. For both samples, a maximum of m was observed at c. 40% RH, while for ZrO2 samples with grain sizes
between 12 and 30 nm, the differences in m were slight. The ideal tribological properties allow the application of nanostructured
zirconia as wear resistant low friction coatings on a large number of materials. According to AFM-based nanotribology tests, the thin
films of nanostructured zirconia on Si(100) have a lower friction coefficient by a factor of two in comparison to the oxidized Si(100)
in dry nitrogen atmospheres and 40% RH. For ZrO2 and oxidized Si(100), a considerable effect of the RH on the friction coefficient
was seen and quantified. In addition, the friction coefficient increased with the increase of humidity, reached a maximum value for
40% RH, and then decreased. An explanation for such an increase in the friction coefficient might be the formation of water capillary
bridges; however, at high humidity, water may act as a lubricant. Friction coefficient measured in samples with grain sizes between
12 and 30 nm indicated no significant difference, where this can be attributed to the ignorable differences in mechanical and
microstructural properties of the samples.
Brus et al. made hybrid organic–inorganic (O–I) epoxide-based products from functionalized organosilicon precursors, olig-
omeric di-, and triamines (18). Also, in some cases, they characterized colloidal silica particles through NMR spectroscopy and AFM.
Furthermore, they applied solid-state NMR spectroscopy to investigate the kinetics and reaction mechanism of condensation
reactions, structure, and segmental dynamics of final films, as well as homogeneity and partial ordering. Finally, they applied the
AFM technique to determine surface morphology and other surface characteristics. They indicated that the advanced solid-state
NMR spectroscopy techniques are considered powerful tools for study of the structure, arrangement, and molecular dynamics at
the atomic and segmental level of complex organic–inorganic films. According to this research, there are significant differences in the
mechanism of final structures development, segmental dynamics, and ordering plus homogeneity of the prepared systems. The
system based on GTMS (trifunctional) and 0230 (tetrafunctional) monomers create a nano-heterogeneous network with highly
condensed cage-like siloxane clusters, which are separated by the organic phase. On the other hand, the systems made of GMDES
(bifunctional) and T403 (hexafunctional) monomers develop a homogeneous, rather flexible random network without any
ordering, which is partially condensed in the siloxane part. Presence of these compact clusters considerably hinders segmental
motions. Study of surface morphology by the AFM technique indicated that the surface of nanocomposite hybrid organic-inorganic
coatings is very smooth and regular. In the case that the colloidal silica nanoparticles are present in the reaction system, they can be
easily detected.
Perry et al. investigated the corrosion behavior of WC–Co–Cr and WC–Co high velocity oxygen fuel (HVOF) sprayed coatings in
static saline conditions (19). Direct current (DC) polarization tests were performed. Applying in situ AFM and scanning electron
microscope show that the electrochemical corrosion behavior is complex because of the composite ceramic-metal nature of the
coating. Once adding chromium (Cr) to the matrix, it was observed that the corrosion resistance of the coating significantly
enhances. According to this work, application of AFM helps determination of corrosion mechanisms on a microscale. Besides,
adding chromium to a cobalt matrix promotes the corrosion resistance of a WC-based HVOF sprayed cermet coating. The extent of
this process has been quantified in this work. Although the WC–Co–Cr coating is subjected to more localized attack at 18 C, once
WC–Co is accentuated at the hard phase–matrix interface, it indicates more uniform corrosion which affects the entire matrix.
A temperature rise results in extensive dissolution of the cobalt matrix, while on the CoCr matrix, more severe attack is further
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localized in regions which are not associated with any particular microstructural features. Alacakir et al. investigated the
morphological effect of gamma irradiation on the acrylic based secondary coating surface which had surrounded the cladding of the
single mode optical fibers (20). They irradiated 9 mm optical fibers (high grade pure silica) with 125 mm and 250 mm cladding and
secondary coating in diameter, respectively, with 60Co g rays at a dose rate of 15 kGy h1. Then, they obtained a few secondary
coating surfaces through AFM after 28, 59, and 100 kGy exposure. Compared to the unirradiated surface, roughness was observed to
considerably increase with dose increase. The number and sizes of the morphological changes was increasing as once analyzing the
irregular hill like structures from the height profiles with hill to trough differences in the order of 120 nm.
Garcia-Ayuso et al. applied AFM to study the relationship between the surface morphology and water vapor diffusivity of barrier
coatings on polymeric polyethylene terephthalate (PET) films (12). Various deposition methods were used to grow the coatings
composed of aluminum oxide and/or silicon oxide. The findings of this work indicated that, because of the inhomogeneous coating
morphology, there is no correlation when measuring the surface roughness over large scanned areas. However, for scan sizes
restricted to the zones with 0.5 m width which are free from bumps and pinholes, it was shown that the films smoother than the PET
substrate involve a low permeability. Hence, this finding might support the idea that some other mechanisms, aside from the
existence of surface irregularities (i.e., bumps, pinholes, etc.), which are related to the growth form, should also control barrier
diffusivity. They presented that the coating roughness at length scales of 0.5 p.m. or smaller might associate with barrier coating
properties. As a result, one can state that films with values of surface roughness smaller than that of the PET substrate show a low
diffusivity, while the deposits rougher than the PET substrate present high permeabilities. It was claimed that pinholes are not the
only cause of the observed diffusivity and also roughness measurements with large scanned areas, such as optical interferometry,
could lead to misleading data (see Figure 1).
Barshilia et al. deposited titanium nitride (TiN) coatings deposited using the DC reactive magnetron sputtering technique (21).
They deposited the films on silicon (111) substrates at different conditions including substrate bias voltage (VB) and nitrogen
partial pressure. In addition, they investigated the mechanical properties of the coatings through the nanoindentation technique.
Force versus displacement curves – which were developed within loading and unloading of a Berkovich diamond indenter, were
utilized to calculate the hardness (H) and Young’s modulus (Y) of the films. In this chapter, the role of substrate bias and nitrogen
partial pressure on the mechanical properties of the coatings was elaborately discussed. In turn, the ion bombardment significantly
affects the microstructure of the coatings. According to the AFM technique, the coatings indicated fine-grained morphology when
being prepared at higher substrate bias voltage. Besides, it was found that the hardness value of the coatings rises with decrease of
nitrogen partial pressure (Figure 2).
Figure 1 AFM average r.m.s. roughness versus water vapor transmission for (a) 2 2 mm2 images and (b) 0.5 0.5 mm2 images: 6,
uncoated PET substrate; *, SiOx PECVD; X, SiOx EBG evaporated; C, Al2O3; -, SiOxAly, co-evaporated; A, SiO2–Al2O3 DOB structure. Reproduced
from Garcia-Ayuso, G.; Vazquez, L.; Martínez-Duart, J. M. Atomic Force Microscopy (AFM) Morphological Surface Characterization of Transparent
Gas Barrier Coatings on Plastic Films. Surf. Coat. Technol. 1996, 80, 203–206.
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Figure 2 Load versus displacement curves for TiN coatings deposited at different bias voltages: (a) 50 V; (b) 140 V; (c) 180 V; and (d) 250 V.
The sputtering power (220 W) and nitrogen flow rate (1f0 sccm) were kept same for all the samples. Reproduced from Barshilia, H. C.;
Rajam, K. S. Nanoindentation and Atomic Force Microscopy Measurements on Reactively Sputtered TiN Coatings. Bull. Mater. Sci. 2004, 27, 35–41.
7.09.2 Basic Performance of AFM
Figure 3 presents components of an AFM device and shows schematic set-up of an atomic force microscope (22).
AFM device has a very sharp delicate head which is attached to an elastic probe called as cantilever. The other end of this
cantilever is connected to a piezoelectric arm. To improve reflection of laser beam – which is to be informed of cantilever orientation
in the space – back of pulser is coated with a metallic thin layer. By applying appropriate voltages to the piezoelectric in x, y, and z
directions it is possible to shift the cantilever attachment spot to the piezoelectric at any desired point of the three-dimensional (3D)
space in angstrom precision (12,23–31). Once the head is touched with sample surface, a force is inserted to the head so that its
magnitude and direction depends on distance between the surface as well as surface type (Figure 4) (32).
The force induced by cantilever leads to bending and displacement of the laser beam in a plane vertical to the horizon. Hence, by
knowing the amount of cantilever bending with optical diodes as well as knowing the final position of the cantilever, spatial
position of the head is determined. By constant change of applied voltage differences to the piezoelectric, the head sweeps the
sample surface and then determines surface points one by one, and then they are plotted in a computer screen as a 3D surface
(Figure 5) (33).
To obtain highest accuracy of the measured results, it must be noticed that during the surface sweep, the distance between the
head and the surface must be remained in an appropriate range since on one hand, the large distance leads to decrease of pulser
aberration and decrease of signal-to-noise ratio; while on the other hand, very close distances leads to insertion of large deals of
forces to the surface which not only brings damages to the surface and head structure, but also reduces resolution level. For instance,
to have best results in contact mode of the AFM (repellant force between head and surface), the distance is adjusted as several
angstroms in which the head inserts a repellant force of 109 N to the surface. The distance between the head and the surface
remains constant during constant surface scanning by an electronic feedback circuit.
Figure 3 Schematic set-up of an atomic force microscope. The cantilever/tip system is the ‘heart’ of the AFM and determines the resolution and
the quality of the measurements. Typical sharp cantilever/tip system for the use in intermitted contact mode. Reproduced from Sitterberg, J.; Ozcetin, A.;
Ehrhardt, C.; Bakowsky, U. Utilising Atomic Force Microscopy for the Characterisation of Nanoscale Drug Delivery Systems. Eur. J. Pharm. Biopharm.
2010, 74, 2–13.
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Figure 4 Schematic diagram of the force dependency to tip-surface distance. Reproduced from Zanette, S. I.; Caride, A. O.; Nunes, V. B.;
Klimchitskaya, G. L.; Freire F. L., Jr.; Prioli, R. Theoretical and Experimental Investigation of the Force–Distance Relation for an Atomic Force Microscope
with a Pyramidal Tip. Surf. Sci. 2000, 453, 75–82.
Figure 5 (a) Light micrograph of a field of metaphase human chromosomes obtained with a 503 objective (N.A.5 0.5). (b) Atomic force microscopy
(AFM) image of the chromosome marked in (a). (c) AFM of the chromosome in (a) after ultra-microdissection with a cantilevered near-field optical
element operating in AFM mode. Bars, 2 mm. Reproduced from Lewis, A.; Radko, A.; Ami, N. B.; Palanker, D.; Lieberman, K. Near-field Scanning
Optical Microscopy in Cell Biology. Trends Cell Biol. 1999, 9, 70–73.
7.09.3 Cantilever
7.09.3.1 Detection of Cantilever Orientation
Determination of cantilever orientation (amount of mode of cantilever bending) is performed using detector of laser beam
reflection from behind the cantilever – if q vector is the angle between radiated and reflected laser beam, cantilever orientation will
be 2q. The amount of displacement created by the radiated laser beam is determined by a 4-zone photodiode. Normally, the pulser
shows no aberration, i.e., no deviating force is inserted to it, and the reflected beam is placed in the middle of the photodiode as it
equally covers each of these four zones. Cantilever bending by insertion of the surface force to the head leads to displacement of the
beam reflected on the plane vertical to the horizon, which also involves the cantilever. As a result, the coat ratios of the laser beam in
the upper and lower halves of the photodiode changes. Besides, cantilever twisting around its axis, due to the force vertical to the
head, results in a horizontal shift of the reflected beam and change of coat ratio of the laser beam in the left and right halves
(Figure 6) (34).
Moreover, photodiode can measure laser beam intensity in each of mentioned for zones. These diodes are made of particular
materials which convert radiated light beam to the electrical current. In this case, based on coating ratio of these four zones, one can
easily determine the amount of horizontal and perpendicular-to-horizon aberrations of the laser beam by simple calculation of the
analytical geometry. It must be noted that the nature of the determination of cantilever orientation change requires that
displacement of the radiated laser beam on the diode to be about 2000 times larger to that of pulser bending changes; and this
indicated potentials of AFM in detection of bends around 1 Å in the cantilever.
7.09.3.2 Cantilever Geometry

The most common cantilevers are in triangular and board-like forms (Figures 7 and 8) (35,36). Typically, triangular arm cantilever
is applied whenever its axial twisting is not proper. Now, the researchers work to determine surface morphology.
Synthetic latex is a widely applied binder in water-based paints. To dehydrate the dispersion, latex particles are joined with
mineral pigments. Such process leads to coating structuration and consolidation. Here, this developed composite layer is described
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Figure 6 Schematic diagram of an AFM tip–cantilever due to a combination of torsion and lateral bending vibration. Reproduced from Lee, H.-L.;
Chang, W.-J. Coupled Lateral Bending–Torsional Vibration Sensitivity of Atomic Force Microscope Cantilever. Ultramicroscopy 2008, 108, 707–711.
Figure 7 Typical images, taken with a scanning electron microscope, of an 18 Am diameter sphere glued to a triangular cantilever. The triangular shape
minimizes possible twisting motions. The left image is a side view showing the thinness of the cantilever. The right image shows the plan view.
Reproduced from Nguyen, A. V.; Nalaskowski, J.; Miller, J. D.; Butt, H. -J. Attraction between Hydrophobic Surfaces Studied by Atomic Force
Microscopy. Int. J. Miner. Process. 2003, 72, 215–225.
as a porous mineral structure with pores covered by latex particles. Accordingly, it is interesting to study the ordering of binder
particles in the coating, and the wetting of pigments by polymer particles, as well as understanding coating properties such as:
optical properties, adhesion, cohesion, sensitivity to water, etc. In regard to this, Joanicot et al. applied small angle neutron scat-
tering and AFM to examine the ordering, spreading, and the adhesion of latex particles on calcium carbonate within the coating
(37). In practical aspects, the major finding of their study is that in standard manufacturing conditions of low PVC paints, there is no
change in the polymer film structure by the pig-characterization of the dispersions (see Figure 9).
The sample is scanned with a sharp triangular tip mounted on a cantilever. The small deflections of the cantilever are measured
using a focused laser beam which is reflected off the gold-coated cantilever to a two-element photodiode detector. The x,y,z
piezoelectric single-tube scanner, located under the sample, provides the precise raster movement of the sample.
Salerno et al. carried out anodization in 0.3 M aqueous oxalic acid for the thin aluminum coating of commercial AFM
microcantilevers for contact mode (38). Owing to the fact that the similar micromechanical devices are widely utilized in modern
chemical sensors and biosensors, having an inert nonporous surface on their top facilitates their efficient functionalization through
physisorption of sensitive molecules or nanoparticles. However, it is required to preserve the useful mechanical properties of the
cantilever as the first priority. It was indicated that by potentiostatic anodization at 40 V stopped after 15 s successful formation of
nonporous alumina can be obtained with no significant changes in either shape and resonance properties, or spring constant of the
cantilevers. Besides, the important mechanical properties of the MCL, applied in both AFM imaging and sensor devices, only
experience minor modifications, with practically unchanged resonance frequency and quality factor; as well as the slight while
increase of the spring constant. They suggest that a similar surface modification strategy, appropriately accompanied by successive
functionalization of the porous surface, might serve as an effective approach to promote the sensitivity of APA-based MCL-sensors;
recently, widely applied in various application fields (see Figure 10).
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Figure 8 SEM images of two types of cantilevers to be investigated: (a) MPP 31120 contact-mode cantilever and (b) TESP tapping mode cantilever.
Reproduced from Kim, M. -S.; Choi, J. -H.; Kim, J. -H.; Park, Y. -K. Accurate Determination of Spring Constant of Atomic Force Microscope
Cantilevers and Comparison with other Methods. Measurement, 43, 520–526.
Figure 9 Cantilever and AFM scanning. Reproduced from Joanicot, M.; Granier, V.; Wong, K. Structure of Polymer within the Coating: An Atomic Force
Microscopy and Small Angle Neutrons Scattering Study. Prog. Org. Coat. 1997, 32, 109–118.
Figure 10 (a) Optical microscope side view, (b) SEM top view, and (c) AFM topography images of a successfully anodized MCL. Reproduced from
Salerno, M.; Patra, N.; Diaspro, A. Anodization of Aluminium Coated Atomic Force Microscopy Microcantilevers for Conversion of the Coating into
Nanoporous Alumina. Microelectron. Eng., 88, 2383–2385.
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To perform noncontact atomic force microscopy (NC-AFM) studies at the atomic scale, it is necessary and ideal to have a sharp
probe tip with atomic scale stability. Naitoh et al. imaged a Ge(001) surface through both a Si cantilever and a tungsten-coated Si
cantilever at room temperature to examine the effect of tip apex structure on NC-AFM images (39). Once utilizing the Si cantilever,
the first four types of image at the atomic scale were obtained, where they can be explained considering a dimer structure on the tip
apex. Besides, the homemade tungsten-coated tip, with atomic scale stability and high electric conductivity, was applied to image
the so-called ordered c(4 2) structure without any artifacts. It was found that the tungsten-coated cantilever has significantly
higher performance for NC-AFM investigations at the atomic scale in comparison to the Si cantilever. Here, four types of NC-AFM
images were obtained with atomic resolution for the first time by Si cantilever. The Type I image indicated a mixture of the so-called
c(4 2) and the p(2 1) structures, which is very similar to previous ones reported using the STM images. The image contrasts of
Type II, III, and IV images exhibited characteristic features never reported by the previous STM studies. It is possible to explain these
image features by a dimer structure model on the tip apex. It was proposed that the Type II image can be explained by a symmetric
dimer model, while Type III and IV images are explained by an asymmetric dimer model. These findings imply that the tip apex
profile from the image feature of the Ge(001) surface.
Copper carbon composites are among prospective materials for employing as heat sink materials in thermal management
applications. A key disadvantage of this material combination is the lack of adhesion between copper and carbon. To promote
interfacial properties in this system, Neubauer et al. conducted a basic study on carbon substrates, in which the effect of an adhesion
promoting intermediate layer was evaluated (4). Also, the effect of a Ti intermediate layer on the growth mode and surface
topography of a copper coating, as well as diffusion of Ti after a heat treatment, was analyzed in this study via application of Auger
electron spectroscopy. To improve interface adhesion in the Cu–C metal matrix composites, Ti was tested as a candidate material.
The thin intermediate layers (<25 nm) promoted the adhesion, although the fracture was observed between Ti and the C substrate.
The layers with average thickness (100 nm) lead to copper coating delamination owing to the stress concentration in the coating. Ti
intermediate layers with different thicknesses affect surface topography of copper coatings and coatings roughness after heat
treatments. Based on the surface topography and the Auger analysis, once can conclude that Ti diffusion from the interface to the top
of the copper coating occur after a heat treatment. Such diffusion, even in the case of applying thin intermediate layers, leads to
degradation of thermal and electrical characteristics in the real composite material through Ti atoms dispersion in the copper matrix.
To confirm this, further works are required to be conducted on the preparation and testing of composite materials through applying
the copper coated carbon fibers by a Ti intermediate layer.
Pandey et al. investigated diamond-like carbon (DLC) films deposited by the microwave plasma CVD technique under varying
bias voltages through AFM and spectroscopic ellipsometry (40). AFM was applied to study the surface morphology, while the
ellipsometric studies are utilized to evaluate density and sp3/sp2 ratio variations of the films. These films have interrelated
surface morphology, density, and sp3/sp2 ratio which follow the subplantation model. The DLC films deposited at low bias voltages
(100 to 300 V) exhibited an increase in the density by the increase of the bias voltage. However, the films deposited in high bias
voltage range (w800 to 1400 V), indicated density saturation. It was also found that sp3/sp2 ratio enhances with the rise in bias
voltage; though only up to a certain limit (w1000 V) beyond which its value has a drop.
Compliance of the substrate is considered among the key parameters in buckling of the thin films. Buckling is clearly regarded as
a global phenomenon for any compliant substrates where it involves both the film and the substrate. Once applying the nickel thin
film on a polycarbonate substrate, the effective critical stress rc decreases by 40% and the deflection is more than twice the one
encountered in the case of a rigid substrate. Such FEM results are in agreement with those of in situ AFM observations obtained for
thin films during the rise in external stresses. Due to applying a soft substrate, a depression is observed near the edges of the straight-
sided wrinkle. Such a depression is related to a stress relaxation in the film over a wide distance from the buckled area. The main
characteristics of buckling, including the critical buckling stress and the nondimensional law which associates with the maximum
deflection of the buckle to the stress in the film, are appropriately defined once applying the rigid substrates. By the introduction of
two correcting factors, these relations can be developed using the nonlinear FEM calculations for any film/substrate couple of
materials. Such parameters which depend on the elastic discrepancy between the film and the substrate are very interesting subjects
for calculating the mechanical properties of the thin films (internal stresses or Young’s modulus) using the shape of the buckling
structures in a large variety of film/substrate systems. As further investigations are considered, it is possible to analyze the profile of
the film after buckling using wavelet functions which can be effective tools to determine the delaminated zone and the resulting
interface energy modification (41).
Partridge et al. applied AFM to investigate the deposition of nanometer-sized clusters by spin coating (8). They indicated that
production of homogeneously distributed nanometer-sized Cu and Rh particles are possible using this technique. However,
development of particles with uniform size and distribution is not only controlled by solute concentration and spin frequency;
rather, it also depends on a set of other factors such as: atmospheric humidity, solvent properties, and the chemistry of the
solute. Once applying a simple set of salts, Cu(NO3)2 and RhCI3 dissolved in ethanol, during spin coating, the particles
precipitate out of the solution and deposit on the substrate. Nevertheless, AFM and XPS analyses indicated that the application
of a Cu(acetate)2 precursor leads to the development of a Cu(acetate) layer on the substrate. An explanation for such behavior
might be the existence of a larger metastable supersaturated region in the Cu(ac)2 solution which is yielded from the presence of
the acetate ligands. It was observed that the Cu(ac)2 layer develops particles on calcination, where the particle size and
distribution is sensitive to the calcination rate. Taking AFM images of the surface after oxidation and reduction of the larger Rh
particles, show that these particles break up because of the treatment. Such behavior is consistent with results of previous
studies. After this treatment, or after direct reduction in H2, the Rh particles demonstrated a particle–substrate interaction, shown
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by the inability of the AFM to sweep the particles across the surface. A similar behavior is also determined to happen after
oxidation of the Cu particles.
7.09.4 Tips
Based on the applied mode of the AFM and the measured property, various types of heads can be applied. Once the measuring
process requires insertion of enormous forces from the head to the surface, diamond heads and diamond-like coated heads are
applied. For instance, to create nano scratching or scanning spreading resistance microscopy, some forces about 105 N are applied
while in contact mode the applied force to the surface is 109 N and this head should be utilized. Coats such as chromium-gold and
platinum are applied to protect the head against harsh environmental conditions. To stop charges (or ions) concentration on the
head surface, particularly in electronic force microscopy, coats such as TiN, C2W, TiD, and doped DLC are applied. To measure
magnetic properties of the points on the surface, it is required to utilize ferromagnetic materials such as Ni, Fe, and Co. The
geometric parameters of the head determining efficiency of the head and accuracy of the obtained results include shape, height,
thinness (apex angle of imaginary pyramid fitted to the tip), and sharpness (radius of the imaginary circle fitted in the tip). T-shape
heads are applied in mapping and recognition of dents on wall-like parts of the sample surface. It is noteworthy that sharp heads
lack such a capability (see Figure 11) (42).
Broad heads are also applied to study friction in various parts of the surface. This is due to the fact that the friction is the
cumulative behavior of surface atoms, rather than an atom size spot. Due to their very extensive contact surface with the sample
surface, spherical heads insert a slight amount of force on the surface unit. Hence, very soft and sensitive samples can be studied by
this method. Nevertheless, due to the effective interaction of a wide area of the surface with various points of these tips, the
resolution level of the final image reduces. Therefore, once a very high resolution level is not required for the research, these heads
are very ideal to develop images of the soft sensitive surfaces without any need to create specific environmental conditions, e.g.,
vibrational isolation of the measured group and precise calibrations. These heads can be applied, for example, in the study of
various biological surfaces. Itoh et al. developed a piezoelectric force sensor to deal with the complexity of the force detector in the
conventional noncontact AFM (43). The sensor was made of a cantilever with a piezoelectric thin film deposited on one side. The
layer is developed on a thermal SiO2 microbeam and then a thin passivation film was applied to encapsulate it. The piezoelectric
film was c-axis oriented ZnO deposited by RF magnetron sputtering, or lead-zirconate-titanate (PZT). This film was formed by the
Figure 11 AFM tip geometries. (a) Pyramidal cantilever (bar is 10 mm) and small tip (inset, bar is 1 mm); (b) microbead glued to the cantilever; and
(c) coated with human trophoblast-type cells. Scale bar is 5 mm. Reproduced from Simon, A.; Durrieu, M.-C. Strategies and Results of Atomic
Force Microscopy in the Study of Cellular Adhesion. Micron 2006, 37, 1–13.
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sol–gel method. The cantilever was excited near its first natural resonance and then the forces were monitored by detecting the
change in the admittance of the layer induced by the piezoelectric effect. Since the force gradient between the tip of the vibrating
cantilever and sample in close distance changes vibration amplitude, it results in the change in admittance of the layer. In their work,
the sensor signal was measured as a function of the tip sample spacing and verified sensor feasibility for a noncontact AFM. The
sensor requires a sharpened conical tip at the lever end for improving lateral resolution of AFM. The Stanford group reported
fabrication processes for producing sharpened cone tips at the end of the cantilever for an AFM device. Thus, it is possible to make
a sharpened conical tip on the patterning of both sides of the thermal SiO2, and depositing and patterning Au/Cr layers for wiring.
An additional SiO2 layer is formed on the patterned layers until its thickness is reached to the height of a conical tip. In the next step,
a metal mask layer was developed on the additional SiO2 layer. In their work, the concept of a force sensor cantilever for
a noncontact AFM was proposed and the planar process for the fabrication of the sensor was developed. Using the sensor output
signal, as a function of the tip-sample spacing, mini detectable f 0 was estimated as 1.8 103 N m1 in air. In the dynamic
operation mode of the MIL contact AFM (vibrating the cantilever near its resonance frequency), the hysteresis of the signal trace can
be explained by the adsorption layer of the tip and sample surface.
Batog et al. investigated the possibility of applying atomic-force acoustic microscopy to measure the elastic properties of thin-
film coatings with a thickness of several to several hundreds of nanometers (44). Technically, this technique allows study of
diamond-like coatings. The key point applied in this work is application of ‘flat’ tips, which provide a constant tip–surface contact
area and, in turn, constant contact stiffness. Application of such tips was owing to the fact that it is not possible to give an adequate
quantitative interpretation for experimental data for thin-film structures gained with standard (rounded) tips. Here, the numerical
simulation was used to examine the thickness and indentation modulus of a coating from contact stiffness kcont, which in turn is
measured by atomic-force acoustic microscopy. They indicated that the standard probes with rounded tips are ineffective in the
evaluation of the thin-film coatings. Here, the flat tips are more appropriate, because they provide a constant contact area no matter
how large the pressing force F is. After experimental determining tip stiffness ktip and contact radius (a) through the calibration
method proposed in this work, it is possible to calculate effective indentation modulus Meff of a thin-film structure. Then, using this
value (Meff), it is easily possible to determine either coating thickness (t) with indentation moduli of the coating (M1) and substrate
(M2) known or indentation modulus M1 of the coating with M2 and t known. Once M1 and t are known, one can determine
modulus M2 in a similar fashion. As a closing mark, note that the simplest way for flat tips preparation for experimentally checking
of the proposed method is attrition wear of the standard tips through long-term scanning over a hard solid surface (Figure 12).
7.09.4.1 Tip Interaction with Surface

Plotting force diagram based on distance is done to determine various properties of the surface as well as the determination of the
optimum distance of the probe from the surface to which the least amount of force is inserted to. It is noteworthy that during the
scanning process, the head surface is required to bring the minimum damage to the surface to maximize measurements precision.
The active forces between the head and surface are long-range and short-range. Van der Waals, electrostatic, and magnetic forces are
among these long-range forces. Here, van der Waals forces, which are the interaction of inductive dipoles attraction and vary as r6,
are very common in experiments. On the other hand, adhesion, quantum forces (induced by inconsistency of complete corre-
spondence of the molecules electronic cloud), and covalence forces are among short-range forces (45–56).
In general, the shape of developed diagram is a function of surface properties (mechanical, electrostatic, magnetic, and adhe-
sion), medium conditions of the sample (vacuum, air, and acidity of the liquid), as well as mechanical features of the head
(sharpness, shape, and material) and cantilever (shape and solidity). Typically, mechanical characteristics of the head and cantilever
are determined through initial calibration of the AFM device. Hence, analysis and study of the force diagram with head distance
from the surface reveals surface properties and its medium. Through analysis and study of the diagram, it is aimed to determine
Figure 12 Schematic representation of a cantilever with a flat tip. Reproduced from Batog, G. S.; Baturin, A. S.; Bormashov, V. S.; Sheshin, E. P.
Calculation of the Thicknesses and Elastic Properties of Thin-film Coatings Using Atomic-force Acoustic Microscopy Data. Tech. Phys. 2006, 51,
1084–1089.
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extremum points, sudden jump or fall, fracture and sharpness, zero force, diagram gradient in various zones, and hysteresis (the
values of different in diagram when coming closer to or away from the surface). Then, each of these states is separately investigated.
Harish et al. characterized Cu/Ni multilayer coatings prepared by RF/DC magnetron sputtering process via XRD, nano-
indentation, and AFM techniques (57). According to the XRD data, the films deposited under certain deposition conditions indicated
the appearance of satellite reflections around the principal reflections, implying the formation of a superlattice structure. They also
performed nanohardness measurements on the films prepared under different deposition conditions including modulation
wavelength (L), copper to nickel thickness ratio (tCu/tNi), and substrate temperature (Ts). Nanohardness data revealed that the
hardness was enhanced by a factor of w2.5 times that of the rule-of-mixtures value. Besides, the hardness increased almost linearly
with substrate temperature up to 200 C and reached saturation state at 250 C. After vacuum annealing of the coatings, the
observations of this work indicated no considerable change in the hardness. Residual imprints imaging through the AFM technique
revealed pile-up, a measure of plastic flow of the material, and formation after indentation. It must be noted that the extent of pile-up
depended on preparation conditions of the multilayer coatings. AFM images of the nanoindentation imprints indicate material pile-
up around the indentation at higher loads. For the harder films, the extent of pile-up and depth of penetration were less (Figure 13).
7.09.5 Various Modes of AFM Devices
Based on vibration and lack of vibration in the cantilever, contact and semicontact mode are categorized into two A.C. and D.C.
groups. Due to negligent amounts of the signal, in the noncontact zone, normally the only applied mode is A.C. For optimal
adjustment of AFM parameters in each mode, the force is first measured in a certain spot based on distance of the head from surface
and then the parameters are selected based on this parameter. However, there are many AFM devices which automatically define
these parameters. In the following lines, each of these categories will be discussed in detail (58–69).
7.09.5.1 Contact Modes

According to the definition, a contact zone is an area in which the force between the head and the surface is repellant. Compared to
the other modes, the force inserted to the surface is larger in contact modes. Furthermore, due to continuous contact of the head
with the surface during the scanning process, a considerable deal of friction forces (plus vertical forces) are applied to the surface and
head, and brings damages to the weak surfaces and leads to pulling off the tip. In this regard, the study of sensitive soft surfaces with
contact modes reduces resolution potential and sometimes creates systematic errors in the results. However, the maximum reso-
lution and accuracy is shown in study of hard surfaces using thin, supersharp hard heads in the contact mode of AFM measurements.
Ritala et al. applied AFM to examine the morphological development of TiO2 thin films deposited on mica and soda-lime substrates
by atomic layer epitaxy using TiCl4 and water as reactants (70). They observed that TiO2 agglomerates and results in the rise of
surface roughening with an increase in the number of deposition cycles. According to the AFM tests, it was found that the surfaces of
ALE-grown TiO2 films roughen as the growth progresses. Also, the roughening rate is at its highest during the first reaction cycles;
where the film growth occurs by the island mode. It seems that roughening occurs due to migration processes which happened by
the minimization of the film–substrate interface energy; since this mechanism leads to the observed island growth; while the gas
phase nucleation processes results in Stranski-Krastanov growth. Their study indicated no remarkable differences in the morphology
between crystalline and amorphous films (Figure 14).
7.09.5.2 Constant Force Mode

In this mode, during the scanning process the head to surface force (distance of the head from surface) is kept as constant using
a feedback circuit. Hence, during the scanning process the travelled pass by the piezoelectric equals to the head pass and topography
and surface diagram is determined by a very high accuracy. Indeed, in each scanning run the feedback control circuit commands
height change to the piezo to make head distance from the surface as constant. One of drawbacks of these techniques is the large
amount of time required for complete scanning of the surface since in each step, the feedback circuit scan issues height change
command to the piezo for several times to make the head and surface distance to its optimum amount. Besides, for having higher
lateral resolutions, it is required to have smaller scanning steps which results in a relative decrease of the scanning rate. Here, the
optimum design of feedback circuit is magnified more. To reach acceptable rates, the feedback circuit should have a frequency
around 10 kHz. Among the main advantages of this technique, one can indicate a very high accuracy in the determination of hard
surfaces topography and simultaneous measuring of the values such as friction, electrical resistance distribution, etc., during surface
scanning, as well as determination of geometrical topography. Determination of soft surfaces properties is among main disad-
vantages of this technique since the topography during head scanning varies – since the head is required to be in contact with the
surface – and as a result, precision and measurement resolution falls.
7.09.5.3 Constant Height Mode

In this mode, the piezoelectric height does not vary during the scanning process and its movement is performed in a completely
horizontal plane. As a consequence, based on piezo distance from the studied surface, a force is inserted to the tip. By recording
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Figure 13 AFM data of a typical Cu–Ni multilayer coating showing (a) a two-dimensional image of the residual nanoindentation imprint; (b) cross-
section profile through imprint; and (c) a three-dimensional image of (a), clearly showing the pile-up of the material as a result of indentation.
Reproduced from Hristu, R.; Stanciu, S. G.; Stanciu, G. A.; Capan, I.; Guner, B.; Erdogan, M. Influence of Atomic Force Microscopy Acquisition
Parameters on Thin Film Roughness Analysis. Microsc. Res. Tech., 75, 921–927.
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Figure 14 AFM images taken (a) from pure phlogopite and after (b) 20, (c) 100, (d) 400, (e) 2000, and (f) 4000 TiO2 deposition cycles. Different z
scales in the first two images should be noted. Reproduced from Ritala, M.; Leskela, M.; Johansson, L. S.; Niinisto, L. Atomic Force Microscopy
Study of Titanium Dioxide Thin Films Grown by Atomic Layer Epitaxy. Thin Solid Films 1993, 228, 32–35.
pulser aberrations during the process, it is possible to measure inserted force to the head within the scanning process; and since this
force depends on the head distance from the height difference, the height of different points of the surface from piezo height
(surface topography) can be determined. The rate of surface scanning in this method is very high, as there is not a height control
process to decelerate speed of feedback circuit cycle. Here, the only determining factor of the process speed is reaction speed of the
pulser within the orientation process which is higher than that of the feedback circuit. The serious limitation of this technique is that
it can only scan partially smooth surfaces. Besides, this lack of control over head might bring some pressure to the surface in some
points and change surface of soft samples and result in the resolution of the results.
7.09.5.4 Semicontact Modes

As previously mentioned, the zone between contact and noncontact are in addition to a small area of contact zone (4–30 Å) is called
as ‘semicontact zone.’ In present literature of the nanosciences, semicontact mode has various names such as ‘tapping mode’ and
‘intermittent contact mode.’ Semicontact mode has a slight overlap with the contact region. To achieve maximum signal-to-noise
ratio, A.C. modes are applied. During the scanning process, the cantilever vacillation zone also extends to contact zone and –
because of repellant force effect – touch the surface in each cyclic period. By decrease of the piezoelectric height, vacillating
cantilever approaches to the surface and its amplitude reduces and then based on amplitude decrease, the distance between
piezoelectric and the surface is determined. Phase difference of cantilever vacillations with the pulse inducing source depends on
mechanical properties of the surface such as Young’s modulus and hardness. Thus, by measuring this phase difference it is possible
to determine mechanical properties of the surface. In addition, it has been proved that resonance frequency of the vacillating
cantilever changes due to the shift in force gradient. Researchers become familiar with details of force–distance diagram by
measuring resonance frequency variations.
Unlike noncontact mode in which force signal is small because of the far distance from the surface and leads to the reduction in
measurements accuracy, force signal in semicontact mode is suitable and is rather equal to most accurate measurements of the
contact mode. Nevertheless, considering the natures of this method, the lateral forces which bring the highest damages to the
samples in contact mode are absent in this technique. Moreover, due to the very short time in which the head is in effective contact
with the surface, and in turn induces repellant force, the effective pressure of the head in this method is smaller than that of contact
mode. Using nonmechanical inducers such as applying an alternative magnetic field to a cantilever whose back part is deposited
with a ferromagnetic layer, lower amounts of noise is produced and as a result ‘signal-to-noise’ ratio rises. Therefore, it is possible to
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have an acceptable amount of signals via smaller amplitudes. Applying smaller amplitudes means decrease of the applied vertical
force of the head to the surface. So, in this way, one can study soft sensitive surfaces with high precision; which is not possible in
contact modes.
The application of this technique is also possible in liquid environments since, first, the capillary forces leading to serious
degradation in the resolution of the measurements are eliminated; and, second, in liquid environments, by changing acidity and
ions concentration it is possible to create a condition in which the head force on the surface is minimized. Thus, this allows for study
of more sensitive surfaces in a more accurate manner.
7.09.5.5 Constant Amplitude Mode

Change in vacillations amplitude compared to the free vacillations depends on magnitude of the active effective force on pulser –
i.e., the average time in one surface scan run – and rather is not controlled by the surface material in the given spot. Besides, by
a good estimation, the magnitude of this effective force corresponds one by one with effective distance of the pulser from surface.
Hence, constancy of the amplitude during the surface scanning process implies constant values of the piezoelectric distance from the
surface during the surface scanning process. Then, through recording the traveled distance by the piezoelectric by a control circuit, it
is possible to determine surface geometry. The main advantage of this technique is its potential in preparing high resolution plots
from soft and vulnerable surfaces. On the other hand, the main disadvantage of the technique is the big matter of time required for
the complete scan of the surface since piezoelectric height varies with the feedback control circuit (to maintain vacillation
amplitude) in each scanning step for several times. The more intense changes in height of new step (like a series of flights), leads to
an increase in the number of height changes. As a result, the more features on their surface and larger gradients result in
a considerable increase in the time required for complete scanning of the surface. However, disregarding some surface information,
it is possible to determine the topography map of the surface with an acceptable speed. This method which is referred to as the
‘semicontact error’ and does not indicate smooth topographies (13,71–83).
7.09.5.6 Phase Difference Imaging Mode

In each scanning step, depending on the surface material parameters, such as adhesion or Young’s modulus of the surface, the
diagram of the force with distance of the piezo with surface will be different. In this state, piezo vacillations will have phase
difference with cantilever vacillations whose magnitude depends on surface material in the given point. Thus, the phase difference
map in various points of the surface is applied as a factor to distinguish material of different spots in the surface. Besides, this map
can be applied for resolution enhancement and improvement of other surface maps such as lateral, friction, and electrical distri-
bution map and, in general, various types of modes for determination of mechanical properties.
Tribofilms developed in the rubbing surfaces are in close association with wear mechanisms and steady-state friction in sliding
contacts. Nevertheless, the low thickness, inhomogeneity, and discontinuity of these surfaces are among the factors hindering the
evaluation of their micromechanical properties. Application of phase contrast images in tapping mode AFM allows measuring the
inhomogeneity in micromechanical properties in sample surfaces. Ahn et al. examined the way in which phase contrast images
assist characterization of thin tribofilms (84). The surfaces of DLC coatings were investigated against a steel ball slider before and
after friction contact (see Figures 15 and 16). A 3D simulation of the real contact area was performed in this study and then
a contrast was made between the pressure distribution obtained by this simulation and the phase contrast image obtained at the
same area. The phase contrast images indicated a considerable inhomogeneity of the worn surfaces. Thin tribofilms were developed
at the real contact regions and their thickness increased at the locations with higher contact pressures. Here, the tribofilms shown as
Figure 15 AFM images of the unworn DLC film surface (zone A): (a) topography image (Rq ¼ 69.4 nm, hmax ¼ 458.4 nm) and (b) phase
contrast image (Fmax ¼ 47.2 ) (scan size ¼ 10.7 mm 10.7 mm). Reproduced from Ahn, H. S.; Chizhik, S. A.; Dubravin, A. M.; Kazachenko, V. P.;
Popov, V. V. Application of Phase Contrast Imaging Atomic Force Microscopy to Tribofilms on DLC Coatings. Wear 2001, 249, 617–625.
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Figure 16 AFM images of the worn surface (zone D): (a) topography image (Rq ¼ 13.8 nm, hmax ¼ 92.2 nm) and (b) phase contrast image
(Fmax ¼ 24.0 ) (scan size ¼ 10.8 mm 10.8 mm). The arrow shows the direction of oscillation of the counterface steel ball. Reproduced from Ahn, H.
S.; Chizhik, S. A.; Dubravin, A. M.; Kazachenko, V. P.; Popov, V. V. Application of Phase Contrast Imaging Atomic Force Microscopy to Tribofilms
on DLC Coatings. Wear 2001, 249, 617–625.
darker gray scale values revealed to be less stiff compared to the initial DLC coating. A comparison between the phase contrast
images and the results of micro-Raman, AES, and SIMS analyses result in this assumption that the tribofilms, which are almost
entirely composed of carbon element, are graphite films or at least they mainly possesses graphitic property. In addition, the phase
contrast imaging in AFM showed a promising horizon for a better understanding of the micromechanical properties in worn
surfaces and wear mechanisms. Figure 17 shows AFM images of the boundary of the wear track.
Figure 17 AFM images of the boundary of the wear track (zones B and C): (a) topography image (Rq ¼ 64.9 nm, hmax ¼ 230.7 nm); (b) phase
contrast image (DFmax ¼ 37.1 ) (scan size ¼ 24.9 mm 24.9 mm); and (c) variation of height (Z) and phase (F) along the diagonal line marked in (a)
and (b), respectively. Reproduced from Ahn, H. S.; Chizhik, S. A.; Dubravin, A. M.; Kazachenko, V. P.; Popov, V. V. Application of Phase Contrast
Imaging Atomic Force Microscopy to Tribofilms on DLC Coatings. Wear 2001, 249, 617–625.
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7.09.6 AFM Applications for Coatings
High accuracy, lack of any limitation in study of many surfaces in various medium conditions, lack of need for sample preparation
in most cases, high measuring speed, development of 3D images, and potentials for the study of various surface features have made
a growing interest for application of AFM in various fields of applied technology including aerospace, electronics, auto industry,
material science, biology, telecommunication, energy, drug synthesis, cosmetics, petrochemistry, etc (84–88). Typically, the main
reasons for application of AFM in various fields of technology are as follows:
1. Study of structures quality and properties of fabricated devices.
2. Study of structural changes and devices’ properties with time and in different conditions.
The main objective of the technologist in following these goals is to understand optimization principles for the fabrication and
parameters of these techniques, increase of design efficiency, and an increase of devices’ lifetime. In the following section, some
instances of AFM applications are introduced.
7.09.6.1 Investigation of Latex Particle Morphology and Surface Structure of the Coatings
Gerharz et al. applied an AFM to evaluate surface topographies of various single latex particles, corresponding latex films, and
varnishes (89). They studied three different latexes, consisting of homogeneous and composite particles and then investigated the
influence of wax and solvent on film formation as well as dependence on the particle morphology. AFM proved to be an appropriate
tool to reveal the surface structure of the films under ambient conditions (see Figures 18 and 19). They investigated the surface
structure of the pure dispersion films based on their Tg and particle morphology. When Tg exceeded room temperature, e.g., for
HomA or for the hard, second phase of Com particles, it was possible to observe individual particles with their original spherical or
hemispherical shape. Once Tg was below the temperature, e.g., for HomB, the particles lost their shape and, as a result, a continuous
film formed. There were two main ingredients responsible for making a varnish rather than a polymer film; i.e., a solvent and wax.
The effect of these ingredients was determined through imaging: (1) the films prepared only with solvents, and (2) the films
prepared with solvent and wax. Unlike the solvent, HomA and HomB films did not have a significant effect on Com films. This
might probably be due to the fact that the solvent softens the polymer, which has the same effect once Tg and MFT drop for few
degrees. Because the particles were soft enough to form a continuous film anyway, no surfaces and morphology changes were
observed in HomB films. Moreover, HomA since the reduction of Tg of few degrees might not have been sufficient, the films did not
significantly change. On the other hand, the hard phase of Com, with a Tg of 33 C, might have become soft enough that the
adjacent particles are partially melted into each other. The interface region between soft phase I and hard phase II might have an
influence on this effect, where the solvent can easily diffuse through this interface. This was directed toward the top layer while the
soft BuA phase probably constituted the deeper region. No such layer was formed for Hom1 films. Although it seems that the surface
of the particles is changed, the wax did not form a well-defined separate phase. This might be attributed to the higher polymer Tg
since translational diffusion cannot occur for the polymeric part.
7.09.6.2 Study on Crystallization

Du et al. applied AFM to investigate surface morphology of sol–gel derived Al2O3–TiO2–SiO2 coatings on microscope glasses (90).
The coatings freshly annealed at 500 C for 1 h were homogeneous on a nanoscale and exhibited a typical glass pattern (see
Table 1). Tetragonal-like crystallites were observed in coatings after 10-month storage in air either before or after annealing. They
also investigated and discussed the effects of chemical compositions and storage processes on the surface topography and
Figure 18 Surface plot of typical HomA latex particles dried on mica (left) and top view of a layer of HomA (right). Reproduced from Gerharz, B.;
Kuropka, R.; Petri, H.; Butt, H. J. Investigation of Latex Particle Morphology and Surface Structure of the Corresponding Coatings by Atomic
Force Microscopy. Prog. Org. Coat. 1997, 32, 75–80.
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Figure 19 Views of Com films prepared with 2% (left), 5% (right), and 10% (middle down) butyldiglycolacetate imaged in height mode. Reproduced
from Gerharz, B.; Kuropka, R.; Petri, H.; Butt, H. J. Investigation of Latex Particle Morphology and Surface Structure of the Corresponding
Coatings by Atomic Force Microscopy. Prog. Org. Coat. 1997, 32, 75–80.
Table 1 Designed composition, thickness, RMS value of coatings, and crystallization status of corresponding gels
Composition (mol%) Status

Sample Al2O3 TiO2 SiO2 Thickness (nm) RMS (nm) 700 C 800 C
A0 0 35 65 80 0.56 o 0.10 am am
A1 10 25 65 80 0.54 o 0.15 am am
A2 20 25 55 70 0.54 o 0.09 am am
A3 10 40 50 75 0.69 o 0.10 am a (tr)
A4 10 50 40 75 a (tr) a
A5 15 25 60 50 0.62 o 0.09 am am
A6 5 40 55 80 0.58 o 0.08 am a
A7 20 40 40 85 0.66 o 0.17 am a
A8 20 50 30 80 0.66 o 0.11 a a
A9 30 40 30 90 0.77 o 0.12 a a
A10 20 60 20 90 1.0 o 0.20 a a
Reproduced from Du, Y.; Frischat, G. H. Atomic Force Microscopy Study on the Anatase Crystallization of Long Term Stored Al2O3-TiO2-SiO2 Coatings on Glass. J. Mater. Sci.
2000, 35, 2561–2564.
crystallization of anatase. The RMS roughness of the freshly annealed Al2O3–TiO2–SiO2 coatings is related to their chemical
composition (see Figures 20 and 21). This roughness increased with the increase of TiO2 and Al2O3 contents. Moreover, the
amount, size, and degree of perfectness in tetragonal anatase crystals in A1–A5 coatings gradually increased with the TiO2 and
Al2O3-content.
In order to understand and predict the performance of corrosion protective coatings, characterization of the metal-coating
interface is a crucial task to perform. By now, such characterization has been incompletely performed in a scale which yields little
microscopic-scale information. Applying AFM and SEM allows having such information. Bierwagen et al. presented the utilization
of such methods to examine the interface between steel and marine coatings and as well as imaging the surface of untreated aircraft
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Figure 20 AFM height mode images of freshly annealed TiO2–SiO2 and Al2O3–TiO2–SiO2 coatings on microscope glasses (a) A0; (b) A2; (c) A3;
and (d) A10. Reproduced from Du, Y.; Frischat, G. H. Atomic Force Microscopy Study on the Anatase Crystallization of Long Term Stored Al2O3-TiO2-
SiO2 Coatings on Glass. J. Mater. Sci. 2000, 35, 2561–2564.
aluminum alloys (91). These aircraft alloys also were imaged after chromate/phosphate pretreatment (see Figures 22 and 23).
Furthermore, AFM and SEM were also applied to evaluate variations in surface morphology, which are along the changes in the
samples due to exposure. In parallel with the AFM/SEM measurements, also electrochemical noise methods, electrochemical
impedance spectroscopy measurements, and ProhesionTM tests were conducted.
Both e-coat systems indicated resistance values 3 times higher than that of the spray coat systems. Besides, their delamination
areas were lower than the spray coats. This leads to the idea that in undamaged systems, the e-coat is a better system for corrosion
control. The differences between the two coatings arose once they were placed in the ProhesionTM chamber for 2000 h. According to
the findings of this project, the spray coats continued to inhibit corrosion because of the strontium (Sr) chromate pigment; however,
the e-coats were unable to achieve this since they contain no inhibitive pigment. Here, the conversion coating applied in parallel
with e-coat process significantly contributed to prevent corrosion spread. The ENM data generated from these systems were in
agreement with the EIS values since they proved to be effective in the characterization of the corrosion resistance properties in these
two epoxy primers. To assess corrosion resistance of aluminum, steel alloys, and possibly determine mechanisms of corrosion, ENM
is a powerful technique. Microscopy by AFM and SEM methods yielded a larger amount of information about the changes occurring
during exposure of the coated panels.
7.09.6.3 Study of DNA Molecules Stretched by Spin-Coating Technique

Ye et al. developed an effective approach for stretching DNA molecules with the flow of fluid generated by spin coating (73). AFM
was applied to observe the well-stretched l DNA molecules, where it was found that the substrate properties significantly affect the
stretching behavior of DNA (see Figures 24 and 25). The experimental findings of this research revealed that a mica surface treated
with crystal violet, a cationic dye molecule, is suitable to the spin-coating of the stretching DNA procedure. In addition, a decreased
height of the stretched DNA was observed compared with relaxed DNA. An explanation for this might be elongation force applied to
the DNA molecules from the fluid flow and strong adhesion force between DNA and the substrate. This simple and effective
technique for stretched DNA preparation could be useful in physical mapping of the genomic DNA in a high throughput. An
effective method was developed to prepare stretched DNA samples for AFM imaging in their work. Such DNA molecules were
obtained through a spin-coating procedure. The interactions between the DNA molecules and the substrates used for spin coating
strongly affected the stretching behavior of the DNA.
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Figure 21 AFM images Al2O3–TiO2–SiO2 coatings (a), (b), (c), and (d) are A1, A2, A3, and A4 coatings kept in a desiccator at room temperature for 10
months after annealed at 500 C for 1 h. Reproduced from Du, Y.; Frischat, G. H. Atomic Force Microscopy Study on the Anatase Crystallization of
Long Term Stored Al2O3-TiO2-SiO2 Coatings on Glass. J. Mater. Sci. 2000, 35, 2561–2564.
7.09.6.4 Morphology Formation in Thin Films Deposited by Different Methods

Behera et al. applied the dip and dry technique using a sodium zincate bath to prepare zinc oxide doped with Al (AZO) thin films on
borosilicate glass substrates (92). They also studied the effects of doping on the structural and optical properties of ZnO film
through XRD, EPMA, AFM, optical transmittance, PL, and Raman spectroscopy (see Figure 26). Doping with Al indicated aggre-
gation of crystallites forming microsize clusters which affect the smoothness of the film surface. In addition, it was found that Al3þ
ions promote chemisorption of oxygen into the film, which in turn affects the roughness of the sample.
7.09.6.5 Study of Friction Process and Nanometric Changes in the Friction Bearing Pieces
Study of friction phenomena and the surfaces subjected to the friction is called as ‘tribology.’ This science involves the study of
friction force (physics), wear (material science), and lubricants (chemistry). It is interesting to know that AFM facilitates surface
studies in these three fields with nanometric precision. The methods in which AFMs are applied in this science are: generation of
friction force and the development of friction map in various spots (study of friction), determination of morphology and geometry
map and various surface properties (wear study), and investigation of adhesion and viscosity of the lubricant layers inside the
surface (study of lubricants role).
7.09.6.6 Characterizing Coating Layer z-Directional Binder Distribution in Paper

Di Risio et al. combined high resolution AFM (Figure 27) and image analysis to characterize spatial arrangement of styrene butadiene
binder in the cross section of paper model coatings applied on plastic film (93). The adhesion maps obtained using pulsed force mode
atomic force microscopy was utilized to observe latex distribution. Then, image analysis techniques were utilized to calculate
z-directional binder profiles. Using the methodology invented in this research, a set of laboratory coated samples including pigments with
various range particle sizes and particle size distributions were investigated. The findings of this work indicated that the cross-sectional
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Figure 22 AFM image of MIL-P85582 spray primer on Al with conversion coating (includes image information). Reproduced from Bierwagen, G. P.;
Twite, R.; Chen, G.; Tallman, D. E. Atomic Force Microscopy, Scanning Electron Microscopy and Electrochemical Characterization of Al Alloys,
Conversion Coatings, and Primers Used for Aircraft. Prog. Org. Coat. 1997, 32, 25–30.
Figure 23 AFM image of e-coat after immersion in electrolyte (10 mm resolution). Reproduced from Bierwagen, G. P.; Twite, R.; Chen, G.; Tallman, D.
E. Atomic Force Microscopy, Scanning Electron Microscopy and Electrochemical Characterization of Al Alloys, Conversion Coatings, and Primers
Used for Aircraft. Prog. Org. Coat. 1997, 32, 25–30.
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Figure 24 (a) An AFM image of DNA molecules spin-coated on a CV-treated mica surface. The height is illustrated in gray code ranging from dark
(0 nm) to light (1.5 nm). (b) The sectional image corresponding to the black line drawn in A. The peak marked with an arrowhead refers to the
height of the stretched DNA. Reproduced from Ye, J. Y.; Umemura, K.; Ishikawa, M.; Kuroda, R. Atomic Force Microscopy of DNA Molecules Stretched
by Spin-coating Technique. Anal. Biochem. 2000, 281, 21–25.
Figure 25 An AFM image of DNA molecules on the APTES-treated mica surface prepared by a spin-coating procedure with a rotation rate of 1000 rpm.
The height is illustrated in gray code ranging from dark (0 nm) to light (2.0 nm). DNA molecules densely adhered on the surface and formed an
interconnecting network. There was essentially no stretching effect on the DNA molecules. Reproduced from Ye, J. Y.; Umemura, K.; Ishikawa, M.;
Kuroda, R. Atomic Force Microscopy of DNA Molecules Stretched by Spin-coating Technique. Anal. Biochem. 2000, 281, 21–25.
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Figure 26 Atomic force microscopic view of the surface of ZnO (a) and 5.0 at. wt.% Al-doped ZnO film (b–d) over different scanning areas.
Reproduced from Behera, D.; Acharya, B. S. Nano-star Formation in Al-doped ZnO Thin Film Deposited by Dip-dry Method and Its Characterization Using
Atomic Force Microscopy, Electron Probe Microscopy, Photoluminescence and Laser Raman Spectroscopy. J. Lumin. 2008, 128, 1577–1586.
binder area fraction in paper coatings is controlled by the pigment packing ability. This is true even in the absence of binder migration
which results in latex distributions with various degrees of uniformity. The method developed in their work was successfully applied to
study of pigment properties impact on distribution of an insoluble binder in the bulk of the coating layer. According to this study, the
arrangement of the binder microdomains within the paper coating layer and the packing ability of the pigments are correlated. Moreover,
even in the absence of the binder migration, the pigment particle size distribution controlled anisotropy degree in the binder configu-
ration. Thus, the coarser pigments produced larger binder microdomains with a higher local variability.
Coupeau et al. studied the mechanical behavior of thin metal films on substrate subjected to the stress and, particularly,
characterized the analysis of the first stage of buckling (74). Also, the nickel/polycarbonate samples were studied using a specific
AFM (see Figures 28 and 29). Such device was allowed in situ observation of the sample surface during the deformation process. The
straight wrinkle-like shapes are induced in thin Ni film above a critical stress perpendicular to the compression axis. On these
debonded regions, also undulations of very low amplitudes appeared. They also discussed dependence on stress of the shape of the
straight wrinkles and of the undulations. They suggest that these experiments may be regarded as an alternative method to estimate
the localized internal stress si and adhesion energy G between the film and the substrate. The straight wrinkles lying perpendicular to
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Figure 27 (a) Adhesion map of the cross section of model coating A1 (left area: 10 mm2, right subarea: 2 mm2); (b) adhesion map of the cross section
of model coating A2 (left area: 10 mm2, right subarea: 2 mm2); (c) adhesion map of the cross section of model coating A3 (left area: 10 mm2, right
subarea: 2 mm2); (d) adhesion map of the cross section of model coating A4 (left area: 10 mm2, right subarea: 2 mm2); and (e) adhesion map of the
cross section of model coating A5 (left area: 10 mm2, right subarea: 2 mm2). Reproduced from Di Risio, S.; Yan, N. Characterizing Coating Layer
z-Directional Binder Distribution in Paper Using Atomic Force Microscopy. Colloids Surf., A 2006, 289, 65–74.
the compression axis increase at the surface above a critical stress value develop towards the center of the sample. In addition,
despite the stress release, the wrinkles remain at this equilibrium position, indicating an irreversible process. Here, the geometric
parameters evolution in the wrinkle, i.e., the width and detection, has been determined as a function of stress; however, the current
models do not prove these experimental results. Besides, undulations of very low-amplitude during the deformation process appear
only on the debonded region. Rising stress values induces an increase of the number of nanoundulations. Owing to the fact that the
undulations disappear when the stress decreases, this process can be characterized by its elastic behavior.
7.09.6.7 Metallurgy and Wear

The unique properties of AFMs have led to the application of this technique in the development of various metallurgical and wear
applications, e.g., study of alloys, structure and crystalline phase of the material, metallic shielding coats, surface in severe medium
conditions (high temperature, corrosive chemicals, and high friction), and composites.
7.09.6.7.1 Characterization of Ultrathin DLC Coatings

Liu et al. characterized DLC coatings ion beam-deposited on AlTiC substrate (70 wt.% Al 2O 3 þ 30 wt.% TiC) (94). It was
found that the island-like topography of DLC-coated AlTiC substrates is very similar to that of an uncoated substrate, which
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Figure 28 Evolution of a straight wrinkle during deformation. The AFM images have been taken in signal error mode and the scan size of each
image is about 16.6 16.6 mm2. The stress induced during the experiment in the Ni thin film is indicated below each image. The top of the wrinkle is
labelled g. Reproduced from Coupeau, C.; Naud, J. F.; Cleymand, F.; Goudeau, P.; Grilhe, J. Atomic Force Microscopy of In Situ Deformed Nickel
Thin Films. Thin Solid Films 1999, 353, 194–200.
indicates full coverage of coatings without any visible defects. They also found that the island height averagely rises either
with film thickness or deposition voltage because of the potential preferential growth of DLC on TiC and possible pref-
erential sputter etching of AlzQ by energetic ions at the initial film growth stage once depositing at enhanced voltages. The
electrochemical measurements indicated that coating with somewhat thick DLC films (>100 nm) at an ion beam depo-
sition voltage of 200 V might significantly increase the impedance of sample/solution interface so as to increase the
corrosion potential of the substrate. However, for a given film thickness, the impedance and the corrosion potential
enhance with deposition voltage up to 200 V and subsequently drop. This is mainly attributed to the kinetic energy-
dependent microstructure of both DLC and the coating/substrate interface. Consequently, it is possible to remarkably
improve the corrosion resistance of AlTiC deposition of DLC under required conditions once it is applied in a corrosive
environment.
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Figure 29 Undulations of low-amplitude on the wrinkle. (a) Topographical mode AFM image. The scan size is 2.53 2.53 mm2 with a gray bar
full extension of 12.2 nm. (b) Perpendicular cross section of the undulations. Reproduced from Coupeau, C.; Naud, J. F.; Cleymand, F.; Goudeau, P.;
Grilhe, J. Atomic Force Microscopy of In Situ Deformed Nickel Thin Films. Thin Solid Films 1999, 353, 194–200.
7.09.6.7.2 Direct Visualization of Sliding-Induced Tribofilm on Nanocomposite Coatings

Kim et al. studied the nanoscale lubrication mechanism in nanocomposite Au/MoS2 solid lubricant coatings using a conductive
atomic force microscopy (c-AFM) (95). Here, the direct visualization of the lubricating process indicates that tribomechanical
formation of a MoS2 tribofilm is the key mechanism. They observed sliding-induced tribofilm formation through a decrease in local
friction and conductivity in nanoscale AFM images. They found that the tribofilm have significant crystallinity and orientation, not
observed in the as-deposited coatings. The observed mechanism can widely be applied to a range of nanocomposite metal/MoS2
coatings. A topographic image (7 nm 7 nm) of a sliding-induced MoS2 tribofilm was studied, where a hexagonal structure and
a lattice spacing of 0.31 nm was observed. This lattice structure is somehow similar to that of a single crystal MoS2 with its basal
plane parallel to the surface.
7.09.6.7.3 AFM of Ion-Etched Cross-Sections for Analyzing the Morphology of Dense Hard Coatings
Jobin et al. described an ion-milling-based sample preparation approach through which it is possible to reveal the morphology of
nanocrystalline hard coatings (9). The technique was successfully applied for columnar TiAlN and nanocomposite TiAlSiN single
and TiAlN/TiAlSiN multilayer films. Besides, the AFM images of cross-sectioned samples were prepared to offer relevant insight
about the nanograins packing and, for that matter, the growth kinetics. While being a simple alternative, TEM observation also
essentially offers complementary information on the density of grain (column) boundaries and the interlamellar growth in
multilayer stacks. Since the sample preparation technique is composition-sensitive, it is possible to identify the layer type in
multilayer film stacks through this technique. The technique is mainly applied for nanoindentation work on selected features such
as interlamellar boundaries, substrate/coating interfaces, grains with a particular composition, as well as the layers with thickness
higher than 20 nm. The differential sputtering at 3.5 keV is an efficient technique to prepare cross-sectioned samples of hard
materials in terms of nanoscale morphological, structural, and nanomechanical characterization. In many cases – assuming that it
is not restricted to the hard coatings – the technique should be an appropriate alternative to the more time-consuming TEM
sample preparation and observation. They used this preparation technique and AFM as a standard routine to observe the inner
structure of hard coatings (see Figure 30). They do this to optimize materials and deposition techniques in order to obtain denser
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Figure 30 Nanoindentation on Al0.7Ti0.3N/Al0.475Ti0.475Si0.05N cross-sectioned and ion-milled samples. (a) AFM topography after indentation,
sowing the location of the indents. Indentations curves (b) at 80 nm on an Al0.7Ti0.3N layer, (c) at 70 nm at the interface of Al0.7Ti0.3N and
Al0.475Ti0.475Si0.05N layers, (d) similar to, (c) but higher load (240 nm). Reproduced from Jobin, M.; Burdet, B.; Santana, A. E.; Bergmann, E. AFM of Ion-
etched Cross-sections: A Method for Analysing the Morphology of Dense Hard Coatings. Thin Solid Films 2004, 469–470, 398–403.
titanium-based coatings with enhanced mechanical properties. Further exploitations of the mentioned technique will be per-
formed for noncoherent multilayers and nanoscale characterization; e.g., in the case of immiscible multiphase structures where an
accurate evaluation of the mechanical properties in the grain bulk might assist in the determination of coherency stresses between
the grains. Application of the developed cross-section revealed to be appropriate and as a determinant for submicron to nanometer
scale structural and mechanical characterization.
7.09.6.7.4 Nanotribological Characterization of Coatings

Podesta et al. studied tribological properties of industrial polytetrafluoroethylene (PTFE)-based coatings, using an AFM (96). Using
a new characterization protocol, they were allowed to assess the friction coefficient and adhesion forces at the submicrometer scale
in a reliable and quantitative manner, even for highly corrugated industrial samples (see Figure 31). They investigated and
compared PTFE coatings charged with various additives in dry and humid environments. Besides, they studied the effect of additives
and humidity on the friction coefficient and adhesion forces through standard silicon nitride tips serving as sliders in the low-load
regime. The friction coefficients and adhesive constants of the coatings in humid and dry environment were measured, assuming
that there is a linear relationship between friction and normal load based on a modified Amonton’s law (friction coefficient plus
adhesive offset). Weak dependence was found for friction coefficients on the relative humidity, except for the case of MoS2 þ Al
coatings, which involves a larger friction coefficient in the presence of humidity. Also, they observed that there is an anomalous
relationship between the adhesive constant and humidity in the case of PTFE þ MoS2; i.e., it decreases by increasing humidity. This
leads to the better structural stability and tribological properties of PTFE þ MoS2 coating compared to the pure PTFE, namely in
a dry environment. Figure 32 shows typical lateral force versus external applied load curve for a PTFE-based coating.
7.09.6.8 Determination of Coating Young’s Modulus

Thome et al. studied a degree of polymerization in thin polymer coatings through following the variation of their local mechanical
properties (97). They applied AFM in an indentation mode to examine the mechanical characteristics of silicone coatings on
polycarbonate substrates. Figure 33 shows schematic representation of the indentation process. In this work the Young’s modulus
evaluation for the silicone coatings was determined as a function of the polymer annealing time. They applied a relative method,
involving a calibration step with as set of reference polymers, to measure Young’s moduli. Here, no change was observed for the
modulus of silicone coatings annealed for more than 40 min at 130 C. This implies that overheating does not change mechanical
properties of the coating. Young’s moduli of silicone coatings were determined for several annealing times to examine coatings’
polymerization, where the samples annealed for 40 and 90 min have identical mechanical characteristics (see Figure 34). One
outcome of this work is that for achieving a good polymerization degree, there is no need to perform annealing processes longer
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Figure 31 Typical AFM topographic map of a PTFE-based coating. The AFM was operated in contact-mode. Scan size is 130 mm and vertical
scale is 3 mm. Reproduced from Podesta, A.; Fantoni, G.; Milani, P.; Guida, C.; Volponi, S. Nanotribological Characterization of Industrial
Polytetrafluorethylene-based Coatings by Atomic Force Microscopy. Thin Solid Films 2002, 419, 154–159.
Figure 32 Typical lateral force versus external applied load curve for a PTFE-based coating. The dotted line is a weighted linear fit of experimental data.
Reproduced from Podesta, A.; Fantoni, G.; Milani, P.; Guida, C.; Volponi, S. Nanotribological Characterization of Industrial Polytetrafluorethylene-
based Coatings by Atomic Force Microscopy. Thin Solid Films 2002, 419, 154–159.
Figure 33 Schematic representation of the indentation process: (1) The tip is lowered into contact with the surface, (2) then indented in to the surface,
and (3) finally lifted off the sample surface. Reproduced from Thome, T.; Fouchez, S.; Delalande, S. Determination of Silicone Coating Young’s
Modulus Using Atomic Force Microscopy. Phys. B 2009, 404, 22–25.
than 40 min. Another finding of this work is that a two-step relative method is necessary to cope with AFM technique limitations,
i.e., the unknown tip and surface contact geometries. In particular, this method can be appealing to good control the mechanical
properties of a multiphased thin polymer layer at a nanometer scale.
Martínez-Martínez et al. examined some carbon-based coatings through AFM and lateral force microscopy (LFM) techniques to
investigate their microstructure and friction properties at the micro- and nanoscales (98). They prepared four samples through the
magnetron sputtering technique. The samples were as an amorphous carbon film (a-C), two nanocomposites TiC/a-C with
different phase ratio (w1:1 and w1:3), and a nanocrystalline TiC sample. In addition, a highly oriented pyrolytic graphite
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Figure 34 AFM morphology image (5 10 mm2) showing the indentation series performed on the silicone coating sample. Reproduced from Thome,
T.; Fouchez, S.; Delalande, S. Determination of Silicone Coating Young’s Modulus Using Atomic Force Microscopy. Phys. B 2009, 404, 22–25.
(HOPG) and an amorphous hydrogenated carbon coating (a-C:H) were included to evaluate the effect of the roughness and the
hydrogen presence, respectively. The topography (roughness) samples were studied through the AFM, while LFM was utilized to
measure the friction properties at the nanoscale by two various approaches (see Figures 35–37). First, the potential friction
contrast on the samples was evaluated via subtraction of forward and reverse images, which is lately confirmed by the study of
lateral force profiles in both directions and the histograms of the subtraction images. As the second step, the average friction
coefficient over the analyzed surface of each sample was analyzed. Considering the tip evolution/damaging, mica was utilized as
a reference before and after each sample and then samples-to-mica friction ratios were calculated. The findings of this work
indicated that LFM is a useful tool to characterize a mixture of phases with different friction coefficients. Typically, the friction
ratios seemed to be dominated by the amorphous carbon phase; owing to the fact that it was not possible to distinguish among
samples with different proportions of the amorphous phase (friction ratios between 1.5 and 1.75). However, one could draw
a conclusion that the differences in friction behavior arose from the chemical aspects (nature of the phase and hydrogen content)
rather than surface characteristics, as the roughness (Ra values up to 5.7 nm) does not occur according to the observed trend.
Finally, the Ogletree method was utilized in this work where lateral force calibration and estimation of the friction coefficient of
the given samples are described.
Figure 35 Diagram of the tip behavior (normal and lateral forces) for complete surface scanning cycle including subtraction and addition of both lateral
force profiles. Reproduced from Martínez-Martínez, D.; Kolodziejczyk, L.; Sanchez-Lopez, J. C.; Fernandez, A. Tribological Carbon-based Coatings:
An AFM and LFM Study. Surf. Sci. 2009, 603, 973–979.
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Figure 36 Topographic data of samples (images and topographic profile): (a) TiC; (b) TiC/a-C (1:1); (c) TiC/a-C (1:3); (d) a–C; (e) a–C:H; and (f) HOPG.
Reproduced from Martínez-Martínez, D.; Kolodziejczyk, L.; Sanchez-Lopez, J. C.; Fernandez, A. Tribological Carbon-based Coatings: An AFM and
LFM Study. Surf. Sci. 2009, 603, 973–979.
7.09.6.9 Surface Topography, Membranes, and Filters

‘Membrane’ is called to very thin layers which segregate a material mix by their selective passing for one of them. There are various
segregating factors including a difference in separation of suspended particles in the fluid, difference in solving in membrane in
segregation of gas oxygen from nitrogen, and difference in electrical charge in segregation of viruses, bacteria, etc., from water. When
using AFMs, it is possible to determine porous structures, holes diameter, and surface properties of membranes, designed filters, or
functioning filters in nano scales. Finally, the results are applied for optimum adjusting of the membrane synthesis parameters and
understanding of performance of and changes occurred in the membrane – for synthesis of more efficient membranes based on
perceived mechanisms – and increase of their lifetime; therefore as the time passes, the deposited materials in membrane pores
leads to the elimination of its segregating properties.
Malherbe et al. selected two different samples including homogeneous and monocrystalline silicon wafers and chromate
conversion coatings to investigate the effect of GD sputtering on samples surface through AFM and rugosimetry measurements –
both at the original samples surface and at the bottom of GD craters (99). Various surface morphology associated changes
might happen during ion bombardment. Different experimental conditions, such as the sputtering time, craters depth, discharge gas
pressure, and rf forward power are applied to evaluated such changes. Based on findings of this work, glow discharge sputtering
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Figure 37 Friction contrast of samples (friction maps and lateral force profiles): (a) TiC; (b) TiC/a-C (1:1); (c) TiC/a-C (1:3); (d) a-C; (e) a-C:H;
and (f) HOPG. Possible friction contrasts are marked in the lateral force profiles with a dashed line. Reproduced from Martínez-Martínez, D.;
Kolodziejczyk, L.; Sanchez-Lopez, J. C.; Fernandez, A. Tribological Carbon-based Coatings: An AFM and LFM Study. Surf. Sci. 2009, 603, 973–979.
created morphology modifications on the samples surface for all studied experimental conditions ranged from the softer GD
conditions (such as application of low pressures, low rf powers, or applying the GD in pulsed mode) to the stronger GD conditions
(including long sputtering times, high pressures, or high rf powers). Furthermore, it must be emphasized that the observed vari-
ations in the sample surface morphology after rf-GD-OES analysis were sample dependent and are related to sputtering time, rf
forward power, and discharge pressure. Formation of microsized patterns with a curved facet-like structure at the bottom of the GD
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crater was obviously shown for the silicon wafers, while the tiny nanometric CCC small holes were seen for all investigated
conditions. Hence, one can claim that GD sputtering results in surface roughness (micro-roughening) modifications at different
scales depending on the sample matrix and; however, such an effect should be carefully assessed for depth-profiling analysis and
sample preparation purposes through glow discharges. It is required to conduct further studies to examine the fundamental process
of glow discharge sputtering and, therefore, better understanding the role of GD operating parameters on the observed morpho-
logical changes. Furthermore, it is required to compare surface roughness evolution for the chromate coatings in nanoscale (AFM
measurements) and microscale (rugosimetry measurements) dimensions for determining the effect of GD experimental parameters
on depth resolution and rf-GD-OES analysis quality. According to the observations of this work, the rf forward power can be
considered among the parameters that control morphology modifications at the sample surface after GD analyses, irrespective to the
roughness of the original sample surface.
7.09.6.10 Testing the Surface Parameters of Coatings of Medical Implants

Klimenov et al. utilized AFM methods to examine calcium phosphate coatings developed on surfaces of various materials, which are
used in medicine (86). They applied radio-frequency magnetron sputtering of a hydroxyapatite target. They determined roughness
parameters and values of the surface potentials of metal, polymer, and hybrid substrates in a semicontact regime. Calcium phos-
phate coatings enhanced the roughness in surfaces of polymer and metal materials. As a result, it indicates a stimulating factor for
osteogenic cells’ attachment and proliferation. It is shown that when using the Kelvin method, calcium phosphate coatings change
the surface potential of substrates.
The findings of this work indicated that: (1) Utilization of the AFM methods allows quantitative evaluation of the surface
roughness parameters and the distribution of the surface potential of biocoatings. Hence, it results in yielding substantial data to
determine for the application field of such coatings. (2) Once applying of the AFM method, it was found that the substrate type
(polished titanium or a polymer coating) does not considerably affect the parameters of CP coatings formed through the method of
RFMS of a hydroxyapatite target. Also, this work indicated that high-quality CP coatings can be developed through the RFMS method
on the surfaces of polymer materials with medical applications. (3) Another finding of this study was that the deposition of coatings
by the RFMS method enhances surface roughness of the polymer and metal materials; hence, it becomes a stimulating factor for
attachment and proliferation of osteogenic cells. (4) Application of the Kelvin method indicated that CP coatings formed by the
method of RFMS of a hydroxyapatite target change surface potential through its shifting to the positive region relative to the ground.
7.09.6.11 Control of Quality and Study of Surface Defects in Magnetic Memory Units
Considering nanoscale units of the memory, AFM is a very ideal tool to prepare 3D maps of the surface structure and topography of
the memory units. Imaging by this method is not as simple as other approaches. Length, width, height, gradient, and homogeneity
of each memory unit is determined in nano precision and structural defects are detected. In this regard, it is possible to recognize
favorability of fabrication approaches and change of memory cell with time induced by contact with head. Finally, optimization of
surface polish process and optimum use of lubricants within head contact with memory units is realized.
7.09.6.12 Parameterization of the Magnetite Coating Surfaces

Misurkin et al. applied AFM to study dynamic behavior of the magnetite coating (MC) developed on a steel 3 (St3) sample by
chemical oxidation in an ammonium nitrate solution (100). According to a definition, the digitized AFM data are a series of profiles
of chaotic roughness which are obtained using a sensing probe which scans the surface of studied fragment. In addition, flicker noise
spectroscopy (FNS) is a technique applied for AFM images analysis selection of the parameters adapted to MC state characterization
at the beginning of their development. Spatial power spectra and transient structure functions were utilized to calculate FNS
parameters introduced to characterize coating surfaces. For different type irregularities (jumps and spikes), these parameters were
considered as the correlation lengths. Also, the dimensionless parameters were introduced to characterize correlation loss in a series
of irregularities when spatial intervals are significantly less than correlation lengths. These FNS parameterization allowed obtaining
information on the state of the initial surface of St3 samples. Besides, it permitted to reveal the structural features which are intrinsic
to the surface of MCs developed after various oxidation times. This finding indicates the correlations of MC structure elements and
characterizes its micro-irregularities features arising at different stages of coating formation.
7.09.6.13 Integration of AFM and Scanning Electrochemical Microscopy (SECM) Techniques

Among many approaches conducted over the past decade, AFM and SECM techniques have had a stronger effect in in situ study of
the local wear of aluminum alloys. In comparison, and unlike many other successful applications, spatial clarity of the SECM is less
than SPM based techniques such AFM. Nonetheless, the common AFMs lack chemical properties. A new approach to deal with this
problem is to fabricate a dual-functional probe which serves as both AFM head and super fine electrode of SECM. It is also possible
to integrate the SECM/AFM probe with other techniques such as photolithography, metal fabrication technology, concentrated ion
beam, equipment for nano syntheses including chemical and ionic etching, and low pressure chemical deposition, and plasma-
assisted CVD. There is little information available about synthesis steps of these techniques. Typically, in all approaches of merging
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AFM and SECM techniques, the main task to be completed is to synthesis a micron or submicron conductive terminal loaded in an
insolent substrate for simultaneous determination of AFM and SEFM records. Mac Ferson et al. made an attempt to develop
a SECM/AFM probe in noncontact conditions. In this probe, a very thin film of dye is deposited on a platinum microwire in
electrophoretic manner. During drying and consolidation of the dye, it starts to shrink from the sharpest point of the probe to
produce the microelectrode required for SECM. The flatted part of the cantilever produces a flexible cantilever for the sensor of the
AFM while the remained part of the probe guarantees that not only the heads end in exposed to the solution. In noncontact mode,
the probe starts the imaging process by its SECM part while it performs imaging in contact mode using its AFM part.
In a newer project performed by the same group, a procedure has been explained for synthesis of fine structures which are
triangular batch from probes of SECM/AFM. Direct electron beam lithography has been applied for batch synthesis to determine the
form of probe in AFM device and geometry of its attached SECM microelectrode which is in the wafer form. EBL is a triangular gold
electrode with a base width of 1 mm and height of 0.65 mm, which is lithographically loaded to the head of an AFM device. Applying
a 3.25 inch wafer to 60 probes in each set leads to an 80% success. The efficiency of the probe using AFM/SECM approach is 1 mm
and 10 mm of platinum disk microelectrode.
Kranz et al. also fabricated a gold nanoelectrode ring as framework shape around one head of AFM for aggregation of the head
for AFM/SECM records. They cut a pyramidal commercial AFM head with FIB mill and then coated it with a gold layer and then
sprayed a silicon nitride film on it using PE-CVD technique. In the next step, the gold end of the head was detected by a cross-section
of the upper part and a loop nanoelectrode was developed. Finally, the head of this AFM device was sharpened again. The elec-
trochemical reaction of the SECM probe with CV characteristics in a solution of ferrocyanide containing solution was characterized;
which corresponds well with calculated limit current. Prinz and his research group from Stanford University have made
a comprehensive effort to produce an array probe head for AFM/SECM. To do so, they have developed a convertor base with
a platinum microelectrode in a submicron regime by merging the etching process of the depth isotropic and anisotropic probe.
Then, using silicon nitride, platinum coat, and insolent deposited layer, a precise end head is developed using uncoated platinum
through metallic mask FIB technology. This technology allows synthesizing both linear probe arrays and 2D probe arrays.
According to several studies, conduct to observe local electrochemical activities, mediate components such oxide-reduction
couples such as I/I3, Fe(CN)3þ 2þ 2þ 2/ 3
6 , Ru(NH3)6 /Ru(NH3)6 , and IrCl6 IrCl6 have been utilized. To determine advantages of
integrated AFM/SECM, recording various numerical simulation techniques have been applied for SECM since the clarity of SECM
part was always less than that of AFM part. Some of these techniques are adaptive final element (AFE), boundary element method
(BEF), and finite element method. In addition, SECM simulations can enhance analysis results including the effect of various
geometrical and electrochemical parameters on, for example, resolution of the image. For instance, to estimate and improve clarity of
SECM device, it is possible to apply numerical simulation to study the effect of geometrical parameters. Fabrication of AFM/SCEM
probes still faces many challenges. Hence, in a technological approach, an expensive simulation process can contribute evaluation of
efficiency and even improvement of probe design. The AFM algorithm for simulation of the SCEM probe was selected optionally as
2D. The response of ammeter steady and transitional ammeter SECM has been simulated in three dimensions using the BEM tool.
7.09.6.13.1 Pitting Mechanism on Stainless Steel Nanocrystalline Coating

Liu et al. applied electrochemical noise (EN) and in situ AFM under anodic potential to study the pitting corrosion behavior of an
austenite stainless steel with polycrystalline (PC) and nanocrystalline (NC) microstructure in 3.5% NaCl solution (101). They
applied power spectral density and wavelet transform for analysis of the EN data. According to the outcomes of this work, the pitting
corrosion resistance of the NC coating was completely higher than that of the PC alloy, with different pitting mechanisms observed
for both specimens. These mechanisms include a slow metastable pit generation and healing for the PC alloy and a fast metastable
pit initiation and death for the NC coating. The findings of this work indicated a good correlation between the EN and the in situ
AFM analysis. In this work, also the pitting corrosion mechanism was discussed based on the EN analysis and the in situ AFM
observations (see Figure 38).
‘In situ’ deposition is a technique applied where a mix of aniline monomer solutions and an oxidizing agent results in the growth
of a uniform polyaniline (PAn), which conducts thin films on submerged substrates. Several substrates including glass and organic
materials can be applied for deposition of PAn films on. In this process, by adjusting the duration of the substrate dipping time, it is
possible to control film thickness; e.g., about 300 Å, was produced during a dipping time of 5 mm. AFM was used to analyze the PAn
film surface morphology and roughness. According to a study conducted by Avlyanov et al., AFM images of the PAn surfaces
presented very smooth surfaces with approximate surface roughness (mean and root mean square) of 30 Å (102). The results of UV,
visible, and near IR techniques for measuring PAn films were consistent with the thickness measurements obtained from AFM.
According to the AFM images, it was found that the morphology of PAn film surface are characterized by particle-like features which
are about 50–100 nm in size and are tightly packed to produce a high density structure. In this work, conductivity of the doped PAn
films was determined as 2–6 S cm1, using a 4-probe measurement process. As previously mentioned, in this work an in situ dipping
method is explained. By using such approach, it is possible to deposit PAn thin films with controlled thickness on glass and organic
polymer substrates. Applying AFM analysis indicated that the PAn films are homogenous, with smooth surfaces (surface roughness
about 30 Å) and conductivity (about 5 S cm1), similar to that of ordinary free-standing doped PAn films. To control the
thickness in this work, the substrate dipping time and/or amount of oxidizing agent were adjusted. AFM images of the films with
a thickness of 300 Å presented a surface morphology which suggests that the PAn particles (with size of 50–100 nm) are tightly
packed together to develop a high density structure. Once applying a 2:l molar ratio of aniline monomer to oxidizing agent, it was
found that film thickness increases almost linearly up to a dipping time of 5 min until saturating at a thickness of about 300 Å.
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Figure 38 In situ AFM images of the PC alloy in pitting stage under anodic polarization in 3.5% NaCl solution. Reproduced from Liu, L.; Li, Y.; Wang, F.
Pitting Mechanism on an Austenite Stainless Steel Nanocrystalline Coating Investigated by Electrochemical Noise and In-situ AFM Analysis.
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The findings of this research suggest that in situ PAn film deposition provides a simple and potentially low-cost direct method to
produce thin films with high conductivity. Such films are as a result smooth and continuous which can be applied in sensors,
photoelectronics, as well as other devices.
7.09.6.13.2 Crystal Growth in Thin Films

Kikkawa et al. performed direct visualization of crystal growth in poly-(L-lactide) thin films through a temperature controlled AFM
(103). The edge-on lamellar crystals nucleated and elongated at the initial stage of crystallization. The formed crystals indicated
S-shaped morphology and they had a change from edge-on to flat-on manner. In this work, the curvature of edge-on lamellar crystal
wad discussed with respect to the inclination and distortion of polymer chains in the crystal. Furthermore, based on in situ AFM
observation of crystal growth and enzymatic degradation mechanism, formation of flat-on crystal from edge-on lamellae was
proposed as derivative growth. AFM observations of PLLA thin film both during the crystal growth process and after enzymatic
degradation proved changing of the orientation from edge-on to flat-on through the secondary nucleation and derivative growth.
An explanation for the formation of curved edge-on crystals was that it might be the chain distortion or chain shift along the
crystallographic c-axis. Direct observation of crystal growth in PLLA thin film indicated the edge-on crystal growth as well as further
formation of flat-on crystals. According to the results of this research, the enzymatic degradation preferentially occurred in
amorphous regions and was used as an etching method for the examination of the crystalline region in thin films. The flat-on crystal
was grown on the edge-on crystal because of the reduction in molecular mobility near the crystal and its suppression by the air–
polymer interface. Based on these findings, it can be proposed that PLLA spherulites have no extinction ring because of the less
spatial suppression in the film. This work indicated that a combination of in situ AFM observation and enzymatic degradation
treatment produces progressive information on the crystal growth mechanism. Moreover, AFM can be applied to align the
molecular chains at a fixed region, and fabrication of the oriented backbone in the thin film.
Li et al. prepared novel polyacrylamide–carbon nanotubes (PAM–CNTs) through the application of ultraviolet radiation
initiated polymerization (104). The main features of PAM–CNTs copolymer were determined through the application of Fourier
transform infrared spectroscopy, UV–VIS absorbance spectra, fluorescence spectra, and transmission electron microscope. Also,
they applied atomic force microscopy/friction force microscopy (AFM/FFM) to investigate morphology and microtribological
properties of PAM–CNTs thin films on mica. Once changing the applied load and friction coefficient, friction of the films was
stable once it was significantly decreased as the CNTs addition. They indicated that the rigid rod-like CNTs in polymer enhances
load-bearing and anti-wear properties of the thin films. In their work, PAM–CNTs copolymer was synthesized by UV radiation
initiated polymerization. As previously mentioned, the spin casting thin films on mica were characterized by AFM and their height
profiles were calculated (see Figure 39). The results indicate the films have a rather flat surface morphology. Moreover, depen-
dence of the friction signals on applied loads was investigated by FFM. Also, the differences between PAM–CNTs and PAM thin
films are noted and discussed based on the rigid rod-like CNTs segments. It must be noted that, it is possible to increase load-
bearing property of the thin films by CNTs.
7.09.6.13.3 Micronanotribology of Ultrathin Hard Amorphous Coatings

Sundararajan et al. conducted microscale scratch and wear resistance tests using an AFM on ultrathin hard amorphous carbon
coatings, often called DLC coatings (105). They deposited these coatings using filtered cathodic arc (FCA), direct ion beam (IB),
electron cyclotron resonance plasma chemical vapor deposition (ECR-CVD), and sputter (SP) deposition processes. They studied
coating thicknesses of 20, 10, 5 nm and, for the first time, 3.5 nm coatings (see Figures 40 and 41). They made an attempt to identify
the thinnest coating that exhibits good wear-resistance, detect the deposition processes that produced superior coatings for wear-
resistance, as well as understanding the failure mechanisms of such ultrathin coatings during wear process. The findings of this
work indicated that typically the thicker coatings exhibit better scratch wear performance compared to the thinner coatings since
they have better load-carrying capacity in contrast to the thinner coatings. ECR-CVD and FCA coatings showed the best wear
resistance at 20 nm. At 10 nm and 5 nm ECR-CVD and IB coating indicated the best wear resistance, respectively. The coatings with
thickness of 5 mm presented reasonable wear resistance; while 3.5 nm coatings exhibited extremely low load-carrying capacity, poor
wear resistance, and evidence of early coating delamination. Although IB and ECR-CVD 3.5 nm coatings had the same wear
resistance values at low loads, the coatings with thickness of 3.5 nm seems to be infeasible for wear-resistant applications. FCA, IB,
and ECR-CVD coatings indicated nonuniform, sudden, catastrophic failure at higher thicknesses. It is believed that the spatial
variance in hardness and fracture toughness is responsible for nonuniformity of failure. Besides, SP coatings exhibited gradual and
uniform wear and it is believed they involve higher spatial uniformity in terms of the mechanical properties, although the properties
being weaker than those of the other coatings.
7.09.6.14 In Situ Thickness Measurements of Ultrathin Multilayer Films

Lobo et al. introduced a method for direct in situ thickness measurements of ultrathin soft polymer films (106). They applied an AFM
tip to create a furrow in the film. To determine thickness of the furrow, the sample was scanned across the furrow by the AFM. Because
the scratching and the measurements were performed with the same device, the sample is not required to be moved. This method is
applied to layer-by-layer polymer/polyelectrolyte ultrathin films on hydrophilic glass and silicon wafer substrates. This procedure can
be performed due to the fact that the polymeric film is less stiff than the substrates and the silicon tip. The results for 10–12-bilayer
films can be compared with those obtained from profilometry, whose accuracy is only reasonable for films which have more than 10
bilayers. The AFM and profilometer results show that film thickness rises linearly with the number of bilayers. In addition, it does not
seem that the film thickness has any reliance to the applied substrate; rather it depends only on the number of deposited bilayers.
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Figure 39 Tapping mode AFM images of spin casting films. Three-dimensional representation of topographic picture of 1 mm 1 mm. (a) PAM film,
(b) PAM-CNTs film, and (c) blending sample of PAM/CNTs film. Reproduced from Li, X.; Guan, W.; Yan, H.; Huang, L. Fabrication and Atomic
Force Microscopy/friction Force Microscopy (AFM/FFM) Studies of Polyacrylamide-carbon Nanotubes (PAM-CNTs) Copolymer Thin Films. Mater. Chem.
Phys. 2004, 88, 53–58.
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Figure 40 AFM 3D images of scratch profiles at various normal loads on selected FCA and SP coatings. Reproduced from Sundararajan, S.; Bhushan, B.
Micro/nanotribology of Ultra-thin Hard Amorphous Carbon Coatings Using Atomic Force/friction Force Microscopy. Wear 1999, 225–229, 678–689.
7.09.6.15 Measurements of Elastic Properties of Ultrathin Coatings

A comparative study was presented by Amelio et al. about the elastic stiffness of ultrathin (5, 20, and 100 nm thick) diamond-like carbon
coatings in which the sampling depth was less than or equal to the thickness of the coating (107). They carried out the experiments using
atomic force acoustic microscopy, as a dynamic operation mode of the atomic force microscope which allows measuring of the elastic
properties with high spatial resolution. The method is based on the examination of the shift in the cantilever resonance frequencies
induced by contact stiffness between the sensor tip and the sample surface. They reported two sets of measurements: in one set the silicon
sensor tips were employed, while in the other diamond-coated tips were used (see Figures 42 and 43). During data acquisition, the
silicon tips indicated considerable wear. However, the wear could be avoided and qualitative measurements of high stability could be
performed applying diamond-coated tips. Accordingly, it allows comparison of coatings obtained through the different deposition
techniques. It was also shown how the obtained results can result in the further quantitative measurements on stiff coatings.
Miller et al. investigated the effect of film roughness on the wetting properties of vacuum-deposited polytetrafluoroethylene
PTFE thin films (108). They applied AFM and contact angle goniometry. They determined characteristics of the surface roughness
AFM in terms of RMS roughness (Ra) and fractal dimensions. According to AFM studies, a contact angle correlation with surface
roughness was evident from findings of their work. Such an angle was discussed based on the wetting theory. Their results also
proved that large water contact angles (>150 ) recently observed at the surface of a new water repulsive coating material (mixture of
PTFE and binder) are mainly owing to the surface roughness. This work confirmed the effect of nanoscale surface asperities on the
wetting properties of hydrophobic coatings. Even at low surface roughness values (Rq ¼ 80 nm), the changes of surface roughness
affect wetting properties of the PTFE thin films. As shown by fractal analysis (fractal dimension ¼ 2.2), the substrate roughness
significantly enhances with water contact angle; then, it decreases wettability of the PTFE thin film. It seems that surfaces reparation/
production with specifically designed surface roughness features is suitable in formation of more efficient water repulsive materials.
7.09.6.16 Coupled Applications

In this section, some reported coupled applications of AFM will be introduced. Muller-Buschbaum et al. applied AFM and grazing-
incidence small-angle neutron scattering (GISANS) to investigate surface morphologies of confined, dewetted polymer films (109).
During the examination of the homopolymer films of deuterated polystyrene (dPS), both techniques indicated a droplet structure,
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Figure 41 2D Surface height and corresponding friction force maps of FCA and SP 10 nm coatings during wear showing the failure process. Brighter
regions correspond to higher surface height and higher friction force in the surface height and friction force images, respectively. Reproduced from
Sundararajan, S.; Bhushan, B. Micro/nanotribology of Ultra-thin Hard Amorphous Carbon Coatings Using Atomic Force/friction Force Microscopy.
Wear 1999, 225–229, 678–689.
characterized by one most prominent in-plane length. Once applying the polymer blend films of dPS and poly(p-methyl styrene),
GISANS allows probing the in-plane composition of the dewetting structure because of the contrast obtained from deuteration. An
additional sub- and superstructure, which is not detectable by AFM, is developed owing to the phase separation process at different
length scales. Furthermore, in this work, the effect of wavelength applied in GISANS experiments on the observed structures was
discussed. Once having confined homopolymer and polymer blend films, the surface topography of the dewetted samples presents
a most prominent in-plane length scale which corresponds to the mean distance of the droplets. Both AFM and GISANS techniques
indicated that they are able to resolve this in-plane length; thereby, it can be regarded as a representative for the whole sample. In
comparison to the droplets resulted from toluene-vapor treatment, those developed by annealing treatment are more irregular in
their contact line. Therefore, the polymer blend samples involve composition inhomogeneities because of a phase-separation
process which is not detectable by AFM. GISANS indicated a smaller substructure and a larger super structure in the case of the
annealed samples and toluene-vapor-treated samples, respectively. So, there is some trend to phase separation in confined blend
films of PpMS:dPS, although the dewetting itself is not obtained by the polymer incompatibility. GISANS technique provides the
typical advantages of neutron experiments with advanced scattering techniques commonly used with X-rays, in the same time.
Tuning the wavelength, it is possible to probe the roughness spectrum from a molecular to a mesoscopic in-plane length scale.
Furthermore, it offers information about the internal composition of the examined samples. It must be noted that GISANS texts can
only be performed at a limited number of experimental facilities due to the need for a high intensity and an excellent collimation.
Gilicinski et al. reported several new applications of AFM with specific values to develop a system of improved waterborne
coatings (110). They developed an AFM method for quantitative assessment of the coalescence and film formation extent for latex
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Figure 42 Mechanical equivalent used for the cantilever in order to determine k* from its vibrational spectra. (a) General case including lateral
and vertical tip-sample interaction forces. The vertical and lateral contact stiffness and damping constants are k*, k
Lat , g, and gLat, respectively. L is
the total length of the cantilever, L1 is the length between the tip and the cantilever base, L0 is the length from the tip to the end of the cantilever with
L ¼ L1 þ L0 , h is the tip height, and a0 is the angle between the cantilever and the sample surface. (b) Simplified case taking into account that the
tip is located at some distance L0 away from the end of the cantilever. Tip-sample contact is modeled by a spring k* and a0 ¼ 0. Reproduced from
Amelio, S.; Goldade, A. V.; Rabe, U.; Scherer, V.; Bhushan, B.; Arnold, W. Measurements of Elastic Properties of Ultra-thin Diamond-like Carbon Coatings
Using Atomic Force Acoustic Microscopy. Thin Solid Films 2001, 392, 75–84.
Figure 43 Experimental set-up for atomic force acoustic microscopy. Reproduced from Amelio, S.; Goldade, A. V.; Rabe, U.; Scherer, V.; Bhushan, B.;
Arnold, W. Measurements of Elastic Properties of Ultra-thin Diamond-like Carbon Coatings Using Atomic Force Acoustic Microscopy. Thin Solid
Films 2001, 392, 75–84.
films. For this aim, they measured particle number density of protruding (uncoalesced) particles in dried coatings. In the second
step, topographic imaging was applied for evaluation of the environmental (temperature) effects on film formation in a waterborne
latex system. Finally, AFM and optical measurements were applied to study specular gloss of waterborne epoxy coatings, as well as
topographic features analysis using power spectral density calculations (see Figures 44 and 45). Also, the mechanisms for gloss
reduction over time (particularly in early pot life coatings) were detected in the studies. It is possible to develop further coating
studies through the development of new AFM modes – including friction force, force modulation, and phase contrast – that can be
applied to map mechanical properties (e.g., friction, stiffness, and adhesion), while simultaneously imaging topography. Finally,
some cases of the utilization of the phase contrast mode for chemical detection of different domains in early pot life waterborne
epoxy coatings were introduced.
The polymer coatings for microelectronics packaging are subjected to ductile–brittle transition on a frequent basis once being in
contact with particular solvents. Such solvents can lead to the local deformation zones to grow from the stress concentrations as well
as resulting in cracking and debonding phenomena. Due to the adhesion to the substrate, the surface opening of the deformation
zones is very narrow. Hence, microstructure investigations cannot be made by optical microscopy or SEM. Yang et al. used AFM and
found that the zones depth rises with immersion time, implying the fact that they grew from the surface toward the interior zones
(111). Here, the stress release induced by the deformation zones can be calculated as a function of position. The zone depth linearly
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Figure 44 An image of 21-Å high silicon oxide patterns on a silicon wafer is an example of a calibration standard used for accurate measurements
of nanometer scale height variations on coating surfaces. Standard courtesy of T. Ohmi (110).
enhances with the zone width. Moreover, in this study the zone growth and film-thickness effect, as well as the cracking of the free-
standing films in different solvents, were investigated. According to the findings of their work (1) Hexane and methanol baths can
result in the development of local deformation zones in the PS thin film adhered to a rigid substrate which is subjected to the driving
force of the residual thermal stress. (2) Hexane cerates deformation zones more easily compared to methanol because of the
diffusion speed of the small molecules into the polymer coatings and the plasticization induced by the solvent. (3) By developing
the line defects during solvent immersion, a considerable amount of stress release was resulted. Here, the stress release values can be
determined as a function of position by AFM topographical observation and plane stress calculation. (4) Data of depth versus
immersion time showed that deformation zones grow from the surface toward the inner parts. (5) Adhesion on a rigid substrate will
limit the deformation growth. Besides, the inner surface of the deformation zone in the free-standing film is much rougher
compared to the adhered film. (6) According to the diffusion and bending beam data, it seems that a case-II diffusion is followed by
the diffusion of hexane and methanol in adhered PS thin films.
Investigation of comb-like versus the arborescent grafted copolymers made of poly(chloroethyl vinyl ether)-g-polystyrene
(PCEVE-g-PS) was conducted. Viville et al. described the manner in which the molecular architecture of the branched polymers
affects their nanoscale organization in thin films, as observed by AFM (112). The surface organization of the (PCEVE-g-PS)
copolymer molecules was strongly conditioned through the interaction between the molecule–substrate and the molecule–
molecule. This, in turn, results in different possible orientations of the lateral branches with regarding the surface and, for that
matter, to different final morphologies. The presence of a large number of densely grafted PS segments was observed in the PCEVE
backbone which stiffens the backbone and results in the molecules adaption to a regular brush conformation. The finding of this
work also showed that the size and surface organization of the molecules is highly affected by the structural complexity of the lateral
side chains. Moreover, TM-AFM images indicated (starting from the same backbone) an increase in structural complexity, from
a comb-like (PCEVE-g-PS) to a hyperbranched [PCEVE-g-(PS-b-(PCEVE-g-PS))] architecture (see Figures 46 and 47). This leads to
the significant increase of the height and the width of the molecules to, while the length of the molecule, measured by AFM, being
the same. Here, also the surface organization of copolymer molecules on graphite was investigated to study the influencing factors
of the coiling behavior in the chains. Furthermore, the elongated conformation of isolated comb-like copolymer molecules seen in
this case was in good agreement with energetically favored interactions between the PS side chains and the surface of graphite. These
interactions make PS side chains favorable to preferentially orient along the graphite surface, which result in a stronger shape
anisotropy of the molecule. It must be noted that the geometrical parameters of the molecules and, in particular, their observed
contour length on graphite and on mica correspond with data obtained from the solution. The findings of this work indicated that
the copolymer molecules can adjust different surface organizations as a function of their molecular architecture, the nature of the
substrate, and the interactions with neighboring molecules. It is possible to apply these surface organizations to provide specific
techniques to produce nanometer-size periodic surfaces with efficiently controlled morphology. In addition, it is allowed to develop
very specific properties molecules through chemically functionalized and designed molecules.
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Figure 45 Analysis of probe tip size for sharp (a) and blunted (b) silicon tapping-mode AFM tips using AFM imaging of gold colloid tip characterizers
on mica. Field emission SEM images of the same probe tips are shown in (c) for the sharp tip and (d) for the blunt tip. The use of a tip calibrator
is a convenient and accurate method for quantitating the effect of tip size on AFM data. Reproduced from Gilicinski, A. G.; Hegedus, C. R.
New Applications in Studies of Waterborne Coatings by Atomic Force Microscopy. Prog. Org. Coat. 1997, 32, 81–88.
Westra et al. applied AFM to examine the microstructure and nanostructure of the sputtered and evaporated columnar thin films
(113). They found that AFM is a useful tool for surface topography studies of these technologically interesting surfaces. Two
structure zone transitions were investigated: the substrate-temperature dependent, zone 2 to zone 3 transition, and the sputter-
pressure dependent zone 1 to T transition. It was observed that the columns in zone 1 films are developed in a number of
different shapes; rounded domed columns, elongated rounded columns, and faceted columns. These differences in the column
shape can be attributed to differences in preferential growth orientations and anisotropic adatom sticking coefficients. Besides, in
this work, it was found that the surfaces of the columns also contained structure. Based on their material, the form of these structures
varies. The surface of the columns was smooth in various films, while in a few number of films the surface of the individual columns
had remarkable texture. For instance, the surface of a Ti–W thin film was made of corrugations less than 10 Å high. Here, the
corrugations were between 100 and 200 Å apart.
Darowicki et al. studied the effect of UV irradiation on morphological changes of a polymeric surface as well as its electrical
properties (114). Thin poly(methyl methacrylate) (PMMA) film was applied onto iron substrate using solution casting technique.
They used UV-C irradiation in range of 200–280 nm as a deteriorative factor to induce polymer degradation. They also applied AFM
method to investigate surface topography of the PMMA coatings before and after exposure to UV-illumination. Photo-induced
variations developed in the polymer surface of the microcracks were indicated using AFM images. Besides, the electrochemical
impedance spectroscopy (EIS) measurements were conducted in this work to support the findings obtained using AFM method.
This technique was selected by the authors of this chapter to confirm whether the changes on the UV-exposed PMMA surface
observed on AFM images could show the potential sites of the polymer coating long before any serious damage occurred on the
surface. To obtain relevant information on durability of PMMA film, both EIS and AFM methods were applied in this study (see
Figures 48 and 49). According to the findings of this work: (1) It was found that the AFM technique is a useful tool to detect surface
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Figure 46 Top: (a) TM–AFM topographic image (2.5 2.5 mm2) of a monolayer of the (760/80) copolymer (left) and (b) phase image (800
800 nm2) corresponding to the area defined by the white square (right). Bottom: (c) cross-sectional analysis of the monolayer. (d) Surface morphology
before thermal annealing at 120 C. Reproduced from Viville, P.; Leclere, P.; Deffieux, A.; Schappacher, M.; Bernard, J.; Borsali, R.; Bredas, J. L.;
Lazzaroni, R. Atomic Force Microscopy Study of Comb-like vs. Arborescent Graft Copolymers in Thin Films. Polymer 2004, 45, 1833–1843.
topography and local electrical properties of the PMMA coating. AFM images indicated the presence of the photo-induced variations
which are also seen on the PMMA surface exposed to UV irradiation. (2) There was found a correlation between 3D-AFM and
scanning spreading resistance images. The latter indicated the cracks at the microscale which can lead to potential failures of the
coating. Therefore, the AFM method should allow the detection of the possible onset degradation of the coating long before
breakthrough defects appear on the surface. (3) Localized current measurements indicated presence of the microcracks in polymer
coating after exposure to UV irradiation, while the classical impedance measurements on macroscale, which yield averaged results,
did not present any changes in the microscale electrochemical performance. It was also found that the AFM method was efficient to
predict durability of the polymer coating and present the potential areas for onset of degradation controlled by particular deteri-
orative factor. (4) Regarding the equipment limitations, the AFM method is not possible to be applied in an outdoor environment.
Nevertheless, the AFM method might be a powerful technique in the evaluation of organic coatings’ durability or effect of particular
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Figure 47 TM–AFM phase images (750 750 nm2) of the internal morphology of the (760/80) copolymer monolayer (left) and the (760/80/50/40)
copolymer monolayer (right). The left inset (a) shows a schematic view of the corresponding cylindrical brush conformation. The central inset (b)
illustrates the intermolecular ordering and the right inset (c) shows a schematic representation of the more complex molecular architecture of the
(760/80/50/40) copolymer. Reproduced from Viville, P.; Leclere, P.; Deffieux, A.; Schappacher, M.; Bernard, J.; Borsali, R.; Bredas, J. L.; Lazzaroni, R.
Atomic Force Microscopy Study of Comb-like vs. Arborescent Graft Copolymers in Thin Films. Polymer 2004, 45, 1833–1843.
Figure 48 3D-AFM images of the PMMA coating exposed to UV-irradiation after (a) 0 h, (b) 90 h, (c) 500 h, (d) 920 h; the scan area is 25 25 mm.
Reproduced from Darowicki, K.; Szocinski, M.; Schaefer, K.; Mills, D. J. Investigation of Morphological and Electrical Properties of the PMMA
Coating upon Exposure to UV Irradiation Based on AFM Studies. Prog. Org. Coat. 2011, 71, 65–71.
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Figure 49 (a) 3D-AFM image of PMMA coating exposed to UV-C radiation for 500 h. (b) Scanning spreading resistance image of iron substrate
coated with PMMA after 500 h of exposure to UV-C illumination (the scan area: 90 90 mm). Reproduced from Darowicki, K.; Szocinski, M.; Schaefer,
K.; Mills, D. J. Investigation of Morphological and Electrical Properties of the PMMA Coating upon Exposure to UV Irradiation Based on AFM
Studies. Prog. Org. Coat. 2011, 71, 65–71.
deteriorative factor on its performance before its introduction to the market. Hence, this procedure can reduce the costs associated to
the maintenance of various constructions in an outdoor environment, which in turn allows more accurate planning of the reno-
vation and repainting periods.
Using the sputter coatings, it is possible to obtain new approaches for surface functionalization of textile materials. Deng et al.
utilized PET nonwoven material as a substrate for creating functional nanostructures on the fiber surfaces (6). They applied
a magnetron sputter coating to deposit functional ZnO nanostructures on nonwoven substrate. Examination of the surface
morphology of the fibers in nonwoven web was conducted using AFM which revealed a significant difference in fibers’ morphology
before and after sputter coating (see Figure 50). AFM images also indicated the influence of the sputtering conditions on surface
morphology of the fibers. According to the findings of this work, an increase in the sputtering time leads to the ZnO grains growth
on the fiber surfaces. The higher pressure in the sputtering chamber might lead to the development of larger grains on the fiber
surfaces, while the higher applied power also results in the creation of larger grains on the fiber surfaces.
The new nanotechnologies in biomaterials for cardiovascular applications target at surface alterations arises from thromboge-
nicity to prevent platelets aggregation and subsequent clotting which is considered as their usual failure. It is required to have the
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Figure 50 PET nonwoven substrate: (a) SEM image and (b) AFM image. Reproduced from Deng, B.; Yan, X.; Wei, Q.; Gao, W. AFM Characterization of
Nonwoven Material Functionalized by ZnO Sputter Coating. Mater. Charact. 2007, 58, 854–858.
information about structural properties of platelets during their adhesion on nanostructure materials for obtaining a comprehensive
understanding of their activation. The traditional imaging tools require special preparation of the samples and do not guarantee
cells’ viability. Karagkiozaki et al. conducted this study using AFM as a nondestructive and nanoscale precision technique to
investigate platelets’ adhesion to amorphous hydrogenated carbon (a-C:H) thin films (115). They considered that the carbon-based
thin films grown by magnetron sputtering under different deposition conditions have the requirements for biomedical applications
and chose them as well-characterized case study materials (see Figure 51). The contribution of various vibration bands of the
platelet bonding groups was indicated and discussed in this work. The influence of nanostructure, surface properties, and wettability
of the carbon thin films on their thrombogenic potential was verified and it was indicated that their structural, surface, and bio-
logical characteristics are controlled by different deposition conditions. Accordingly, customization of the surface properties of
biomaterials and the informative study of platelets–nanomaterials interactions with AFM and FTIRSE will be a breakthrough in
development of less thrombogenic biomaterials.
Lipids are among the essential ingredients of the biological structures such as cellular membranes. They have been studied in
various studies, because of their biological relevance and potential applications. To deposit ordered lipid films on etched surfaces, it
is possible to apply different techniques such as Langmuir–Blodgett and vesicle-fusion deposition. Currently, a novel technique for
lipid film deposition has been proposed which allows preparation of stacks of small and well-controlled sets of bilayers on
a suitable substrate by a spin-coater. Pompeo et al. studied morphological properties of multilayers consisting of cationic and
neutral lipids (DOTAP and DOPC) and their mixtures via dynamic mode AFM (7). After adaption and optimization steps, the spin-
coating technique was performed to deposit lipids on a chemically etched silicon (1,0,0) substrate and then morphological
nanometer-scale characterization of the mentioned samples was carried out. According to the AFM studies, it was found that an
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Figure 51 AFM topography image of (a) platelets on a-C:H (biased) after 1 h incubation time (3D image with scan size 10 m 10 m). The circles show
the activated ‘egglike’ type platelets. (b) Platelets on a-C:H (biased) after 2 h incubation time (scan size 21 mm 21 mm). The arrows indicate the
platelets aggregation and the formation of clusters. Reproduced from Karagkiozaki, V.; Logothetidis, S.; Laskarakis, A.; Giannoglou, G.; Lousinian, S.
AFM Study of the Thrombogenicity of Carbon-based Coatings for Cardiovascular Applications. Mater. Sci. Eng., B 2008, 152, 16–21.
initial layer of ordered vesicles is formed and then, based on details of the spin-coating preparation protocol and silicon substrate
dimension, vesicle fusion and structural rearrangements of the lipid layers is likely to happen. They revealed feasibility of the lipid’s
structures control via acting on spin-coating parameters with promising perspectives for the new applications of lipid films.
According to the microwear experiments conducted by Schiffmann, it was demonstrated that the material fatigue on a micro-
scopic scale strongly enhances the wear of Me-C:H coatings (116). It was also found that the fatigue behavior of the film is
considerably affected by factors including particle percolation, columnar growth structure, and the type of metallic component.
Based on the findings of this work, it is possible to propose some points for further improvement of Me-C:H coatings. One can claim
that a relative movement, rotation, or alternated tilting of substrate and target during the vacuum deposition process might prevent
the development of the typical columnar growth structure, which can in turn reinforce the film structure. Moreover, the findings of
this work indicated that materials with low percolation threshold and metal concentrations just above this threshold present an
optimum wear resistance for a certain range of loads or applications, respectively. As a result, the electrical determination of
percolation threshold might be an additional indicator for appropriate tribological properties of the Me-C:H coatings. In experi-
mental perspective, AFM wear tests are notably considered as a tool for the development or examination of microscopic wear
models because of their well-defined single asperity contacts. It might result in new insights into wear process dynamics and the
effect of sample microstructure. The results of this work indicated a significant correlation in macroscopic wear tests; however,
the impact of different effective loads in macro- and microwear test has to be seriously considered. It is also important to study the
extension of tribological tests to ultrathin films and microscopic samples (microsystems and micromechanics).
Metal containing amorphous hydrocarbon films (Me-C:H) present excellent tribological properties and as well as adjustable
electrical conductivity. Schiffmann applied friction force microscopy experiments on Au–C:H and -C:H coatings with different metal
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contents and realized a nonlinear dependence of friction on the load in the nanonewton-range which can be explained by Hertz
model of elastic contact (117). By assuming that the friction is proportional to the real contact area and applying the Hertz model of
elastic contact to compute this area, a reasonable explanation for the load dependence of friction forces was yielded. The findings of
his work indicated that the values of (effective) friction coefficients and the shear stresses are strongly controlled by metal type and
concentration inside the film. Here, the mixing is not completed on a linear basis. It seems that the shear stress is not independent
from the contact pressure, unlike those samples in which the wear affects friction values. This study also indicated a strong
correlation between friction coefficients determined in microscopically and macroscopically mode. Although it is not possible to
directly compare the absolute values, since microfriction depends on the load and on the tip radius of the curvature, friction force
microscopy is still a conducive and reliable tool for the friction investigation of technical surfaces on microscopic scale.
Through spin-coating of microgels consisting of the cross-linked copolymer poly(N-isopropyl acrylamideco-acrylic acid)
[P(NIPAM-co-AA)], it is possible to fabricate thermosensitive coatings on silicon wafers. Schmidt et al. synthesized microgels with
two different cross-linker molar ratios (118). Also, they prepared the thin films at pH 2 in which particles are negatively charged just
because of the starter used for the polymerization. Using SEM images, dense packing of the particles and strong flattening in the
adsorbed state was observed. For microgels with less cross-linker content, this effect is stronger. Coatings composed of such microgel
particles exhibit a reversible thermoresponsive swelling/shrinking in the region of the lower critical solution temperature of NIPAM.
In this research, a standard setup was modified for the ellipsometric study of this process to allow performing temperature
dependent measurements of the optical thickness in a liquid cell. Once having microgels with a lower amount of cross-linker, the
temperature induced transition is sharper while it smears out with increasing amount of cross-linker. According to the AFM of the
dried films before and after the ellipsometric measurements, no significant desorption of the particles was observed at pH 2. The
average thickness of the prepared films in the dry state was about 30 nm. Therefore, in the swollen state, a thickness of about 400 nm
was obtained.
Spirkova et al. applied several techniques to evaluate surface properties (morphology, hardness, wear) of organic–inorganic
nanocomposite coatings prepared from silicon-containing precursors and Jeffamines (119). They indicated that the current AFM
methods are applicable not only for the determination of surface topography, but also for the scratch resistance determination. No
matter what method is applied (scratch resistance, nanoindentation, or pendulum), the outcomes indicated that coatings show the
best surface hardness in the main transition region at ambient temperatures. The rubbery coatings exhibited better scratch resis-
tances, while glassy samples displayed higher resistance to nanoindentation and better pendulum test results. According to this
work, addition of admixtures (20 wt.% of colloidal silica or 1 wt.% of montmorillonite) improves the wear properties of coatings,
namely their abrasion resistance. Remarkable advantages of AFM were indicated to test thin hybrid nanocomposite films and
coatings. Application of various AFM modes allows performing detailed surface morphology analysis as well as various tests of
surface properties on the nanometer scale. Comparing the results of AFM with those of classical tests applied in industry implied
that there is not always a clear relationship between nanoscopic and macroscopic test procedures and their results. It indicated that
the results obtained by different techniques depend on the thermomechanical state and properties of tested materials. The authors
of this work identified several sources of complications that may occur and should be avoided. Examination of synthesized coatings
with inorganic additives indicated that the added particles may concentrate in the surface layer. Therefore, substantial differences in
particles shape can differently influence the surface and bulk properties. Finally, initiation of the observable influence may occur at
very different concentrations.
Strel’tsov et al. applied AFM to examine morphology of poly(p-xylylene) ultrathin films prepared by vapor deposition poly-
merization on the surface of single crystal silicon (100) and on the cleaved surface of mica at a substrate temperature of 20 C (120).
At the initial stage, the growth of the poly(p-xylylene) coating is performed according to the island mechanism. The mean average
length for monomer p-xylylene is calculated in the pyramidal model framework of island growth, as 15 3 nm and 9 2 nm for
the single crystal silicon and the cleaved surface of mica, respectively. The nature of the substrate and defects on its surface indicate
an interesting effect on the structure of the poly(p-xylylene) coating. Hence, a homogenous nucleation of polymer islands on the
surface of silicon at a low monomer flow is shown, while it is heterogeneous for the cleaved surface of mica. The monomer flow
variations highly affects nucleation rate of the polymer islands.
Tarasova et al. applied plasma polymerization technique to investigate the use of allylamine and heptylamine monomers for the
deposition of thin, smooth, and stable polymer films (121). After the deposition process, only a very small share of oxygen was
observed, where this can be attributed to short exposure of the sample to air on transfer to the XPS chamber. Allylamine film was
oxidized quite rapidly when placing in an aqueous medium, which results in a shift of carbon and nitrogen groups to species with
higher oxidation states; e.g., amides, esters, and carboxylic acids. Also, the oxidative trends shown by heptylamine films were
qualitatively similar with the overall lower degree of oxidation compared to allylamine films. AFM direct interaction force
measurements of amine plasma polymer films were applied using a silica probe to verify film oxidation in the solution with time.
The long range interaction forces between the silica probe and ALLA-pp films in solutions with changing ionic strengths and pH
values are well explained by DLVO theory. As expected from solving the nonlinear Poisson-Boltzmann equation, the magnitude of
the measured forces varied with ionic strength and the pH of the solution. The additional repulsive forces recorded at small
separation distances did not correspond with the DLVO predictions. A possible explanation for this might be the steric compression
of the plasma film and/or of the hydration layer present on the surface of the sphere. DLVO fitting of the experimental data
produced diffuse double layer potentials for the ALLA-pp film, which indicates density decrease for positive surface charges as well
as increase of the negative surface charges with aging. In their fresh states, the film showed a strong positive potential of about
þ50 mV. This potential became increasingly negative and reached to a double layer potential of 54 mV after total time of 24 h. The
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similar results were obtained for HA-pp films; however, under these conditions they appeared to oxidize more rapidly than the
ALLA-pp films. The diffuse double layer potential estimations of the aged allylamine plotted against the solution pH made it
possible to estimate pzc of the aged film at a pH value of 4.2.
Turrion et al. coated AR-Glass fibers with the coupling agent 3-aminopropyltriethoxysilane (122). The obtained poly-
aminosiloxane coating was characterized as: (1) at a molecular scale through fluorescence response of pyrene moiety attached to the
polymer coating in chemical manner and (2) at a nanoscopic scale by AFM. After modifying the polymer structure of the coating
through applying various solvents, the data obtained from both techniques were jointly discussed. Using AFM measurements, it was
confirmed that the f the coupling agent is deposited on the fibers in the form of homogeneously distributed ‘islands.’ Besides, the
differences in the size of the silane islands were seen when exposing silanized fibers to different solvents. The fluorescence emission
from PSA indicated that the solvents result in a noticeable structural change in the polyaminosiloxane coating. The correlation
between information at a nanoscopic scale (morphology) with those at molecular scale (structure) implies that certain solvents
under a subsequent specific evaporation rate lead to rearrangement of the polymer chains in the glass fibers coating. This rear-
rangement is rather similar to a solvophobic effect with a degree depending on the quality of the solvent and the evaporation rate.
Zhang et al. measured electrochemical behaviors and topography observation of four organic coatings used in seawater through
both EIS and AFM to examine environment behaviors of various coatings as well as the effects of their film formation, pigments, and
fillers on anticorrosion behaviors (123). They indicated that materials including polyurethane, epoxy, and chlorinated rubber
coatings all have one capacitive loop in their tested EIS which phenomenally contains only one time constant, while alkyd coating
exhibit two capacitive semicircle arcs. Having two capacitive loops, the capacitive semicircle shows barrier layer property in the high
frequency range, while in the low frequency range it indicates corrosion reaction of metals under the film. Polyurethane coating
utilized in seawater represented an adequate anticorrosion property in a seawater immersion test. At their surface topography, the
appearance features of different layers are seen as different between different layers of tested coatings. The polyurethane paint film
coated on metal indicates more desirable properties compared to other layers, whereas film of alkyd coating has many pits at its
surface. To obtain further detail about surface topography of these four organic coatings and to approve effects of topography of
these coatings on its electrochemical behaviors, AFM images were prepared from two views of both height and phase modes.
AFM is a powerful tool to investigate surface properties and structure of materials in nanometric scale. Flexibility, large number of
potential signals, and its performance in various modes have been a great assistance for researchers to study different surfaces and
different media, including vacuum, air, and liquid. Unlike many other techniques for the study of surface properties, in this
technique the type of surface and environment are not considered as important limitations. Researchers evaluated properties of the
AFM probe using various nanostructured coatings to understand performance of the probe for materials topography and microwave
signals propagation. In addition, the open structure of the waveguide at the tip of the probe was introduced through the fabrication
of focused ion beam. This flexible technique can be used to obtain high-resolution nanoscale images and study local sites in air or
liquid. The principles of AFM in both air and electrolytes are reviewed and special applications of AFM for micro/nanostructured
coatings are discussed.
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96. Podesta, A.; Fantoni, G.; Milani, P.; Guida, C.; Volponi, S. Nanotribological Characterization of Industrial Polytetrafluorethylene-based Coatings by Atomic Force Microscopy.
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7.10 Application and Advances in Microprocessing of Natural Fiber
(Jute)–Based Composites
MM Alam and M Maniruzzaman, Islamic University, Kushtia, Bangladesh
MM Morshed, Dublin City University, Dublin, Ireland

7.10.2 Jute: Jute Plant and Jute Fiber 244
7.10.2.1 Separation of Jute Fibers from Their Plants 245
7.10.2.2 Uses and Prospects of Jute 245
7.10.2.3 Chemical Composition and Structure of Jute Fiber 245
7.10.2.3.1 Cellulose 246
7.10.2.3.2 Hemicellulose 247
7.10.2.3.3 Lignin 247
7.10.2.4 Physicochemical Properties of Jute Fibers 248
7.10.2.4.1 Physical Properties 248
7.10.2.4.2 Chemical Properties 248
7.10.3 Treatment of the Fiber 249
7.10.4 Principles of Fiber Reinforcement 249
7.10.4.1 Stress–Strain Relationship 249
7.10.4.2 Effective Fiber Length 250
7.10.4.3 Fiber Orientation 251
7.10.4.4 Interfacial Bond 251
7.10.5 Matrix Considerations 251
7.10.5.1 Thermoplastic Polymers as Matrix 251
7.10.5.2 Thermosetting Polymers as Matrix 252
7.10.5.3 Metal Matrix Materials 252
7.10.5.4 Moisture Effect and Resin Compatibility 252
7.10.6 Experimental Procedure for Composite Preparation 253
7.10.6.1 Preparation of the Specimen 254
7.10.6.1.1 Jute Fiber Cutting 254
7.10.6.1.2 Mixing 254
7.10.6.1.3 Casting 255
7.10.6.1.4 Curing and Controlling 255
7.10.6.1.5 Cooling 255
7.10.6.1.6 Demolding 255
7.10.6.1.7 Density Calculation 255
7.10.7 Composite Fabrication 256
7.10.7.1 Hand Lay-Up/Spry-Up 256
7.10.7.2 Resin Transfer Molding 256
7.10.7.3 Compression Molding 257
7.10.7.4 Pultrusion 258
7.10.7.5 Injection Molding 258
7.10.7.6 Filament Winding 259
7.10.8 Conclusions 259
References 259
7.10.1 Introduction
Composite materials are made by bringing together more than one material to create a unique combination of properties in which
one of the materials is a reinforcing phase (fibers, sheets, or particles) and the other is a matrix phase (polymer, metal, or ceramic).
In a composite, one material is made up of stiff long/short fibers and the other is a binder or matrix that holds the fibers in place.
Composites are a versatile and valuable family of materials that can promote different applications, improve productivity, reduce
cost, and facilitate the introduction of new properties in materials. Among all the synthetic fibers, glass fibers are now dominant due
to their low cost (compared to carbon and aramid) and comparatively better physicomechanical properties (1). Long glass fibers in
random array have proven to be very successful in high-volume markets, notably the automotive industry. Because of their excellent

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244 Application and Advances in Microprocessing of Natural Fiber (Jute)–Based Composites
price-performance ratio, E-glass fibers are by far the most important fibers for these types of composites. However, these fibers do
have some disadvantages. Glass fibers are nonrecyclable and cause problems with respect to ultimate disposal at the end of
a material’s lifetime since they cannot be thermally recycled by incineration and are left behind as a residue that can damage
a furnace. They are also very abrasive, which leads to increased wear of processing equipment such as extruders and molds. Next to
some ecological disadvantages, glass fibers can cause problems with respect to health and safety. For example, they cause skin
irritation during the handling of fiber products as well as the processing and cutting of fiber-reinforced parts.
Due to an increase in population, natural resources are being exploited substantially as alternatives to synthetic materials. The
utilization of natural fibers (NFs) for the reinforcement of composites has received increasing attention. NFs have many remarkable
advantages over synthetic fibers. Nowadays, various types of NFs have been investigated for use in composites including flax, hemp,
jute straw, wood, rice husk, wheat, barley, oats, rye, cane (sugar and bamboo), grass, reeds, kenaf, ramie, oil palm, sisal, coir, water
hyacinth, pennywort, kapok, paper mulberry, banana fiber, pineapple leaf fiber, and papyrus (2). NFs are largely divided into three
categories depending on their origin: mineral based, plant based, or animal based. For this reason, alternative reinforcement with
NF in composites has recently gained attention due to low cost, low density, acceptable specific properties, ease of separation,
enhanced energy recovery, CO2 neutrality, biodegradability, and recyclable nature (3,4). NFs are low in cost, are easier to handle,
have good specific mechanical properties, and require only around 20–40% of the production energy. The first NF-reinforced
composites were based on thermoset matrices, such as unsaturated polyester or phenolic resins, together with sisal and jute. More
recently, developments shifted to thermoplastic matrix composites (5–11).
At present, ecological concerns have resulted in renewed interest in natural materials, and issues such as recyclability and
environmental safety are becoming increasingly important for the introduction of new materials and products. Environmental
legislation and consumer advocacy are increasing the pressure on manufacturers of materials and end products to consider the
environmental impact of their products at all stages of their life cycle, including ultimate disposal, viz. a ‘from cradle to grave’
approach. At this moment, the ‘ecodesign’ philosophy is being applied to more and more materials and products. In view of all of
this, NFs based on lignocellulose, such as flax, hemp, sisal, and jute (12), are interesting and environmentally friendly alternatives to
the use of glass fibers as reinforcement in engineering composites. These vegetable fibers are renewable, nonabrasive, and can be
incinerated for energy recovery since they possess a good calorific value. Moreover, they cause less concern with respect to health and
safety during the handling of fiber products. In addition, they exhibit excellent mechanical properties, especially when their low
price and density (1.4 g cm3) in comparison to E-glass fibers (2.5 g cm3) is taken into account. These fibers are abundantly
available, especially in developing countries such as Bangladesh and India.
7.10.2 Jute: Jute Plant and Jute Fiber
Jute (local name kushta) is a long, soft, shiny vegetable fiber that can be spun into coarse, strong threads (Figure 1(a)). The fibers of
jute are collected from different places in the southern part of west Bangladesh. After the fresh jute sticks are collected, they are
submerged in water to allow microbial degradation. Within 20–25 days the leaves degrade appreciably to extract the fibers. The
fibers are isolated from the degraded jute sticks by washing three times in deionized water and subsequently dried in open air. After
complete drying, fibers used for study are stored in moisture-proof packets. The fibers are usually off white and have flat surfaces
(Figures 1(b) and 1(c)).
Jute is a fiber of rather coarse character and dark color. It is a long mostly unbranched and monocotyledonous type of plant that
belongs to the genus Corchorus, in the family Tiliaceae or lime family. The genus Corchorus contains about 40 species e.g., Ref. (13).
Corchorus capsularis
Corchorus olitorius
Corchorus fuscus
Corchorus japonicus
Corchorus monopoxensis
Figure 1 (a) Jute tree, (b) jute fibers, and (c) SEM image of jute fiber.
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Application and Advances in Microprocessing of Natural Fiber (Jute)–Based Composites 245
Among these, the most important variety is C. capsularis, which is grown throughout tropical Asia not only as a fiber plant but
also as a vegetable. Other varieties are C. olitorius, C. fuscus, and Corchorus decemangulatus; the latter two, however, yield only a small
proportion of the jute fiber found in trade. One variety found in panama, the C. monopoxensis, is used for brewing and infusion
similar to tea. Corchorus japonicus is found in Japan and is converted into fiber. Arabs and Egyptians have used C. olitorius for
generations as a port herb (14). An extensive survey of the jute-growing areas in India was made to determine the kinds of jute being
grown. Based on morphological characteristics of the plant, color markings of stem and flowers, maturity, and chemical properties
of the fiber, 33 distinct types of C. capsularis were described, 30 of which were grown for fibers and three as vegetables; five types of
C. olitorius were described (15). Later studies at the Jute Agricultural Research Institute indicated more than 70 races or types of
capsularis and at least 12 races or types of olitorius have been identified (16).
7.10.2.1 Separation of Jute Fibers from Their Plants

The jute plant grows particularly well in a warm, humid climate where the land is constantly enriched by alluvial deposit (mud)
(17,18). Most of the world’s supply of jute comes from India and Bangladesh, where it is cultivated in the alluvial soils of the Delta
Region of the Ganges and the Brahmaputra rivers (16). The harvest of jute gets ready for gathering in about 3 months, and the
correct stage is recognized by the formation of the flower buds. These are not allowed to break and bloom, for that would take too
much goodness from the fibers (17). After the plants have fully grown, they are cut down by hand with homemade knives and are
ready for retting, which is the operation to make the jute plant ready for the separation of the bast layer from the stem of the plant.
This operation requires a large supply of water, since the plants must be completely submerged in water. There are two types of
retting: (1) pit water retting and (2) flow water retting. Flow water retting is better, but in a place where flow water for retting purpose
is lacking, pit is practiced, i.e., retting in stagnant water is ponds, ditches, etc. (19). In either of the retting processes, bundles of canes
are immersed in water and weighted down by planks or stones, bacterial action then separates the outer bast layer of fibers from the
canes and from each other. This action may take place in 10–15 days, depending on the weather, the temperature of water, the
ripeness of the cane, and the area where it is grown. During immersion, the crop is under constant surveillance to prevent over-
retting, which produces weak fiber. Underretted fibers are course, gummy, and most difficult to remove from the cane. When the
fibrous layer separates freely from the cane, the retting is complete. Then the fiber is washed free from stalk and vegetable debris,
finally washed in clean water, dried in the sun, and ready for market (17,20).
7.10.2.2 Uses and Prospects of Jute

About 95% of the world’s jute is produced in Bangladesh and India (16,21). Bangladesh produces the best-quality jute in the
world. Jute fiber is extensively used for the manufacture of gunny sacks, wool packings, all jute carpets, wall coverings, lamp
shades, curtains, jutton, carpet backings, etc. It is also used largely in the manufacture of twine, window cord, and rope in
smaller sizes. During the last decade, a variety of end uses of jute has been developed, particularly in the United States and the
United Kingdom, some of which are brattice cloth, filter cloth, tarpaulins, decorative fabrics, lanitin kosmos fibers, ‘artificial
wool’ etc. These are all manufactured from jute. It is also used as shoulder bags, shopping bags, fabric for embroidery purposes,
and allied articles. Jute stick, an agricultural by-product, is used as domestic fuel and for fencing purposes. Recent investigators
have shown that jute stick contains a good amount of a-cellulose that can be used for pulp, paper, rayon, and similar products.
A superior quality hard board sold under the trade name ‘Partex’ is also being made of jute sticks. Xylose, xylic acid, activated
charcoal, furfural, and resins have been obtained from jute sticks. Jute leaf is used as a vegetable and also for medicinal purposes.
A natural dye can also be isolated from jute leaf. Jute seed may also be regarded as jute waste. Two important substances with
medicinal value, such as protein and vitamins, can be obtained from jute seed. Jute seed oil can successfully be used as an
ingredient for soap.
The prospect of using jute fabrics for decorative purposes is promising in Western Europe. As regards immediate market
prospects, jute already has a wide application as wall-covering fabric in the United Kingdom, Sweden, France, and West
Germany, and to a lesser extent in Belgium and the Netherlands due to the tie-up of jute manufacturers with the wallpaper
manufacturers and distributors in these countries. NF composites enjoy excellent potential as wood substitutes in the building
industry in light of their low cost, easy availability, energy saving potential, and pollution-free production. In order to improve
upon the laboratory–industry linkages towards application development and commercialization, the Advanced Composites
Mission launched projects on jute composites such as jute-coir composite boards, jute-glass composite components for railway
coaches, thermoplastic composite-based synthetic wood, and others. Jute-based handicrafts and novelties vary from toys, table
lamps, wall paintings, pencil boxes, and a large variety of splendid gift items. They have a huge export potential. The big
advantage is the capability of rapid manufacture of large, complex, high-performance structures, such as the F22 frames pre-
sented in Figure 2.
7.10.2.3 Chemical Composition and Structure of Jute Fiber

Jute fiber is a complex mixture of chemical compounds that are built up by a natural process (photosynthesis) during the growth
of the fiber in the plant stem. The composition of jute fiber is not uniform. The condition of the soil, climate, maturity of the
plants, retting, etc. creates considerable variation in the constituents of the fiber (22). The composition of the capsularis and
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Figure 2 Some uses of natural fiber composite.
olitorius fibers are more or less the same, with minor differences in constituents. The average composition of jute fiber is as
follows (23):
Constituents Amounts (percentage dry basis)
1. a-Cellulose 60.00
2. Hemicellulose 22.00
3. Lignin 12.00
4. Nitrogenous matter (as protein) 1.00
5. Fatty and waxy matter 1.00
6. Mineral matter (ash) 1.00
7. Miscellaneous 3.00
Total 100.00
As is evident from the composition of jute fiber, the main constituents are a-cellulose, hemicellulose, and lignin; the rest are very
minor in proportion and give very little influence to the fiber’s structure. Hence, it is clear that the jute fiber is mainly composed of
a-cellulose, hemicellulose, and lignin. The following is an attempt to discuss the structure of cellulose, hemicellulose, and lignin
and the nature of possible combinations that exist between these constituents.
7.10.2.3.1 Cellulose
Cellulose pertains to the class of carbohydrates. It contains 44.4% carbon, 6.2% hydrogen, and 49.4% oxygen (24). Cellulose, the
principal constituent of all plant life, is a linear polymer of anhydroglucose units linked in the 1 and 4 positions by a b-glucoside
links. The empirical formula of cellulose (C6H10O5)n corresponds to a polyanhydride of glucose. The two terminal glucose residues
of a cellulose molecule contain two different end groups: one contains a reducing hemiacetal group in the position C1 and is
therefore known as the reducing end group, whereas the other contains an extra secondary hydroxyl group in the position C4 and is
known as the nonreducing end group. The structure of cellulose is written as follows:
There are two secondary and one primary alcoholic hydroxyl groups in each basic anhydro-D-glucose unit (C6H10O5)n, which are
arranged in positions 2, 3, and 6, respectively, on the basic unit. The reactivity of the hydroxyl groups varies in different reactions.
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In many reactions (mainly esterification), the primary hydroxyl groups have a greater reactivity. The two secondary hydroxyls, at the
second and third carbon atoms, differ somewhat in their reactivity. The primary hydroxyls of cellulose elementary units are
responsible for the sorbability and dyeability of cellulose materials. Cellulose is highly stereospecific. The high hydroxyl content of
cellulose might suggest high water solubility. This is because of stiffness of the chains and hydrogen bonding between hydroxyl
groups of adjacent chains, as shown in the following (25): Besides hydrogen bonding, another type of linkage called ‘semiacetal
linkage’ is present between the adjacent chain molecules of cellulose (26).
From X-ray diffraction diagram, it has been concluded that cellulose has two regions: crystalline and amorphous. In the
amorphous region the polymer chains tend to be folded, and consequently, they will have rather different properties than the
crystalline region. It is in disordered regions that the most of the chemical reactions take place with cellulose. Again, polymeric fibers
are never completely crystalline. This interconnection of crystalline and amorphous regions enhances the strength of the polymer.
As early as 1920, Herzog and Janeke recognized that cellulose from such widely different sources as cotton, ramie, wood, jute, and
flax gave identical X-ray diagrams and concluded that these fibers had identical crystalline structures (27).
7.10.2.3.2 Hemicellulose
Hemicellulose is a group of cell wall polysaccharides. The isolated hemicelluloses are amorphous substances. The cellulose and
lignin of plant cell walls are closely interpenetrated by a mixture of polysaccharides called hemicellulose. It is soluble in dilute alkali
and readily hydrolyzed to pentose and hexose with some uronic acids.
Sarker and others showed that xylose linked with methyluronic acid formed the basic building units of hemicellulose in jute
(28). It appeared that six xylose units were linked with 1-methyl glucuronic acid units (29).
The structure of the repeating unit of jute hemicellulose 3-methoxy galacturonic acid is linked with xylose units. The hemi-
cellulose are relatively short-chain compounds and, therefore, occupy longitudinally the same space as the anhydroglucose unit in
the cellulose chain. The short-chain polysaccharides would, therefore, pack rigidly into the oriented cellulose structure between
which some cross-bridging or looping may also occur.
7.10.2.3.3 Lignin
Most plant tissues contain, in addition to carbohydrate and extractives, an amorphous polymeric gummy material called lignin
(30,31). The nature of lignin and its relationship to cellulose and other constituents of jute fiber are still uncertain. Unlike cellulose
and hemicellulose, lignin gives a series of color reactions that indicate the presence of compounds for which these reactions are
typical. Isolated lignin is generally an amorphous material with average high molecular weight (32).
Lignin is an insoluble, resinlike substance of phenolic character. It is built, to a large extent, of phenyl propane building stones,
often having a hydroxyl group in the para position and methoxyl group/groups in meta position/positions to the side chain (33,34).
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Besides, there may be carbon-to-carbon or carbon-to-oxygen bonds joining the aromatic ring to the portions of structure. The lignin
molecule, thus being polyfunctional due to the presence of alcoholic and phenolic hydroxyl groups, may exist in combination with
two or more neighboring chain molecules, cellulose or hemicellulose, serving the function of a cross-linking agent. Postulated
monomer in lignin as shown below (35):
7.10.2.4 Physicochemical Properties of Jute Fibers

An ordinary staple of jute fibers is as long as 4–7 feet, and often reach 12 feet in exceptional cases. But in spite of this, the ultimate
fibers are exceedingly short, ranging only from one-eighth of an inch to one-twelfth of an inch (36).
7.10.2.4.1 Physical Properties

Physical properties of fiber, such as breaking strength, extensibility, flexibility, moisture absorption, etc. all depend on a number of
factors, of which the length of the fiber molecules, the mode of alignment among them, and the nature and intensity of interchain
cohesive forces are most important. In pure cellulosic fiber the lateral cohesive forces, including hydrogen bonds, have maximum
intensity in the crystalline regions, where the chain molecules are arranged in a more organized manner. The crystalline portions
contribute to the strength and rigidity of the fibers, while amorphous portions, which allow a better freedom of movement of the
chain molecule, account for extensibility, flexibility, and moisture affinity. In jute fiber, crystallinity is exhibited only by a limited
portion of the cellulosic fraction, amounting to about 40% of the fiber mass, while in cotton, the corresponding value is about 70%;
this low crystallinity as compared to cotton arises due to the presence of noncellulosic constituents in jute. The noncrystalline region
of jute contributes to a considerable extent to its strength by the cross-linkages of incrustants which are distributed entirely in the
amorphous regions. If these cross-linkages are ruptured, appreciable loss of wet strength of the fiber results (37). Like tensile strength,
the other properties of jute fibers, such as extensibility and flexibility, are also influenced to a great extent by the cross-linkages in the
amorphous regions. Usually, the low interchain cohesion in the amorphous regions permits a better freedom of movement to the
chain molecules, as a result of which these regions impart the above useful qualities to the fiber. In jute, however, due to the presence
of cross-linkages, the relative movement of the carbohydrate chains is much restricted, which ultimately affects both flexibility and
extensibility (37). Jute has a fairly high affinity for moisture, and high hydroscopicity of the fiber compared to other pure cellulosic
fibers is attributable to its low crystalline/noncrystalline ratio. However, jute is the second widely used vegetable fiber, exceeded only
by cotton. The yield of the fiber is only about 4.5% of the green weight of stem; in fact, the yield of fiber is extremely small (38).
7.10.2.4.2 Chemical Properties

In its chemical composition, jute is quite different from cotton, being composed of a modified form of cellulose known as
lignocellulose or bastose which, properly speaking, is a compound of cellulose with lignin (38). Unlike pure cellulose fiber, jute
fiber is highly reactive towards various chemical reagents such as acids, alkalies, and oxidizing reagents; the higher reactivity arises
mainly from the noncellulosic constituents of the fiber, namely, hemicellulose and lignin. Lignin is unhydrolyzable by acids, readily
oxidizable, and soluble in hot alkali, while carbohydrates are easily hydrolyzed by strong mineral acids to water-soluble sugars and
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relatively resistant to oxidizing agents (36,39). Jute fiber is highly susceptible to the action of light, the main features of the
photochemical changes being loss of tensile strength and development of a yellow or brown color. The degradation to jute caused
by light has been found to be the greatest among all natural cellulosic fibers. The reactions involved in photochemical degradation
of textiles are mainly oxidative in nature, and on prolonged exposure to light the constituent chain molecules are gradually oxidized
in all possible manners and ultimately broken down to smaller fragments. As a result, the tensile strength of the fiber is adversely
affected. It has been observed that all the main fiber components, including cellulose, suffer degradation, and the components
lignin and hemicellulose are much more reactive to light. Due to the influence of light, ligneous residues (phenolic group) are
transformed into colored quinoid derivatives resulting in a yellow or brown color. It is established that lignin is responsible for the
yellowing of jute fiber. In the absence of moisture or atmospheric oxygen, it is claimed that this photochemical action of light on
jute fiber is minimal (37,40,41).
7.10.3 Treatment of the Fiber
The treatment is done in two steps: (1) scouring and (2) bleaching.
1. Scouring
The removal of impurities such as dirty materials and gummy substances from textile materials is called scouring. It is carried out
by the use of a surface-active agent, such as soda, and detergent. Jute fiber was scored in a solution containing 6.5 g of soap flake and
3.5 g of soda per liter at 70–75 C for 30 min in a large beaker. The ratio of fiber to solution was 1:50. The fiber was thoroughly
washed with distilled water, dried in the open air, and finally stored in a desecrator.
2. Bleaching
For the purpose of bleaching, 1 g of jute fiber was dried at 105 C and treated with 0.75% or 7.5 g l1 sodium chlorite (NaClO2)
solution dissolved in a known volume of water; its pH was 10.6, lowered to 4 by the acetic acid. A buffer mixture of pH 4 was
prepared and added to the chlorite solution in the proportion of 1 ml of buffer solution for every 10 ml of chlorite solution, to
ensure that pH remained at 4 throughout the progress of the reaction. The bleaching process was carried out by digesting the fiber for
about 90 min at 85–90 C. For each group, 80 ml of the mixture was used. After bleaching, the fibers were washed with distilled
water. It was then treated with Na2S2O3. The fibers were washed and dried in open air and then stored in a desecrator.
7.10.4 Principles of Fiber Reinforcement
The mechanical properties of a composite can depend on many factors, as alluded to in the introduction. Basically, these factors
include the specific properties of the matrix and the reinforcing agent; their respective volume fractions; the shape, size distribution,
and orientation of the reinforcing phase; and the bond between the reinforcement and its matrix. Let us examine in more detail the
relationships between these factors and their influence on the mechanical behavior of composite materials.
7.10.4.1 Stress–Strain Relationship

In order to analyze the stress–strain behavior of a composite, we will consider a simple situation where a matrix containing
continuous cylindrical fibers is deformed in the direction parallel to the long axis of the fibers, as illustrated in the following Figure 3
(42). Assume that no slippage occurs at the interface between the fibers and matrix, the elongation is the same in both phases.
Therefore, the engineering strain in the composite may be expressed as
Dl
ec ¼ ef ¼ em ¼
l0
where
ef ¼ strain in fibers,
em ¼ strain in matrix.
Furthermore, when these strains are elastic the engineering stress in the respective composite can be determined by applying
Hooke’s law as follows:
s f ¼ E f ef
sm ¼ Em em
where
sf ¼ stress in fiber,
sm ¼ stress in matrix,
Ef ¼ elastic modulus of fiber,
Em ¼ elastic modulus of matrix.
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Figure 3 Axial deformation due to the load (p) in a composite reinforced with continuous cylindrical fibers.
In most cases, the modulus of the fiber is greater than that of the matrix, but for a given strain the stress in the fiber is greater than
the matrix stress. Although this is a very simplified analysis it serves to illustrate the extremely important concept of fiber rein-
forcement. Generally, the fibers are more highly stressed than the matrix when a load is applied to the composite. The mechanism
permits transfer of the stresses from the matrix to the reinforcing phase. As a result, the composite can sustain greater stresses than
the nonreinforced matrix material. This concept of utilizing the advantages of one material such as high modulus or high strength,
in conjunction with the advantages of another, such as low density or corrosion resistance, is the very essence of composite material.
Fiber considerations: Since the fiber-reinforced composite material relies on the fiber for its strength and stiffness, it is essential
that this constituent possess high strength and high modulus compared to the matrix, then with the appropriate volume traction
accompanied by control of fiber orientation and fiber dimensions, mechanical behavior such as strength, toughness, and stiffness
can be optimized.
Variability in strength of fibers is also a concern in composite materials, since some fibers are inherently stronger than others. For
example, consider a situation where bundles of fibers are axially strained. The water fibers fail first, thereby increasing the load on
the remaining fibers. Even though the surviving fibers are stronger, their number is decreased, and as the load increases, they
continue to fail in a progressive manner. If this process continues, eventually the effective strength of the composite becomes
insufficient to support the applied load and the composite material fails.
7.10.4.2 Effective Fiber Length

Thus far, composite materials with continuous fibers embedded in a matrix have been considered. However, some composites
contain discontinuous fibers. Such reinforcement may fail as a result of the fiber fracturing during loading. In any event, the
composite properties no longer obey the rule of mixtures under these circumstances, and the reinforcement may be ineffective
unless the fibers are considerably longer than a certain ‘critical length.’
If one examines the stresses occurring at the ends of a hypothetical fiber embedded in a matrix as illustrated in Figure 4, the
tensile stress in the fiber drops from the nominal fiber (43) stress to zero at the fiber end. Correspondingly, the interfacial shear stress
Figure 4 Schematic of composite stress at the ends of a fiber, when the matrix exhibits elastic deformation (lc is the critical length).
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increases from the nominal shear stress to a maximum value near the fiber end. The portion of fiber over which this process occurs is
denoted as lc/2 and represents the length of fiber that is ineffective with regard to tensile loading, because the stresses carried by the
end portion of the fiber are lower than the nominal stress. Since any fiber must be comprised of two ends, a reinforcing fiber must be
longer than lc in order to be effective. In other words, discontinuous fibers in a composite must be greater than lc if the load-carrying
capability of that composite is to be maximized.
Although many factors, such as fiber shape, end geometry, respective elastic and shear moduli of fiber and matrix, and interfacial
bond strength affect these stresses, the effective fiber length, when the matrix behaves as an ideal plastic material (i.e., no strain
hardening), can be expressed as
lc sfmax
¼
df 2smv
where
lc ¼ critical fiber length,
df ¼ fiber diameter,
sfmax ¼ maximum fiber stress,
smv ¼ shear strength of the matrix.
The value lc/df is referred to as the critical aspect ratio and is independent of volume fraction for matrices that behave plastically.
In cases where the matrix deforms elastically, the critical aspect ratio decreases for increasing values of Vf (fiber volm fraction). Thus,
for a specific fiber diameter, the critical length (lc) decreases as the fiber volume fraction increases (43).
7.10.4.3 Fiber Orientation

The alignment of fibers in reinforced composites is also a very important factor. Misalignment of fibers occurs during fabrication
simply becomes short fibers and slender filaments are difficult to align. Orientation of the fibers with respect to the direction of
applied loading affects the tensile strength of a composite; for small angles of disorientation (up to about 8) the strength of the
composite is unaffected. But when the fibers are misaligned and greater than this critical value (fcrit ), the strength of the composite
decreases precipitously.
7.10.4.4 Interfacial Bond

In addition to the aspect ratio and the orientation of the fibers, the strength and the bond between the fiber and matrix is a prime
factor in determining the mechanical behavior of a composite. A strong bond between these constituents is necessary for them to act
together during loading or service (42). To develop this bond, it is essential that the matrix wets the surface of the fiber during
fabrication. Such wetting is necessary to obtain good molecular atomic interaction between the constituents.
If the matrix material does not readily wet the fiber, special finishes called coupling agents can be used to promote mounding
between the matrix and its reinforcement. Such finishes are usually applied to the fiber reinforcement; fabrication of the composite
during the process referred to as ‘sizing.’
Surface roughness of the fiber phase is another important consideration in promoting bonding between the constituents of the
composite: If the surface is very rough, containing many minute disparities, the matrix material may not penetrate the depressions
and a poor interfacial bond will result (43).
7.10.5 Matrix Considerations
Matrix materials utilized in most commercial composites can be divided into two general categories: polymeric, including a number
of thermosetting and thermoplastic resins, and metallic, consisting of pure metals and alloys. The function of the matrix in
a composite material is usually multifold. Matrices are designed to protect the reinforcing phase from structural damage, corrosive
attack, and reactions that would degrade the reinforcement properties. The matrix phase also serves to transmit applied stresses to
reinforce constituents and stabilize them against buckling in situations where compressive stresses are axially applied to the
cylindrical fibers.
In other cases, the matrix may share load-carrying responsibility with the reinforcing phase. This aspect is important in
particulate strengthened composites; furthermore, the matrix may be selected for its physical properties, such as density, thermal,
and electrical conductivity (or electrical sensitivity), thermal expansivity, melting or softening temperature, and translucency or
opacity.
7.10.5.1 Thermoplastic Polymers as Matrix

This type of polymer consists of linear molecular chains that are not cross-linked. Instead, the attractive forces between the chains are
the weaker secondary bonding forces, i.e., van der Waals forces. Thus, they are not as rigid as the thermosets, and exhibit softening
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upon heating. Essentially, the thermoplastic resins are heated until soft and flowable, then they are simply molded into the desired
shape and allowed to cool. They are generally reinforced with short or chopped fibers, and the composite material is prepared as
cylindrical pellets. Subsequently, the composite pellets are processed by a fabricator in the conventional manner for thermoplastics,
such as injection or compression molding. The thermoplastics commonly used as matrix materials for fiber-reinforced plastics
include polycarbonates, polyamide (nylon 66), polystyrene, polyethylene, and polypropylene (PP). In general, the polymeric
materials display low tensile strengths compared to metals and ceramics. However, as a group they also exhibit relatively low
specific growth, which makes them attractive candidates for lightweight matrix applications.
7.10.5.2 Thermosetting Polymers as Matrix

This group of polymers is characterized by three-dimensional networks. Such nonlinearity occurs when there are more than two
reactive sites per monomer, and cross-linking takes place between linear chains. Indeed, this type of polymer is initially cured or
hardened by the application of heat, hence the term thermosets. These matrix materials are generally used in liquid formulations, so
they can be cast into any desired shape. In addition to cast ability, the initial liquid form facilitates infiltration of the reinforcing
phase and enhances setting of the fibers. The thermosetting resins commonly used as matrix materials include epoxies, polyesters
phonetics, and melamine.
7.10.5.3 Metal Matrix Materials

Metallic matrices serve the same basic function in composites as the polymeric materials just discussed. For instance, they protect the
reinforcing phase from structural damage and environmental degradation. They also transmit stress to the reinforcement phase and
stabilize the composite against buckling in compressive loading situations. The selection of matrix material strength, elastic
modulus, plasticity, density, and melting temperature, in addition, the interaction between the potential metallic matrix and its
reinforcement must be considered and if the composite is to function properly. Factors including the wetting and bonding char-
acteristics between fiber and matrix are extremely important, as well as chemical reactivity between these constituents after the
composite material is fabricated and put in service. Some of the matrix materials commonly employed in metal matrix composites
include aluminum, magnesium, nickel, copper, and titanium.
7.10.5.4 Moisture Effect and Resin Compatibility

The main problem leading to reduced mechanical properties in natural FRPs is the poor compatibility/adhesion between the
hydrophilic fibers and the hydrophobic matrix materials (44). Many researchers have been developing treatments to modify the
surface characteristics of the fibers to improve compatibility and adhesion. The three factors affecting the bond between two
materials are the mechanical interlocking, the molecular attractive forces, and the chemical bonds. Ideally, hydroxyl groups in
a resin would bond with the hydroxyl groups that are available in all NFs, creating hydrogen bonds. The bond strength between
resins and fibers is significantly lowered by the presence of moisture while curing due to the fact that H2O molecules will bond with
the available hydroxyl groups on the surface of the fiber, lessening the connections available for matrix bonding. When the water
evaporates, this then leaves voids in the cured composite. If fibers are properly dried before a suitable matrix is introduced, then
a better bond ought to result and future moisture uptake ought to be limited due to the lack of available hydroxyl bonding
locations. Nearly every researcher who has worked with NF composites agrees that there are significant challenges impeding their
advancement into the field of primary structural components. Applications for NFs are often limited to interior and nonstructural
applications due to their lower mechanical properties and poor moisture resistance, but these properties appear to have significant
room for improvement through the use of innovative surface treatments, resins, additives, and coatings. Many researchers have been
working to address these issues, with particular attention paid to the surface treatment of fibers and improving the fiber/matrix
interface. Because of their positive economic and environmental outlook, as well as their ability to uniquely meet human needs
worldwide, natural composites are showing good potential for use in infrastructure applications. The most common way to reduce
the moisture absorption capability of a NF seems to be through the process of alkalization (also known as mercerization). Alkali
treatment (usually with KOH or NaOH) reduces the hydrogen bonding capacity of the cellulose, eliminating open hydroxyl groups
that tend to bond with water molecules. Alkalization can also dissolve hemicellulose. The removal of hemicellulose, which is the
most hydrophilic part of NF structures, reduces the ability of the fibers to absorb moisture (45). If the fibers are not carefully washed
after alkalization, the alkali will continue to degrade the fibers long after exposure, eventually leading to significant fiber swelling
and breakdown. Some negative aspects of the alkali treatment process include high pH values, high surfactant content, polluted
wastewater, and the degradation of cellulose fibers. Alternatively, Kreze et al. (46) explored the use of pectin-dissolving enzymes.
While their research showed that the alkali-treated fibers were more effective at lowering moisture absorption, the enzyme-treated
fibers produced less polluted wastewater. Another process that shows promise for reducing the moisture content in NFs is the
Duralin steam treatment process (47–50). This process depolymerizes the hemicellulose and lignin into aldehyde and phenolic
functionalities, which are subsequently cured into a water-resistant resin. Untreated fibers reached a maximum moisture content of
over 42% in 100% RH while the fibers treated by the Duralin process reached a maximum moisture content of only around 14%
(48). The moisture diffusion time was also slowed for the fibers treated by the Duralin process. Some advantages of the Duralin
process include the omission of dew retting, increased fiber yield and quality, better dimensional and temperature stability, better
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Figure 5 Optical emission spectrum of environment-friendly natural jute fiber. Reproduced from Morshed, M. M.; Alam, M. M.; Daniels, S. M.
Plasma Chem. Plasma Process. 2012, 32, 249–258.
resistance to fungal attack, and generally improved mechanical properties. On the other hand, there is a significant amount of added
embodied energy to the fibers due to the steaming process.
The surface properties of NFs play an important role in the biocomposite manufacturing process. Conventional methods of
surface treatment, like chemical treatment, produce large amounts of waste materials (51). Therefore, an environmentally friendly
plasma treatment of materials with less pollution and various applications is required for the twenty first century. Recently,
increasing interest in biodegradable plastics has been revived due to new technologies (52). A low-temperature plasma process is an
effective alternative method compared to the conventional vacuum drying method for removing moisture. Plasma drying removes
the moisture from fibers faster and to a lower level than conventional methods. It also improves the surface properties of the fibers.
Plasma treatment improves fiber-matrix adhesion largely by introducing polar or excited groups or even a new polymer layer that
can form strong covalent bonds between the fiber and the matrix, and sometimes by roughening the surface of fibers to increase
mechanical interlocks between the fiber and the matrix. The macromolecular and microstructural changes of cellulose have
confirmed change by plasma treatment. Plasma treatment may cause strain to develop in the crystallite by changing the lattice plane
due to line shifting.
Optical emission spectroscopy (OES) is one of the useful in situ methods for monitoring the moisture removal method. The OES
technique enables an analysis of the chemical species in the plasma without interfering for perturbing the plasma. Emission
spectrum of argon plasma while treating a fiber, in the range at 200–1100 nm, is shown in Figure 5, which shows the emission lines
of argon (w750.8 nm), hydrogen (w656.3 nm), and molecular bands of OH (w309 nm). The OH radical represents the result of
dissociation of H2O molecules from the fiber and humid air present inside the chamber. The presence of basic atomic line of
hydrogen (Ha) is due to the excitation of hydrogen atoms generated by dissociation of H2O molecules under the action of energetic
electrons in the plasma. The relative intensities of the atomic and molecular emission for Ha, Ar, and OH as a function of treatment
time are shown in Figure 6. For H and OH emissions, it was found that both intensities decreased with increasing process time,
which indicates that the dissociated molecules of moisture were pumped out from the chamber. This process can remove up to 90%
of the moisture within 600 s. The pre- and postprocessing of chamber diagnostics show that the moisture removal rates in both cases
are the same, which indicates that there was some moisture present inside the chamber as a result of loading and unloading the
samples (53).
7.10.6 Experimental Procedure for Composite Preparation

1. Raw materials:
(a) PP, (b) low-density polyethylene (LDPE) or any synthetic polymers, and (c) jute fibers (Figure 7)
2. Preparation of the specimen:
(a) Mixing, (b) casting, (c) curing and controlling, (d) cooling, and (e) demolding
3. Measurement of bulk density
4. Tensile testing
5. Water intake
6. Flexural testing
During fabrication the chief raw materials used are (1) PP, collected from a local market, (2) LDPE, also collected from a local
market, (3) jute fibers, collected from a rural area. Untreated light brown jute fiber is used as a reinforcement agent, obtained from
a rural area. In the thesis work no coupling agent is used.
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Figure 6 (a) Intensity of Ha emission line as a function of plasma process time. (b) Intensity of OH emission line as a function of plasma process
time. Reproduced from Morshed, M. M.; Alam, M. M.; Daniels, S. M. Plasma Chem. Plasma Process. 2012, 32, 249–258.
Figure 7 Jute fiber and polypropylene composites. (a) LDPE-fiber and (b) PP-fiber composites.
7.10.6.1 Preparation of the Specimen

7.10.6.1.1 Jute Fiber Cutting
To get sized jute fiber, bundles were cut into different lengths of 2–3 mm on average. With the help of a knife, the sized jute fibers
were manually agitated to loosen the jute fibers from each other. The jute fiber was kept at a dry environment for 7 days for the
partial removal of moisture.
7.10.6.1.2 Mixing
Mixing is the major part of this experimentation. If the mixing of the chopped fibers and matrix is not done homogeneously, the
quality of the products obtained will be very poor. So the more homogeneously the raw materials are mixed, the more improved the
resulting properties of the products. To obtain homogeneous mixing, a blender was used; blending was done for 3 min at 400 rpm
for each specimen.
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7.10.6.1.3 Casting
A special molding device is made from steel to a very close tolerance for the molding process. The mixture of fiber and matrix is cast
by simply pouring the mixture into the mold and leveling it to the desired thickness. Only a slight stamping or hammering on the
mold is required for sufficient compaction. However, a vibration table or such will give a more efficient compaction and creates
a denser matrix.
7.10.6.1.4 Curing and Controlling

On pouring the fiber or matrix mixture into the special molding device, sufficient pressure of 50–105 KN is applied to get the
desired shape and possible homogeneity. The applied pressure is measured by using a pressure gauge set in the device. Heating is
done electrically, and the temperature set at 180 C for PP and 160 C for LDPE. Only 30–40 min is required to reach
temperatures of 180 C and 160 C. The temperature was maintained for 30 min. After completion of heating, the initial pressure
was set to zero and an additional pressure of 50 KN was applied to avoid any voids and to have a thickness. This additional
pressure was kept for 1 h.
7.10.6.1.5 Cooling
Cooling is essential throughout the curing operation. Cooling was done by tap water through the outer area of the heating plates of
the hydraulic press machine. The required cooling time is 15 min.
7.10.6.1.6 Demolding
The specimen was made by the Weber Pressen hydraulic press. After cooling, it adhered very strongly so we could not separate it
from the mold. It was removed by a makeshift setup device that we made.
7.10.6.1.7 Density Calculation
D ¼ Ws =V
where
D ¼ density of the specimen, kg m3,
Ws ¼ weight of the specimen, kg, and
V ¼ volume of the specimen, m3.
In this way the density of each sample is measured.
1. Tensile strength:
A tensile specimen was prepared according to ASTM D638M-91a. The sample type was M-II. The test speed was 5 mm min1.
Applied load
Tensile strength ¼
Cross sectional area of the load bearing area
2. Tensile strain: Tensile strength is calculated according to ASTM D638M-91a.
Extension
Tensile strain ¼
25
3. Flexural strength:
A flexural specimen was prepared according to ASTM D790M, 3-point loading. The specimen dimension was 125 10
6–8 mm, and the support span was 96 mm. The test speed was taken as 2.6 mm min1. The strength may be calculated for any point
of the load deflection by means of the following equation:
S ¼ 3PL=2BD2
where
S ¼ stress in the outer fibers at midspan, MPa,
P ¼ load at a given point on the load–deflection curve, N,
L ¼ support span, mm,
B ¼ width of specimen tested, mm,
D ¼ depth of tested specimen, mm.
In this way the flexural strength of each sample is measured.
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4. Flexural strain
A flexural specimen was prepared according to ASTM D790M, 3-point loading. The specimen dimension was 125 10
6–8 mm, and the support span was 96 mm. The test speed was taken as 2.6 mm min1. Nominal fraction change in the length of an
element of the outer surface of the test specimen at midspan, where the maximum strain occurs. It may be calculated for any
deflection using the following equation:
εf ¼ 6Dd=L2
where
εf ¼ main strain in the outer surface, mm mm1,
D ¼ maximum deflection of the center of the beam, mm,
L ¼ support span, mm, and
d ¼ depth, mm.
7.10.7 Composite Fabrication
Biocomposites are emerging as a realistic alternative to glass-reinforced composites. Because biocomposites are derived from
renewable resources, material costs can be markedly reduced with their large-scale usage (54). There are several techniques for the
fabrication of NF composites. Most of the techniques used for making glass fiber composites are applicable for making NF
composites. However, the well-known methods for making composite are as follows: hand lay-up, resin transfer molding (RTM),
compression molding, pultrusion, injection molding, etc.
7.10.7.1 Hand Lay-Up/Spry-Up

Hand lay-up/spry-up is the simplest and oldest open molding method of the composite fabrication process. It is a low-volume,
labor-intensive method suited especially for large components, such as boat hulls. Fiber or other reinforcing mat or woven fabric or
roving is positioned manually in the open mold, and resin is poured, brushed, or sprayed over and into the chopped fiber where the
secondary spray-up layer imbeds the core between the laminates, resulting in composite. Entrapped air is removed manually with
squeegees or rollers to complete the laminate structure. Room temperature curing polyesters and epoxies are the most commonly
used matrix resins. Curing is initiated by a catalyst in the resin system, which hardens the fiber-reinforced resin composite without
external heat. For a high-quality part surface, a pigmented gel coat is first applied to the mold surface.
7.10.7.2 Resin Transfer Molding

To define RTM, the process is described as follows: Fiber reinforcement is placed in a mold set, the mold is closed and clamped, and
the resin is injected into the mold cavity under pressure. The motive force in RTM is pressure. Therefore, the pressure in the mold
cavity will be higher than atmospheric pressure.
In contrast, vacuum infusion methods use vacuum as the motive force, and the pressure in the mold cavity is lower than
atmospheric pressure. RTM (Figure 8) (55) is used when parts with two smooth surfaces are required or when a low-pressure
Figure 8 Resin transfer molding system. Reproduced from Chakraborty, S.; Chakraborty, L.; Joshi, V. K. A Review on Natural Fiber Composites,
www.fiber2fashion.com.
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molding process is advantageous. Fiber reinforcement fabric or mat is laid by hand into a mold and resin mixture is poured or
injected into the mold cavity. The part is then cured under heat and pressure.
7.10.7.3 Compression Molding

Compression molding is a method of molding in which the molding material, generally preheated, is first placed in an open, heated
mold cavity. The mold is closed with a top force or plug member, pressure is applied to force the material into contact with all mold
areas, while heat and pressure are maintained until the molding material has cured. Compression molding is the oldest mass
production process for polymer products. The main reason for this choice of process in this case gives a clue to one of the features of
the process, namely the low level of orientation in the moldings. Compression molding is a simple, discontinuous technique using
a mold inserted between heated metal platens in a hydraulic press. The polymer compound is molten in the heat mold and kept
under pressure to fill the mold completely. In the case of a thermoplastic compound, the whole package has to be cooled under
pressure before the article can be ejected from the mold. This is very impractical and only applied for single productions in the
laboratory.
However, for thermosetting compounds, cooling is not necessary for ejection of the article, as it has already solidified at the
processing temperature due to strong cross-linking. Complete filling of the mold during cross-linking is rather tricky, but never-
theless compression moldings are very often used for processing of thermosetting resins. Figure 9 shows the compression molding
process.
The principle of the compression molding process can be outlined as follows:
1. The mold is held between the heated platens of the hydraulic press.
2. A prepared quality of molding compound is placed in the mold, usually by hand, and the mold is placed in the press.
3. The press closes with sufficient pressure to prevent or minimize flash at the mold part line.
4. The compound softens and flows to shape; the chemical cure then occurs as the internal mold temperature becomes high enough.
5. If necessary, cooling takes place, although for the vast majority of thermosets this is not needed.
6. The press is opened and the molding is removed. Frequently, the mold is removed from the press and opened on the bench to
extract the molding. It is reloaded with a fresh charge before returning it to the press to commence another cycle.
Figure 9 Compression molding system.
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7.10.7.4 Pultrusion
The term pultrusion combines the words ‘pull’ and ‘extrusion.’ Extrusion is the pushing of material, such as a billet of aluminum,
through a shaped die, whereas pultrusion is the pulling of material, such as fiberglass and resin, through a shaped die. Pultrusion is
a continuous process for manufacture of composite materials with constant cross section. Reinforced fibers are pulled through
a resin, possibly followed by a separate preforming system, and into a heated die, where the resin undergoes polymerization. Many
resin types may be used in pultrusion, including polyester, polyurethane, vinylester, and epoxy.
Pultrusion is a continuous process to manufacture composite profiles at any length. The impregnated fibers are pulled through
a hole (the heated mandrel), which is shaped according to the desired cross section of the product (Figure 10).
The resulting profile is shaped until the resin is dry. The advantages are the manufacturing of thin-wall shapes of ‘endless’ length,
large variety in cross-sectional shape, and the possibility for a high degree of automation. A disadvantage is the restriction to one
cross section, as shape variation in transverse direction is not possible. Pultrusion technology for manufacturing fiber composites
with polymer matrix appears to be energy efficient and resource saving. Economic and environmental factors favor use of a ther-
moplastic matrix, but due to the high viscosity of melts it is difficult to achieve high productivity and high quality of fiber fill
impregnation with this type of matrix (56).
7.10.7.5 Injection Molding

Injection molding is a manufacturing process for producing parts by injecting material into a mold. Injection molding can be
performed with a host of materials, including metals, glasses, elastomers, confections, and most commonly thermoplastic and
thermosetting polymers. Material for the part is fed into a heated barrel, mixed, and forced into a mold cavity where it cools and
hardens to the configuration of the cavity (57). Injection molding machines have many components and are available in different
configurations, including a horizontal configuration and a vertical configuration (Figure 11) (58).
Figure 10 Pultrusion process system. 1 – Continuous roll of reinforced fibers/woven fiber mat, 2 – Tension roller, 3 – Resin impregnator,
4 – Resin soaked fiber, 5 – Die and heat source, 6 – Pull mechanism, and 7 – Finished, hardened, fiber-reinforced polymer.
Figure 11 Injection molding overview. Reproduced from http://www.custompartnet.com/wu/InjectionMolding.
www.iran-mavad.com
However, regardless of their design, all injection-molding machines utilize a power source, injection unit, mold assembly, and
clamping unit to perform the four stages of the process cycle. The injection unit is responsible for both heating and injecting the
material into the mold. The first part of this unit is the hopper, a large container into which the raw plastic is poured. The hopper has
an open bottom, which allows the material to feed into the barrel. The barrel contains the mechanism for heating and injecting the
material into the mold. This mechanism is usually a ram injector or a reciprocating screw. A ram injector forces the material forward
through a heated section with a ram or plunger that is usually hydraulically powered. Today, a more common technique is the use of
a reciprocating screw. A reciprocating screw moves the material forward by both rotating and sliding axially, powered by either
a hydraulic or electric motor. The material enters the grooves of the screw from the hopper and is advanced towards the mold as the
screw rotates. While it is advanced, the material is melted by pressure, friction, and additional heaters that surround the recipro-
cating screw. The molten plastic is then injected very quickly into the mold through the nozzle at the end of the barrel by the buildup
of pressure and the forward action of the screw. This increasing pressure allows the material to be packed and forcibly held in the
mold. Once the material has solidified inside the mold, the screw can retract and fill with more material for the next shot.
7.10.7.6 Filament Winding

Composite fiber is recognized by the industry as an engineered material that is capable of replacing conventional material in
producing durable and cost-effective products that are able to perform in adverse conditions. In general, composite fiber winding
machines are developed due to technological advances in various industries including aerospace, marine, electrical, chemical,
transportation, as well as piping systems. The first filament-winding machine was developed in 1950 in accordance with the
revolutions of filament winding applications (59). Filament winding consists of winding resin impregnated fibers or rovings of
glass, aramid, or carbon on a rotating mandrel in predetermined patterns. The method provides the greatest control over fiber
placement and uniformity of structure. In the wet method, the fiber picks up the low viscosity resin either by passing through
a trough or from a metered application system. In the dry method, the reinforcement is in the preimpregnated form. After the layers
are wound, the component is cured and removed from the mandrel. Traditionally used to produce pressure vessels, rocket motor
cases, tanks, ducting, golf club shafts, and fishing rods, filament winding technology has been expanded; noncylindrical,
nonspherical composite parts are now commonplace. Typical thermoset resins used in filament wound parts include polyesters,
vinyl esters, epoxies, and phenolics.
7.10.8 Conclusions
Due to various environmental concerns, NF has been gaining special attention of technologists, engineers, industrial engineers, and
manufacturers for its enormous potential for application in different engineering utilities in the area of building construction,
railway, automotive, packaging, defense, etc. Prior to making the natural jute fiber base composite, the fiber should be modified.
Plasma modification processes have taken on increased importance in the current climate since aqueous based wet chemical
cleaning is environmentally deleterious. The plasma process removes moisture from fibers faster and more effectively than the
conventional drying method. The temperature sensitive jute fibers were dried more effectively in argon plasma without damaging its
constituents. From the above discussion, it may be concluded that the NF-reinforced thermoplastic composites may be processed
with emphasis on improvement of microstructure and properties of NFs, processing techniques, chemical modification, and
physical and mechanical properties of the composites.
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20. Grave-Palmer, F. Dyer and Calico Printer 1928, 60, 124–125.

21. Kirby, B. H. Vegetable Fibers; Leonard Hill. Ltd., London (Interscience Publisher Inc. New York), 1963.
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Gilmar Ferreira Batalha

NANO- AND MICROSCALE PROCESSING – MODELING

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD

British Library Cataloguing in Publication Data

Library of Congress Cataloging-in-Publication Data

For information on all Elsevier publications

Printed and bound in Italy

Project Manager: Gemma Tomalin

Joseph A. McGeough is an honorary professorial fellow in the School of Engineering at the

Syed H. Masood is professor of Mechanical and Manufacturing Engineering at Swinburne

Mustaﬁzur Rahman is currently a professor at the Department of Mechanical Engineering at

D. Abliz S.B. Mansour

7.01 Introduction to Nano- and Microscale Processing e Modeling 1

7.01.1 Chapters in This Volume 2

Comprehensive Materials Processing, Volume 7 http://dx.doi.org/10.1016/B978-0-08-096532-1.00700-7 1

7.01.1 Chapters in This Volume

7.01.2 Concluding Remarks

7.02.2 Micro/Nano Scale Energy Transport Model for Thin Films

Comprehensive Materials Processing, Volume 7 http://dx.doi.org/10.1016/B978-0-08-096532-1.00701-9 3

ðElectron energyÞin ðElectron energyÞout ðTe Þin ðTe Þout

ZN Yð2s xÞ jx sj  

ZN Yð2s xÞ jx sj

Total electron energy carried into dx during dt is

ZN Yð2s xÞ jx sj

Therefore, the conservation of energy yields

ZN Yð2s xÞ jx sj

ZN Yð2s xÞ jx sj

Combining eqns [18] and [20] yields

where c1 is the wave speed in the solid.

The initial conditions for eqn [36] are as follows:

qx ðx; tÞ ¼ vx fu ðx; tÞZuDðuÞdudU

¼ 2p vmfu ðx; tÞZuDðuÞdudm [51]

The ﬁrst term on the left-hand side of eqn [52] is simpliﬁed to

fu ðx; tÞzfuo ðTðx; tÞÞ [57]

where fuo ðTðx; tÞÞ is the equilibrium

The energy conservation relation is given as

Substituting the last expression in eqn [67] and simplifying yields

where a is the thermal diffusivity.

Then, Uðs; pÞ can be given as

After Laplace inversion, as explained in the appendix, we have

7.02.5 Findings and Discussions

Table 1 Properties used in the solution of temperature and stress ﬁelds

Property Numerical value

Cl 2.8 106 J m3 K1

7.02.5.2 Temperature Field due to the Solution of Radiative Phonon Transport

Table 2 Properties used in the simulations

Distance = 0 m Beta = 0.05E13 1/s

7.02.6 Concluding Remarks

7.02.6.1 Electron Kinetic Theory Approach

7.02.6.2 Radiative Phonon Transport

Comprehensive Materials Processing, Volume 7 http://dx.doi.org/10.1016/B978-0-08-096532-1.00702-0 21

7.03.2 Analytical Treatment of Thermal Stresses at Micro/Nanosized Length Scales

7.03.2.1 Analysis of Temperature Field

ZN Yð2s xÞ jx sj ZN Yð2s xÞ jx sj

Total electron energy after collision is

Total electron energy carried into dx during dt is

Therefore, the conservation of energy yields

DE ¼ AdxCl Tl ðx; tÞ [9]

7.03.2.2 Analysis of Stress Field

For boundary conditions, two cases are considered.

7.03.2.2.1 Stress-Free Boundary Condition

7.03.2.2.2 Stress Continuity Boundary Condition at the Surface

ZN Yð2s xÞ jx sj